CN103650063A - Conductive particles, conductive material and connection structure - Google Patents

Conductive particles, conductive material and connection structure Download PDF

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Publication number
CN103650063A
CN103650063A CN201280033707.1A CN201280033707A CN103650063A CN 103650063 A CN103650063 A CN 103650063A CN 201280033707 A CN201280033707 A CN 201280033707A CN 103650063 A CN103650063 A CN 103650063A
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particle
conductive layer
electroconductive particle
mentioned
weight
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CN201280033707.1A
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CN103650063B (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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    • 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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    • 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
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    • 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

Provided are: conductive particles capable of suppressing the clumping of a plurality of conductive particles, and reducing the connection resistance between electrodes when used in the connection between electrodes; and a conductive material using the conductive particles. These conductive particles (1) have substrate particles (2), and a conductive layer (3) disposed on the surface of the substrate particles (2) and including at least one type of metal component selected from the following: nickel, boron, tungsten and molybdenum.

Description

Electroconductive particle, electric conducting material and syndeton body
Technical field
The present invention relates to be provided with the electroconductive particle of conductive layer on the surface of basis material particle, more specifically, relate to the electroconductive particle that for example can be used in interelectrode electrical connection.In addition, electric conducting material and the syndeton body of above-mentioned electroconductive particle have been the present invention relates to use.
Background technology
The anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are 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 connection and the IC chip of IC chip and flexible printed wiring board and has the connection etc. of the circuit substrate of ITO electrode.For example, 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 be electrically connected to.
As an example of above-mentioned electroconductive particle, in following patent documentation 1, a kind of electroconductive particle is disclosed, its surface by the spherical basis material particle at average grain diameter 1～20 μ m utilizes electroless plating method to form nickel conductive layer or nickel alloy conductive layer obtains.This electroconductive particle has the microspike of 0.05～4 μ m on the top layer of conductive layer.This conductive layer is connected in fact continuously with this projection.
In addition, a kind of electroconductive particle that has basis material particle and be formed at the conductive layer of this basis material particle surface is disclosed in following patent documentation 2.In order to form basis material particle, as a part for monomer, used divinylbenzene-ethyl vinyl benzol mixture.With regard to this electroconductive particle, modulus of elasticity in comperssion when displacement occurs 10% of particle diameter is 2.5 * 10 9n/m 2compression response rate below, is more than 30% and failure strain is more than 30%.In patent documentation 2, recorded following content: state in the use electroconductive particle when being electrically connected between the electrode of substrate, contact resistance reduces, and connection reliability increases.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2000-243132 communique
Patent documentation 2: TOHKEMY 2003-313304 communique
Summary of the invention
The problem that invention will solve
Use the electroconductive particle of recording in patent documentation 1 by situation about connecting between electrode, cause sometimes interelectrode contact resistance to increase.In addition, use the anisotropic conductive material that comprises the electroconductive particle of recording in patent documentation 1 by situation about connecting between electrode, sometimes the resinous principle between electrode and electroconductive particle fully cannot be got rid of.Therefore the interelectrode contact resistance, connecting by electroconductive particle contained in above-mentioned anisotropic conductive material increases sometimes.
In addition, with regard to the electroconductive particle of the embodiment of patent documentation 1, be formed with the conductive layer that comprises nickel and phosphorus.At the conductive layer surface of the electrode connecting by electroconductive particle and electroconductive particle, multiform becomes to have oxide film thereon.Use has the electroconductive particle of the conductive layer that comprises nickel and phosphorus by situation about being connected between electrode, and the conductive layer that comprises nickel and phosphorus is comparatively soft, therefore sometimes the oxide film thereon on electrode and electroconductive particle surface cannot be got rid of fully, causes contact resistance to increase.
In addition, while strengthening the thickness such as such conductive layer that comprises nickel and phosphorus of recording in patent documentation 1 in order to reduce contact resistance, cause sometimes connecting object parts or substrate because the existence of electroconductive particle sustains damage.When connecting object parts or electrode damage, easily cause contact resistance to increase.In addition, when electrode or connecting object parts are impaired, can cause interelectrode conducting reliability to reduce.
In addition,, with regard to such conventional conductive particle of recording in patent documentation 1, there is sometimes the cohesion of a plurality of electroconductive particles.Use a plurality of electroconductive particles after cohesion when connecting between electrode, the short circuit between generating electrodes sometimes.
In addition, with regard to the electroconductive particle of recording in patent documentation 2, also there is sometimes the problem that cannot fully get rid of oxide film thereon, maybe cannot suppress the damage of connecting object parts or substrate.Therefore, in the situation that the electroconductive particle of recording in using patent documentation 2 is also difficult to fully reduce interelectrode contact resistance.
The object of the present invention is to provide and can suppress that a plurality of electroconductive particles condense and can reduce the electroconductive particle of interelectrode contact resistance when for interelectrode connection, and the electric conducting material and the syndeton body that use this electroconductive particle.
Limited object of the present invention be to provide when for interelectrode connection, can effectively get rid of electrode and electroconductive particle surface oxide film thereon, can reduce the electroconductive particle of interelectrode contact resistance, and the electric conducting material and the syndeton body that use this electroconductive particle.
Limited object of the present invention is to provide when for interelectrode connection can effectively get rid of the resinous principle between electrode and electroconductive particle, the electric conducting material that can reduce interelectrode contact resistance and syndeton body.
The method of dealing with problems
According to wide in range aspect of the present invention, a kind of electroconductive particle can be provided, it has basis material particle and conductive layer, and this conductive layer is arranged on the surface of above-mentioned basis material particle, and comprises at least one metal ingredient in tungsten and molybdenum and nickel, boron.
In a certain particular aspects of electroconductive particle of the present invention, in whole 100 % by weight of above-mentioned conductive layer, the content of above-mentioned boron is more than 0.05 % by weight and below 4 % by weight.
In a certain particular aspects of electroconductive particle of the present invention, in whole 100 % by weight of above-mentioned conductive layer, the content of above-mentioned metal ingredient is more than 0.1 % by weight and below 30 % by weight.
In a certain particular aspects of electroconductive particle of the present invention, in whole 100 % by weight of above-mentioned conductive layer, 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, the modulus of elasticity in comperssion during by this electroconductive particle compression 10% is 5000N/mm 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 below 70%.
In a certain particular aspects of electroconductive particle of the present invention, above-mentioned metal ingredient comprises molybdenum.
A certain particular aspects at electroconductive particle of the present invention, above-mentioned conductive layer comprises nickel and molybdenum, and in whole 100 % by weight of above-mentioned conductive layer, the content of nickel is that 70 % by weight are above and 99.9 % by weight are following, content molybdenum is more than 0.1 % by weight and below 30 % by weight.
In a certain particular aspects of electroconductive particle of the present invention, its modulus of elasticity in comperssion compressed 5% time is 7000N/mm 2above, and, this electroconductive particle on compression direction, take be greater than electroconductive particle before compression particle diameter 10% and when compressing particle diameter compressed below 25% of front electroconductive particle, 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 μ m and below 0.5 μ m.
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.
Syndeton body of the present invention possesses the 1st connecting object parts, the 2nd connecting object parts and connects connecting portions above-mentioned the 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 that comprises 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 of at least one metal ingredient of comprising in tungsten and molybdenum and nickel, boron on the surface at basis material particle, therefore can suppress a plurality of electroconductive particles and condense.And then, while connecting, can reduce contact resistance between use electroconductive particle of the present invention is by electrode.
Accompanying drawing explanation
Fig. 1 is profile, shows the electroconductive particle of the 1st execution mode of the present invention.
Fig. 2 is profile, shows the electroconductive particle of the 2nd execution mode of the present invention.
Fig. 3 is profile, shows the electroconductive particle of the 3rd execution mode of the present invention.
Fig. 4 is front cross-sectional view, schematically shows the syndeton body of the electroconductive particle that has used the present invention's the 1st execution mode.
Fig. 5 is schematic cross sectional view, and the state when to compression conductive particle describes.
Fig. 6 is schematic diagram, shows an example of relation between compressive load value when compression conductive particle causes that conductive layer breaks and compression displacement.
Symbol description
1 ... electroconductive particle
1a ... projection
2 ... basis material particle
3 ... conductive layer
3a ... projection
4 ... core material
5 ... megohmite insulant
11 ... electroconductive particle
11a ... projection
12 ... the 2nd conductive layer
13 ... conductive layer
13a ... projection
21 ... electroconductive particle
22 ... conductive layer
22a ... break
51 ... syndeton body
52 ... the 1st connecting object parts
52a ... above
52b ... electrode
53 ... the 2nd connecting object parts
53a ... below
53b ... electrode
54 ... connecting portion
71 ... stand
72 ... compression member
72a ... level and smooth end face
Embodiment
Below, the present invention is specifically described.
Electroconductive particle of the present invention has basis material particle and is arranged on the surface of this basis material particle and comprises at least one metal ingredient in tungsten and molybdenum and the conductive layer of 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 to metal ingredient M.Below, also the conductive layer that comprises nickel, boron and metal ingredient M is denoted as to conductive layer X.
By making electroconductive particle of the present invention take above-mentioned formation, can suppress a plurality of electroconductive particles and condense.The result that cohesion occurs a plurality of electroconductive particles can be suppressed, interelectrode short circuit can be effectively prevented.In addition,, by making electroconductive particle of the present invention take above-mentioned formation, while connecting, can reduce contact resistance between use electroconductive particle of the present invention is by electrode.
When the electroconductive particle that has a conductive layer that comprises nickel in utilization connects between by electrode, interelectrode contact resistance reduces.In electroconductive particle of the present invention, when the content of nickel is 50 % by weight when above in whole 100 % by weight of conductive layer X, interelectrode contact resistance significantly reduces.Therefore, in whole 100 % by weight of above-mentioned conductive layer X, more than the content of nickel is preferably 50 % by weight.
In addition, for having the electroconductive particle of the nickel conductive layer of boracic not, the nickel conductive layer of boracic is too not soft for this, during for interelectrode connection, sometimes cannot fully get rid of the oxide film thereon on electrode and electroconductive particle surface, causes contact resistance to increase.For example, with regard to thering is the electroconductive particle of the conductive layer that comprises nickel and phosphorus, cannot fully get rid of the oxide film thereon on electrode and electroconductive particle surface, easily cause contact resistance to increase.Particularly, in whole 100 % by weight of above-mentioned conductive layer, the content of phosphorus is 10.5 % by weight when above, easily causes contact resistance to increase, and the content of phosphorus is 1 % by weight when above, easily causes contact resistance further to increase.
On the other hand, while strengthening the thickness of the conductive layer that comprises nickel and phosphorus in order to reduce contact resistance, cause sometimes connecting object parts or substrate because the existence of electroconductive particle sustains damage.
On the other hand, because the hardness of the above-mentioned conductive layer X that comprises nickel and boron is higher, therefore can reduce interelectrode contact resistance.When connecting between electrode, can get rid of the oxide film thereon on electrode and electroconductive particle surface, can reduce contact resistance.
In addition,, in electroconductive particle of the present invention, because above-mentioned conductive layer X not only comprises boron, also comprises at least one the metal ingredient M in tungsten and molybdenum, therefore can make the conductive layer X that comprises boron and above-mentioned metal ingredient M become quite hard.Therefore, the oxide film thereon on electrode and electroconductive particle surface can be fully got rid of, contact resistance can be significantly reduced.Particularly, in the bossed situation of outer surface tool that above-mentioned conductive layer X comprises above-mentioned metal ingredient M and above-mentioned conductive layer X, the oxide film thereon on electrode and electroconductive particle surface can be more effectively got rid of, contact resistance can be further reduced.
In addition, by making above-mentioned conductive layer X comprise above-mentioned metal ingredient M, can make above-mentioned conductive layer X become quite hard, its result, even to the syndeton body being formed by connecting between electrode being applied to impact by electroconductive particle, is also difficult for occurring poor flow.That is, can also improve the resistance to impact of syndeton body.
In addition, the conductive layer surface of conventional conductive particle sometimes magnetic is higher, and, the surface magnetism of the conductive layer that comprises nickel and boron is higher, therefore, when being electrically connected between electrode, under the impact of electroconductive particle that cohesion has occurred because of magnetic, there is the tendency that easily produces connection between transversely adjacent electrode.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, can suppress a plurality of electroconductive particles condenses.Therefore, when being electrically connected between electrode, can suppress to cause producing and connecting between transversely adjacent electrode owing to having there is the existence of the electroconductive particle of cohesion.That is, can further prevent the short circuit between adjacent electrode.
Preferably, in whole 100 % by weight of above-mentioned conductive layer X, the content of nickel is that 70 % by weight are above and 99.9 % by weight are following and content above-mentioned metal ingredient M is more than 0.1 % by weight and below 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 whole 100 % by weight of above-mentioned conductive layer X lower than 1 % by weight.
Preferably in whole 100 % by weight of above-mentioned conductive layer X, the content of nickel is more than 70 % by weight and below 99.9 % by weight, the content of above-mentioned metal ingredient M is that 0.1 % by weight is above and below 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 whole 100 % by weight of above-mentioned conductive layer X lower than 1 % by weight.When having this electroconductive particle preferably forming for interelectrode connection, can effectively get rid of the oxide film thereon on electrode and electroconductive particle surface.Thus, can further reduce the interelectrode contact resistance of gained syndeton body.In addition, because the nickel content having in this electroconductive particle preferably forming is more than 70 % by weight, therefore, interelectrode contact resistance significantly reduces.
In addition, the content of above-mentioned metal ingredient M in whole 100 % by weight of above-mentioned conductive layer X is more than 0.1 % by weight and when 30 % by weight are following, compares with the conductive layer that does not contain above-mentioned metal ingredient M, and it is quite hard that conductive layer X becomes.Thus, can effectively get rid of the oxide film thereon on electrode and electroconductive particle surface, its result, interelectrode contact resistance further reduces.In addition, electroconductive particle is being coordinated with adhesive resin, using electric conducting material when connecting between electrode, can effectively get rid of the resinous principle between electrode and electroconductive particle, also can make thus interelectrode contact resistance further reduce.
Modulus of elasticity in comperssion during by electroconductive particle compression 10% of the present invention (10%K value) is preferably 5000N/mm 27000N/mm more preferably above, 2above, be preferably 15000N/mm 210000N/mm more preferably below, 2below.Above-mentioned modulus of elasticity in comperssion (10%K value) is when above-mentioned lower limit is above, the oxide film thereon that can more effectively get rid of electrode and electroconductive particle surface, and can more effectively get rid of the resinous principle between electrode and electroconductive particle, its result, interelectrode contact resistance further reduces.
Above-mentioned modulus of elasticity in comperssion (10%K value) can be measured as described below.
Use slight compression testing machine, under the condition of compression speed 2.6mN/ second and maximum test load 10gf, with the level and smooth pressure head end face of cylinder (diameter 50 μ m, Buddha's warrior attendant made of stones), electroconductive particle is compressed.Measure load value (N) and compression displacement (mm) now.Can be according to gained measured value, utilize following formula to obtain above-mentioned modulus of elasticity in comperssion.As above-mentioned slight compression testing machine, can use " the Fischer Scope H-100 " that such as Fischer company, manufacture etc.
K value (N/mm 2)=(3/2 1/ 2) FS -3/ 2r -1/ 2
F: load value when 10% compression occurs electroconductive particle (N)
S: the compression displacement (mm) when 10% compression occurs electroconductive particle
R: the radius of electroconductive particle (mm)
The compressive recovery rate of above-mentioned electroconductive particle is preferably more than 5%, more preferably more than 20%, be preferably below 70%, more preferably below 60%, more preferably below 50%.Compressive recovery rate is more than above-mentioned lower limit and when the above-mentioned upper limit is following, the oxide film thereon that can more effectively get rid of electrode and electroconductive particle surface, and can more effectively get rid of the resinous principle between electrode and electroconductive particle, its result, interelectrode contact resistance further reduces.In addition,, in the part except electroconductive particle of solidfied material and connecting portion and the interface between electroconductive particle and connecting object parts, be more difficult for producing peeling off.And, can suppress the repulsive force for the electroconductive particle of interelectrode connection, its result, electric conducting material is difficult for peeling off from substrate etc. more.Thus, also can make interelectrode contact resistance further reduce.
Above-mentioned compressive recovery rate can be measured as described below.
On sample bench, scatter electroconductive particle.Use slight compression testing machine along the center position of electroconductive particle, to apply load (reverse load value) until electroconductive particle reaches 30% compression to 1 electroconductive particle scattering.Then, unload until reach load value for initial point (0.40mN).Measure load-compression displacement during this period, utilize following formula can obtain compressive recovery rate.Wherein, making load speed is 0.33mN/ second.As above-mentioned slight compression testing machine, can use " the Fischer Scope H-100 " that such as Fischer company, manufacture etc.
Compressive recovery rate (%)=[(L1-L2)/L1] * 100
L1: start to the compression displacement reaching till reverse load value with load value from the initial point that applies when load
L2: the reverse load value when discharging starts to reaching the unloading displacement till load value for initial point
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 basis material particle, above-mentioned basis material particle, in whole 100 % by weight of above-mentioned conductive layer X nickel content, in whole 100 % by weight of above-mentioned conductive layer X above-mentioned metal ingredient M content, in whole 100 % by weight of above-mentioned conductive layer X phosphorus content, in whole 100 % by weight of above-mentioned conductive layer X the content of boron, the thickness of above-mentioned conductive layer X etc. suitably adjust.
With regard to electroconductive particle of the present invention, the modulus of elasticity in comperssion in the time of compressed 5% (5%K value) is preferably 7000N/mm 2above.
In addition, with regard to electroconductive particle of the present invention, preferably electroconductive particle on compression direction compressed be greater than conductivity particle diameter before compression 10% and be 25% when following, above-mentioned conductive layer breaks.In other words, in the situation that electroconductive particle of the present invention is compressed, preferably this electroconductive particle on compression direction, be greater than conductivity particle diameter before compression 10% and when compressing the compression displacement below 25% of front conductivity particle diameter, above-mentioned conductive layer breaks.That is the compression displacement of the electroconductive particle that, conductive layer breaks is preferably greater than 10% and be below 25%.For example, significantly during compression conductive particle, can moderately there is partial rupture in conductive layer.The electroconductive particle with such character is not only enough high in the hardness of compression initial stage, when by moderate compression, can break.When connecting between electrode, at electroconductive particle, by the stage of moderate compression, conductive layer can break, thereby can suppress the damage of electrode.Its result, can further reduce the interelectrode contact resistance of gained syndeton body, further improves interelectrode conducting reliability.
With regard to electroconductive particle of the present invention, preferably the modulus of elasticity in comperssion (5%K value) compressed 5% time is 7000N/mm 2above, and in compression electroconductive particle of the present invention in the situation that, on compression direction compressed be greater than conductivity particle diameter before compression 10% and be 25% when following, above-mentioned conductive layer breaks.When having this electroconductive particle preferably forming for interelectrode connection, can further reduce interelectrode contact resistance.
Modulus of elasticity in comperssion (5%K value) during electroconductive particle of the present invention compressed 5% is 7000N/mm 2in above situation, the electroconductive particle of compression initial stage has sufficient hardness.Thus, while connecting between by electrode, electroconductive particle can effectively be got 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, thereby further reduce interelectrode contact resistance.
Modulus of elasticity in comperssion while on the other hand, using compressed 5% (5%K value) is lower than 7000N/mm 2electroconductive particle by situation about being electrically connected between electrode, the modulus of elasticity in comperssion (5%K value) when using compressed 5% is 7000N/mm 2above electroconductive particle is compared situation about being electrically connected between electrode, the tendency that exists the removing property of the oxide film thereon on electrode and electroconductive particle surface to decline, the tendency that exists interelectrode contact resistance to increase.
From the viewpoint of the interelectrode contact resistance of further reduction, above-mentioned 5%K value is 8000N/mm more preferably 29000N/mm more preferably above, 2above.The upper limit of above-mentioned 5%K value is not particularly limited.Above-mentioned 5%K value can be for example 15000N/mm 2below, can be also 10000N/mm 2below.
Above-mentioned modulus of elasticity in comperssion (5%K value) can be measured as follows.
Use slight compression testing machine, under the condition of compression speed 2.6mN/ second and maximum test load 10gf, with the level and smooth pressure head end face of cylinder (diameter 50 μ m, Buddha's warrior attendant made of stones), electroconductive particle is compressed.Measure load value (N) and compression displacement (mm) now.Can be according to gained measured value, utilize following formula to obtain above-mentioned modulus of elasticity in comperssion.As above-mentioned slight compression testing machine, can use " the Fischer Scope H-100 " that such as Fischer company, manufacture etc.
K value (N/mm 2)=(3/2 1/ 2) FS -3/ 2r -1/ 2
F: load value when 5% compression occurs electroconductive particle (N)
S: the compression displacement (mm) when 5% compression occurs electroconductive particle
R: the radius of electroconductive particle (mm)
Above-mentioned modulus of elasticity in comperssion (10%K value and 5%K value) generally and quantitatively represents the hardness of electroconductive particle.By using above-mentioned modulus of elasticity in comperssion, can represent the hardness of electroconductive particle quantitative and beyond all doubtly.
From the viewpoint of the interelectrode contact resistance of further reduction, the compression displacement that above-mentioned conductive layer breaks more preferably more than 12%, more preferably below 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 the electroconductive particle that the 1st execution mode of the present invention relates to.
As shown in Figure 1, electroconductive particle 1 has basis material particle 2, conductive layer 3, a plurality of core material 4 and a plurality of megohmite insulant 5.
Conductive layer 3 is arranged on the surface of basis material 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 basis material particle 2 is coated by conductive layer 3 coating particles forming.
Electroconductive particle 1 has a plurality of projection 1a on surface.Conductive layer 3 has a plurality of projection 3a at outer surface.A plurality of core materials 4 are arranged on the surface of basis material particle 2.A plurality of core materials 4 are embedded in conductive layer 3.Core material 4 is arranged at the inner side of projection 1a, 3a.Conductive layer 3 is coated by a plurality of core materials 4.The outer surface of conductive layer 3 swells because of the existence of a plurality of core materials 4, forms projection 1a, 3a.
Electroconductive particle 1 has the megohmite insulant 5 on the outer surface that is arranged at conductive layer 3.It is coated that at least part of region of the outer surface of conductive layer 3 is insulated material 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 on the outer surface that is arranged at 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 the electroconductive particle that the 2nd execution mode of the present invention relates to.
Electroconductive particle 11 shown in Fig. 2 has basis material particle 2, the 2nd conductive layer 12 (other conductive layer), conductive layer 13 (the 1st conductive layer), a plurality of core material 4 and a plurality of megohmite insulant 5.
Only conductive layer is different with electroconductive particle 11 for electroconductive particle 1.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 the 2nd conductive layer 12 and conductive layer 13.
Conductive layer 13 is arranged on the surface of basis material particle 2.Between basis material particle 2 and conductive layer 13, be provided with the 2nd conductive layer 12 (other conductive layer).Therefore, on the surface of basis material particle 2, be provided with the 2nd conductive layer 12, on the surface of the 2nd conductive layer 12, be provided with conductive layer 13.Conductive layer 13 comprises nickel, boron and tungsten.Conductive layer 13 has a plurality of projection 13a at outer surface.Electroconductive particle 11 has a plurality of projection 11a on surface.
Fig. 3 is profile, shows the electroconductive particle that the 3rd execution mode of the present invention relates to.
Electroconductive particle 21 shown in Fig. 3 has basis material particle 2 and conductive layer 22.Conductive layer 22 is arranged on the surface of basis material 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 for spherical.In addition, electroconductive particle 21 does not have megohmite insulant.But it should be noted that, electroconductive particle 21 also can have the lip-deep megohmite insulant that is arranged at conductive layer 22.
With regard to electroconductive particle 1,11,21, preferably at conductive layer 3,13, in 22 integral body 100 % by weight, the content of nickel is that 70 % by weight are above and 99.9 % by weight are following, content above-mentioned metal ingredient M is more than 0.1 % by weight and below 30 % by weight.In addition, preferably conductive layer 3,13,22 is not phosphorous, or conductive layer 3,13,22 comprise phosphorus but phosphorus at conductive layer 3,13, the content in 22 whole 100 % by weight is lower than 1 % by weight.
Electroconductive particle 1,11,21 above-mentioned 5%K value is preferably 7000N/mm 2above.In addition, at compression conductive particle 1,11, in 21 situation, preferred electroconductive particle 1,11,21 on compression direction, occurred to be greater than compression before electroconductive particle 1,11,21 particle diameters 10% and for compression before electroconductive particle 1,11, during the compression displacement below 25% of 21 particle diameters, conductive layer 3,13,22 break.That is, for electroconductive particle 1,11,21, by electroconductive particle 1 before the compression on compression direction, when 11,21 particle diameter is made as X, preferred electroconductive particle 1,11 on compression direction, 21 particle diameter is that 0.75X is above and during lower than 0.90X, conductive layer 3,13, and 22 break.For example, before compression on compression direction, the particle diameter of electroconductive particle 1,11,21 is in the situation of 5 μ m, preferably to electroconductive particle 1,11,21 compress and make electroconductive particle 1,11 on compression direction, it is above and during lower than 4.5 μ m that 21 particle diameter reaches 3.75 μ m, conductive layer 3,13,22 break.It should be noted that, for electroconductive particle 11, be not only conductive layer 13, the 2 conductive layers 12 and also can break.
It should be noted that, what above-mentioned " breaking " represented on conductive layer that (the 1st time) first occur breaks.Therefore the electroconductive particle 1,11, relating to for present embodiment, 21, preferably to thering is non-cracked conductive layer 3,13, when 22 electroconductive particle 1,11,21 compresses, when electroconductive particle 1,11,21 on compression direction, be greater than compression before electroconductive particle 1,11,21 particle diameters 10% and while being the compression displacement below 25%, conductive layer 3,13,22 break.
Particularly, conductive layer 3,13, the mensuration of 22 compression displacements while breaking can be carried out as follows.It should be noted that, what in Fig. 5, use is electroconductive particle 21.
As shown in Figure 5, electroconductive particle 21 is placed on stand 71.Use slight compression testing machine (Fischer company system " Fischer Scope H-100 "), under the condition of compression speed 0.33mN/ second and maximum test load 10mN, using cylinder (diameter 50 μ m, Buddha's warrior attendant made of stones) as compression member 72, make the level and smooth end face 72a of this compression member 72 towards electroconductive particle 21, along the direction shown in arrow A, decline.Utilize level and smooth end face 72a to compress electroconductive particle 21.Proceed compression until the local 22a that breaks that produces of the conductive layer 22 of electroconductive particle 21.For the situation of electroconductive particle 1,11, also can utilize same method to measure.
It should be noted that, in the profile shown in Fig. 5, what illustrate is on conductive layer 22, to have formed the state of the 22a that breaks in the top and the bottom of electroconductive particle 21, but produce the position of breaking for conductive layer, is not particularly limited.
As described above during compression conductive particle, while preferably there is to be greater than 10% compression displacement of conductivity particle diameter before compression on compression direction at electroconductive particle, above-mentioned conductive layer breaks, and in the compression displacement occurring, is 25% when following, and above-mentioned conductive layer breaks.
When compressive load value and compression displacement are measured in compression conductive particle limit, limit, the relation between compressive load value and compression displacement as shown in Figure 6.In Fig. 6, from A0 point, start compression, at A1 point, conductive layer breaks.Along with conductive layer breaks, the compression displacement (particle diameter) of electroconductive particle on compression direction changes, and compression displacement is transferred 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 that applies compressive load to electroconductive particle is moved, and the compression displacement (particle diameter) of electroconductive particle on compression direction changes.
It should be noted that, in Fig. 6, the slope of the line of ordering to A1 from A0 point is larger.Above-mentioned 5%K value at electroconductive particle 21 is 7000N/mm 2above, in the harder situation of electroconductive particle 21, it is large that the slope of the line of ordering to A1 from A0 point becomes.
[basis material particle]
As above-mentioned basis material particle, can enumerate resin particle, the inorganic particulate except metallic, organic inorganic hybridization particle and metallic etc.Above-mentioned basis material particle is preferably the basis material particle except metallic, is preferably resin particle, the inorganic particulate except metallic or organic inorganic hybridization particle.
The resin particle of preferred above-mentioned basis material particle for being formed by resin.Use above-mentioned electroconductive particle when connecting between electrode, after above-mentioned electroconductive particle is arranged between electrode, by carrying out pressing, above-mentioned electroconductive particle is compressed.When basis material particle is resin particle, while 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 that is used to form above-mentioned resin particle, can enumerate such as vistanex, acrylic resin, phenolic resins, melmac, benzoguanamine 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., can enumerate divinylbenzene-styrol copolymer and divinylbenzene-(methyl) acrylate copolymer etc.Owing to can easily the hardness of basis material particle being controlled in to suitable scope, therefore, the resin that is used to form above-mentioned resin particle is preferably the polymer being polymerized by the one kind or two or more polymerizable monomer with a plurality of ethylenically unsaturated groups.
As the inorganic matter that is used to form above-mentioned inorganic particulate, can enumerate silicon dioxide and carbon black etc.As above-mentioned organic inorganic hybridization particle, can enumerate organic inorganic hybridization particle forming such as the alkoxysilyl polymer by being cross-linked and acrylic resin etc.
In the situation that above-mentioned basis material particle is metallic, as the metal that is used to form this metallic, can enumerate silver, copper, nickel, silicon, gold and titanium etc.
The particle diameter of above-mentioned basis material particle be preferably 0.1 μ m above, more preferably 1 μ m above, more preferably 1.5 μ m above, be particularly preferably 2 μ m more than, be preferably 1000 μ m following, more preferably 500 μ m following, more preferably 300 μ m following, more preferably 50 μ m following, be particularly preferably 30 μ m following, most preferably be below 5 μ m.The particle diameter of basis material particle is when above-mentioned lower limit is above, and because the contact area between electroconductive particle and electrode increases, therefore, interelectrode conducting reliability further improves, and the interelectrode contact resistance connecting by electroconductive particle further reduces.In addition,, while forming conductive layer by electroless plating on the surface of basis material particle, difficult cohesion, is difficult for forming the electroconductive particle condensing.Particle diameter is when the above-mentioned upper limit is following, and electroconductive particle is easy to by fully compression, interelectrode contact resistance further reduces and interelectrode interval reduces.At basis material particle, for just spherical in the situation that, the particle diameter of above-mentioned basis material particle represents diameter, and at basis material particle, be not just spherical in the situation that, the particle diameter of above-mentioned basis material particle represents maximum diameter.
More than the particle diameter of above-mentioned basis material particle is especially preferably 2 μ m and below 5 μ m.The particle diameter of above-mentioned basis material particle is in the scope of 2～5 μ m time, and interelectrode interval diminishes, even and the thickness that strengthens conductive layer also can access little electroconductive particle.
[conductive layer]
Electroconductive particle of the present invention has on the surface that is arranged at basis material particle and comprises at least one metal ingredient M in tungsten and molybdenum and the conductive layer X of nickel, boron.Above-mentioned conductive layer X can directly be stacked on the surface of basis material particle, also can be arranged on the surface of basis material particle across other conductive layer etc.In addition, also other conductive layer can be set on the surface of above-mentioned conductive layer X.Other conductive layer is not preferably set on the outer surface of above-mentioned conductive layer X.Preferably the outer surface of electroconductive particle is the conductive layer X that comprises nickel.The electroconductive particle that utilization has a conductive layer X that comprises nickel is when connecting between electrode, and contact resistance further reduces.
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, can be also 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, can be also 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,
Figure BDA0000453941260000141
(seaborgium).
In addition, for having the two the electroconductive particle of nickel conductive layer of not tungstenic and molybdenum, in this two compression initial stage of nickel conductive layer of tungstenic and molybdenum not, it is lower that hardness easily becomes.Thus, when connecting between electrode, the tendency that the effect that exists the effect of the oxide film thereon that causes getting rid of electrode and electroconductive particle surface to diminish, reduce contact resistance diminishes.
On the other hand, when to reduce the effect of contact resistance or adding the two the thickness of nickel conductive layer of very much not tungstenic and molybdenum in order to be applicable to the purposes that large electric current flows through in order further to obtain, exist connecting object parts or substrate easily because of the impaired tendency of the existence of electroconductive particle.Its result, the interelectrode conducting reliability of syndeton body is tended to reduce.
Therefore on the other hand, because above-mentioned conductive layer X comprises at least one metal ingredient M and the nickel in tungsten and molybdenum, easily make more than above-mentioned 5%K value reaches above-mentioned lower limit.In addition, electroconductive particle on compression direction, take be greater than conductivity particle diameter before compression 10% and when compressing front conductivity particle diameter compressed below 25%, easily make above-mentioned conductive layer X moderately break.By moderately breaking when being compressed, be more difficult for the damage of generating electrodes, therefore, interelectrode contact resistance further reduces.
In addition,, by making above-mentioned conductive layer X comprise at least one metal ingredient M and the nickel in tungsten and molybdenum, above-mentioned conductive layer X has appropriate hardness, therefore, while connecting between by electrode at compression conductive particle, can on electrode, form appropriate impression.It should be noted that, the impression forming on electrode is electroconductive particle extruding electrode and the recess of the electrode that produces.
Preferred above-mentioned conductive layer X comprises nickel as principal component.From the viewpoint of the interelectrode initial stage contact resistance of effective reduction, the nickel content in whole 100 % by weight of above-mentioned conductive layer X is The more the better.Therefore, in whole 100 % by weight of above-mentioned conductive layer X, the content of nickel be preferably 50 % by weight above, more preferably 60 % by weight above, more preferably 70 % by weight above, more preferably 75 % by weight above, be further preferably 80 % by weight above, be particularly preferably 85 % by weight above, be more particularly preferably 90 % by weight above, most preferably be 95 % by weight more than.Nickel content in whole 100 % by weight of above-mentioned conductive layer X also can be above for 97 % by weight, also can be above for 97.5 % by weight, can also be for more than 98 % by weight.The content of above-mentioned nickel is when above-mentioned lower limit is above, and interelectrode contact resistance further reduces.In addition, in the few situation of the oxide film thereon of electrode and conductive layer surface, above-mentioned nickel content is more, and interelectrode contact resistance more tends to reduce.
The upper limit of nickel content can be according to the content of boron and above-mentioned metal ingredient M etc. and suitably change.Nickel content in whole 100 % by weight of above-mentioned conductive layer X be preferably 99.9 % by weight following, more preferably 99.85 % by weight following, more preferably 99.7 % by weight following, particularly preferably lower than 99.45 % by weight.
For thering is the electroconductive particle of the nickel conductive layer of boracic not, at this, the compression initial stage of the nickel conductive layer of boracic is comparatively not soft, while carrying out interelectrode connection, the tendency that the effect that exists the effect of the oxide film thereon cause getting rid of electrode and electroconductive particle surface to diminish, reduce contact resistance diminishes.In addition, conductive layer comprises phosphorus rather than boron sometimes.For thering is the electroconductive particle of the conductive layer that comprises nickel and phosphorus, the tendency that the effect that exists the effect of the oxide film thereon that easily causes getting rid of electrode and electroconductive particle surface to diminish, reduce contact resistance diminishes.
On the other hand, in order further to obtain, to reduce the effect of contact resistance or in order to be applicable to the purposes that large electric current flows through, add very much not the thickness of the conductive layer of boracic or during the thickness of the conductive layer that increasing comprises nickel and phosphorus, exist connecting object parts or substrate easily because of the impaired tendency of the existence of electroconductive particle.Its result, the interelectrode conducting reliability of syndeton body is tended to reduce.
Therefore on the other hand, because above-mentioned conductive layer X comprises boron, easily make more than above-mentioned 5%K value reaches above-mentioned lower limit.In addition, electroconductive particle on compression direction, take be greater than conductivity particle diameter before compression 10% and when compressing front conductivity particle diameter compressed below 25%, 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 more than above-mentioned 5%K value reaches above-mentioned lower limit.In addition, electroconductive particle on compression direction, take be greater than conductivity particle diameter before compression 10% and when compressing front conductivity particle diameter compressed below 25%, easily make above-mentioned conductive layer X more moderately break.By moderately breaking when being compressed, be more difficult for the damage of generating electrodes, therefore, interelectrode contact resistance further reduces.
In addition, by making above-mentioned conductive layer X comprise boron, above-mentioned conductive layer X has appropriate hardness, therefore, is more difficult for the damage of generating electrodes, and therefore interelectrode contact resistance further reduces.In addition, by making above-mentioned conductive layer X comprise boron, above-mentioned conductive layer X has appropriate hardness, therefore, while connecting between by electrode at compression conductive particle, can on electrode, form appropriate impression.
Particularly, because above-mentioned conductive layer X comprises nickel, boron and above-mentioned metal ingredient M, therefore can realize high compression modulus of elasticity.Thus, the compression initial stage of the electroconductive particle while connecting between by electrode, the oxide film thereon that can effectively get rid of electrode and electroconductive particle surface, and, electroconductive particle while connecting between by electrode is by the stage of moderate compression, above-mentioned conductive layer X breaks, and can suppress thus the damage of electrode.Its result, can reduce the interelectrode contact resistance of gained syndeton body, can improve interelectrode conducting reliability.
Boron content in whole 100 % by weight of above-mentioned conductive layer X be preferably 0.01 % by weight above, more preferably 0.05 % by weight above, more preferably more than 0.1 % by weight, be preferably 5 % by weight following, more preferably 4 % by weight following, more preferably 3 % by weight following, be particularly preferably 2.5 % by weight following, most preferably be below 2 % by weight.Boron content is when above-mentioned lower limit is above, and above-mentioned conductive layer X becomes harder, can more effectively get rid of the oxide film thereon on electrode and electroconductive particle surface, can further reduce interelectrode contact resistance.Boron content is when the above-mentioned upper limit is following, and the content of nickel and above-mentioned metal ingredient M increases relatively, therefore can reduce interelectrode contact resistance.
In addition, the surface magnetism of the above-mentioned conductive layer X that comprises nickel and boron is high, when being electrically connected between electrode, under the impact of electroconductive particle that cohesion has occurred because of magnetic, has the tendency that produces 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, can suppress a plurality of electroconductive particles condenses.Therefore, when being electrically connected between electrode, can suppress to cause producing and connecting between transversely adjacent electrode owing to having there is the existence of the electroconductive particle of cohesion.That is, can further prevent the short circuit between adjacent electrode.
In addition, by making above-mentioned conductive layer X comprise above-mentioned metal ingredient M, above-mentioned conductive layer X has appropriate hardness, therefore, while connecting between by electrode at compression conductive particle, can on electrode, form appropriate impression.In addition, by making above-mentioned conductive layer X comprise at least one in tungsten and molybdenum or comprise boron, can make above-mentioned conductive layer X become stone, its result, even to the syndeton body connecting between electrode being applied to impact by electroconductive particle, be also difficult for occurring poor flow.That is, can also improve the resistance to impact of syndeton body.
In whole 100 % by weight of above-mentioned conductive layer X the content (total content of tungsten and molybdenum) of above-mentioned metal ingredient M be preferably 0.01 % by weight above, more preferably 0.1 % by weight above, more preferably 0.2 % by weight above, more preferably 0.5 % by weight above, be further preferably 1 % by weight above, be particularly preferably greater than 5 % by weight, most preferably be 10 % by weight more than.The content of above-mentioned metal ingredient M is when above-mentioned lower limit is above, and the hardness of the outer surface of conductive layer further improves.Therefore, in the situation that the surface of electrode or conductive layer has formed oxide film thereon, the oxide film thereon that can effectively get rid of electrode and electroconductive particle surface, and can effectively get rid of the resinous principle between electrode and electroconductive particle, contact resistance reduces, and the resistance to impact of gained syndeton body improves.In addition, the content of above-mentioned metal ingredient M is when above-mentioned lower limit is above, and the magnetic of the outer surface of above-mentioned conductive layer X weakens, and is difficult for occurring the cohesion of a plurality of electroconductive particles.Thus, can effectively suppress interelectrode short circuit.
In whole 100 % by weight of above-mentioned conductive layer X, the upper limit of the content of above-mentioned metal ingredient M can be according to the content of nickel and boron etc. and suitably change.In whole 100 % by weight of above-mentioned conductive layer X the content of above-mentioned metal ingredient M be preferably 40 % by weight following, more preferably 30 % by weight following, more preferably 25 % by weight following, be particularly preferably below 20 % by weight.
In addition, in the situation that above-mentioned conductive layer X comprises tungsten, W content in whole 100 % by weight of above-mentioned conductive layer X be preferably 0.01 % by weight above, more preferably 0.1 % by weight above, more preferably 0.2 % by weight above, more preferably 0.5 % by weight above, be further preferably 1 % by weight above, be particularly preferably greater than 5 % by weight, most preferably be 10 % by weight more than, be preferably 40 % by weight following, more preferably 30 % by weight following, more preferably 25 % by weight following, be particularly preferably below 20 % by weight.In the situation that above-mentioned conductive layer X comprises molybdenum, molybdenum content in whole 100 % by weight of above-mentioned conductive layer X be preferably 0.01 % by weight above, more preferably 0.1 % by weight above, more preferably 0.2 % by weight above, more preferably 0.5 % by weight above, be further preferably 1 % by weight above, be particularly preferably greater than 5 % by weight, most preferably be 10 % by weight more than, be preferably 40 % by weight following, more preferably 30 % by weight following, more preferably 25 % by weight following, be particularly preferably below 20 % by weight.
From the viewpoint of the interelectrode initial stage contact resistance of effective reduction, the above-mentioned nickel in whole 100 % by weight of above-mentioned conductive layer X and the total content of above-mentioned metal ingredient M are The more the better.Therefore, in whole 100 % by weight of above-mentioned conductive layer X, the total content of nickel and above-mentioned metal ingredient M be preferably 75.1 % by weight above, more preferably 80.1 % by weight above, more preferably 85.1 % by weight above, be particularly preferably 90.1 % by weight more than, most preferably be 95.1 % by weight more than.Nickel in whole 100 % by weight of above-mentioned conductive layer X and the total content of above-mentioned metal ingredient M also can be above for 97.1 % by weight, also can for 97.6 % by weight above, can also be for more than 98.1 % by weight.
From the viewpoint of the interelectrode contact resistance of further reduction, preferred above-mentioned conductive layer X is not phosphorous, or above-mentioned conductive layer X comprise phosphorus but the content of phosphorus in whole 100 % by weight of above-mentioned conductive layer X lower than 1 % by weight.From further reducing the viewpoint of 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 whole 100 % by weight of above-mentioned conductive layer X lower than 0.5 % by weight.From more effectively reducing the viewpoint of interelectrode contact resistance, the phosphorus content in whole 100 % by weight of above-mentioned conductive layer X more preferably 0.3 % by weight following, more preferably below 0.1 % by weight.By making phosphorus content below the above-mentioned upper limit, when connecting between electrode, can more effectively get rid of the oxide film thereon on electrode and electroconductive particle surface.Its result, can reduce interelectrode contact resistance.In addition,, owing to can effectively getting rid of the resinous principle between electrode and electroconductive particle, therefore, interelectrode contact resistance further reduces.Owing to can making interelectrode contact resistance significantly reduce, therefore, especially preferred above-mentioned conductive layer X is not phosphorous.
Particularly, 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 in the situation that outer surface has projection, the oxide film thereon that can more effectively get rid of electrode and electroconductive particle surface, and can effectively get rid of the resinous principle between electrode and electroconductive particle, can further reduce contact resistance.
In addition, by making above-mentioned conductive layer X comprise above-mentioned metal ingredient M and phosphorus content below the above-mentioned upper limit, above-mentioned conductive layer X becomes stone, its result, even to the syndeton body connecting between electrode being applied to impact by electroconductive particle, be also difficult for occurring poor flow.That is, can also improve the resistance to impact of syndeton body.
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, can enumerate absorptiometric analysis method or spectra methods etc.In above-mentioned absorptiometric analysis method, can use flame spectrophotometer and electric furnace formula spectrophotometer etc.As above-mentioned spectra methods, can enumerate plasma emission spectroscopy method and plasma ion source mass spectrometry etc.
While measuring each content of nickel, boron, tungsten, molybdenum and phosphorus in above-mentioned conductive layer X, preferably use ICP emission spectrum device.As the commercially available product of ICP emission spectrum device, can enumerate the ICP emission spectrum device of HORIBA company manufacture etc.In addition, while measuring each content of nickel, boron, tungsten, molybdenum and phosphorus in above-mentioned conductive layer X, also can use ICP-MS analyzer.
The metal that is used to form above-mentioned other conductive layer (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, can enumerate tin-doped indium oxide (ITO) and scolding tin etc.Wherein, owing to can making interelectrode contact resistance further reduce, so some alloy that comprises tin, nickel, palladium, copper or gold, more preferably nickel or palladium.The metal that forms above-mentioned other conductive layer preferably comprises nickel.
The method that forms conductive layer (other conductive layer and conductive layer X) on the surface of above-mentioned basis material particle is not particularly limited.As the method that forms conductive layer, can enumerate such as: utilize electroless plating method, utilize electric plating method, utilize the method for physical vapor deposition and by metal dust or comprise metal dust and the thickener of adhesive is coated on the surperficial method etc. of basis material particle or other conductive layer.Wherein, because the formation of conductive layer is easy, therefore preferably utilize the method for electroless plating.As the above-mentioned method of utilizing physical vapor deposition, can enumerate the methods such as vacuum evaporation, ion plating and ion sputtering.
The particle diameter of above-mentioned electroconductive particle be preferably 0.1 μ m above, more preferably 0.5 μ m above, more preferably 1 μ m above, be particularly preferably 2 μ m more than, be preferably 1000 μ m following, more preferably 500 μ m following, more preferably 300 μ m following, more preferably 100 μ m following, be further preferably 50 μ m following, be particularly preferably 30 μ m following, be more particularly preferably 20 μ m following, most preferably be below 5 μ m.The particle diameter of electroconductive particle is more than above-mentioned lower limit and when the above-mentioned upper limit is following, uses electroconductive particle when connecting between electrode, and the contact area between electroconductive particle and electrode fully becomes greatly, and when forming conductive layer, is difficult for forming the electroconductive particle condensing.In addition, it is excessive that the interelectrode interval connecting by electroconductive particle can not become, and conductive layer is difficult for the sur-face peeling from basis material particle.
In addition, during for electric conducting materials such as anisotropic conductive materials, the particle diameter of electroconductive particle be preferably 0.5 μ m above, more preferably more than 1 μ m, be preferably 100 μ m following, more preferably below 20 μ m.The particle diameter of electroconductive particle is more than above-mentioned lower limit and when the above-mentioned upper limit is following, uses electroconductive particle when connecting between electrode, and the contact area between electroconductive particle and electrode fully becomes greatly, and when forming conductive layer, is difficult for forming the electroconductive particle condensing.In addition, it is excessive that the interelectrode interval connecting by electroconductive particle can not become, and conductive layer is difficult for the sur-face peeling from basis material particle.
At electroconductive particle, for just spherical in the situation that, the particle diameter of above-mentioned electroconductive particle represents diameter, and at electroconductive particle, be not just spherical in the situation that, the particle diameter of above-mentioned electroconductive particle represents maximum diameter.
The thickness of above-mentioned conductive layer X be preferably 0.005 μ m above, more preferably 0.01 μ m above, more preferably more than 0.05 μ m, be preferably 1 μ m following, more preferably below 0.3 μ m.The thickness of above-mentioned conductive layer X, more than above-mentioned lower limit and when the above-mentioned upper limit is following, can obtain sufficient conductivity, and electroconductive particle can not become really up to the mark, and when connecting between electrode, electroconductive particle can fully deform.
Conductive layer is in the situation of 2 layers of above laminated construction, the thickness of conductive layer X be preferably 0.001 μ m above, more preferably 0.01 μ m above, more preferably more than 0.05 μ m, be preferably 0.5 μ m following, more preferably 0.3 μ m following, more preferably below 0.1 μ m.The thickness of above-mentioned conductive layer X is more than above-mentioned lower limit and when the above-mentioned upper limit is following, can make the coated homogeneous that becomes that utilizes conductive layer X to carry out, and interelectrode contact resistance fully reduces.
Conductive layer is in the situation of 2 layers of above laminated construction, the thickness of the conductive layer integral body that comprises conductive layer X be preferably 0.001 μ m above, more preferably 0.01 μ m above, more preferably 0.05 μ m above, be particularly preferably 0.1 μ m more than, be preferably 1 μ m following, more preferably 0.5 μ m following, more preferably 0.3 μ m following, more preferably below 0.1 μ m.The thickness of above-mentioned conductive layer integral body is more than above-mentioned lower limit and when the above-mentioned upper limit is following, can make the coated homogeneous that becomes that utilizes conductive layer integral body to carry out, and interelectrode contact resistance fully reduces.
Particularly preferably the thickness of above-mentioned conductive layer X is more than 0.05 μ m and below 0.5 μ m.Further, particularly preferably the particle diameter of basis material particle is that 2 μ m are above and 5 μ m are following and thickness above-mentioned conductive layer X is more than 0.05 μ m and below 0.5 μ m.Most preferably the thickness of above-mentioned conductive layer X is more than 0.05 μ m and below 0.3 μ m.Further, most preferably the particle diameter of basis material particle is that 2 μ m are above and 5 μ m are following and thickness above-mentioned conductive layer X is more than 0.05 μ m and below 0.3 μ m.While meeting the thickness of these preferred above-mentioned conductive layer X and the particle diameter of basis material particle, can make the electroconductive particle purposes flowing through for large electric current preferably.In addition, the in the situation that of connection between electroconductive particle is compressed electrode, can further suppress electrode and damage.
The thickness of the thickness of above-mentioned conductive layer X and above-mentioned conductive layer integral body can be by being used for example transmission electron microscope (TEM) to observe to measure to the section of electroconductive particle.
As the method for controlling the content of nickel, tungsten, molybdenum, boron and phosphorus in above-mentioned conductive layer X, for example can enumerate: when forming conductive layer X by process for electroless nickel plating, the method that the pH of nickel-plating liquid is controlled; When forming conductive layer X by process for electroless nickel plating, the method that the concentration of boracic reducing agent is regulated; The method that tungsten concentration in nickel-plating liquid is regulated; The method that molybdenum concentration in nickel-plating liquid is regulated; And the method that the nickel salt concentration in nickel-plating liquid is regulated etc.
In the method forming by electroless plating, conventionally to carry out catalyst chemical industry order and electroless plating operation.Below, for an example of method that forms the alloy layer of at least one that comprise in tungsten and molybdenum, nickel and boron by electroless plating on the surface of resin particle, describe.
In above-mentioned catalyst chemical industry order, make catalyst be formed at the surface of resin particle, described catalyst becomes for form the starting point of coating by electroless plating.
As making above-mentioned catalyst be formed at the surperficial method of resin particle, for example can enumerate: in the solution that comprises palladium bichloride and stannic chloride, add resin particle, then utilize acid solution or aqueous slkali to make the surface active of resin particle, thus the method that palladium is separated out on the surface of resin particle; And add resin particle in the solution that contains palladium sulfate and aminopyridine, then utilize the solution comprise reducing agent to make the surface active of resin particle, thereby make method that palladium separates out on the surface of resin particle etc.As above-mentioned reducing agent, preferably use boracic reducing agent.In addition, as above-mentioned reducing agent, also can use the phosphorous reducing agents such as sodium hypophosphite.
In above-mentioned electroless plating operation, can use the nickel plating bath of at least one that comprise in Tungstenic compound and molybdate compound, nickel salt and above-mentioned boracic reducing agent.By resin particle be impregnated in nickel plating bath, separate out on the surface that can make nickel be formed with the resin particle of catalyst on surface, thereby can form the conductive layer that comprises nickel, boron and above-mentioned metal ingredient M.
As above-mentioned Tungstenic compound, can enumerate tungsten boride and sodium tungstate etc.
As above-mentioned molybdate compound, can enumerate molybdenum boride and sodium molybdate etc.
As above-mentioned boracic reducing agent, can enumerate dimethylamino borine, sodium borohydride and potassium borohydride etc.
Preferred electroconductive particle of the present invention has projection on surface.The conductive layer that preferably comprises above-mentioned conductive layer X has projection at outer surface, and preferred above-mentioned conductive layer X has projection at outer surface.At the electrode surface connecting by electroconductive particle, be mostly formed with oxide film thereon.In addition, the conductive layer surface at electroconductive particle is formed with oxide film thereon mostly.By using the bossed electroconductive particle of tool, after electroconductive particle is arranged between electrode, by carrying out pressing, can utilizes projection and oxide film thereon is got rid of effectively.Thus, can make electrode contact more effectively with electroconductive particle, can reduce interelectrode contact resistance.In addition, in the situation that the surface of electroconductive particle has megohmite insulant, or, in the situation that electroconductive particle is scattered in adhesive resin and is used as electric conducting material, can utilize the projection of electroconductive particle and the resin between electroconductive particle and electrode is got rid of effectively.Thus, interelectrode conducting reliability improves.
Above-mentioned projection is preferably a plurality of.More than the projection of the above-mentioned conductive layer outer surface of every 1 above-mentioned electroconductive particle is preferably 3, more preferably more than 5.The upper limit of above-mentioned bump count is not particularly limited.The upper limit of bump count can be in the situation that consider the suitably selections such as particle diameter of electroconductive particle.
[core material]
By above-mentioned core material is imbedded in above-mentioned conductive layer, can easily make above-mentioned conductive layer there are a plurality of projections at outer surface.But in order to form projection at electroconductive particle and conductive layer surface, also not must use core material.
As the method that forms above-mentioned projection, can enumerate: core material is attached to behind the surface of basis material particle, by electroless plating, form the method for conductive layer; And forming after conductive layer on the surface of basis material particle by electroless plating, core material is adhered to, and then by electroless plating, form the method etc. of conductive layer.
As the method for core material is set on the surface at above-mentioned basis material particle, for example can enumerate: in the dispersion liquid of basis material particle, be added to the conductive material of core material, make core material in the effect next part coalescence of for example Van der Waals force, be attached to the surperficial method of basis material particle; And the conductive material that is added to core material at the container of having put into basis material particle, under the mechanism producing because of container rotation etc., make core material be attached to surperficial method of basis material particle etc.Therefore wherein, owing to easily the amount of the core material adhering to being controlled, preferably make core material gather and be attached to the surperficial method of the basis material particle in dispersion liquid.
As the conductive material that forms above-mentioned core material, can enumerate such as the electrically conductive, non-metallics such as the oxide of metal, metal, graphite and electric conductive polymer etc.As electric conductive polymer, can enumerate polyacetylene etc.Wherein, owing to can improving conductivity and can effectively reducing contact resistance so preferable alloy.Above-mentioned core material is preferably metallic.
As above-mentioned metal, can enumerate such as alloy that the metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium and tin-lead alloy, tin-copper alloy, tin-silver alloy and tin-lead-silver alloy etc. are formed by two or more metal etc.Wherein, preferred nickel, copper, silver or golden.The metal that forms above-mentioned core material can be same with the Metal Phase that forms above-mentioned conductive layer, also can be different.The metal that preferably forms above-mentioned core material comprises the metal that forms above-mentioned conductive layer.The metal that preferably forms above-mentioned core material comprises nickel.The metal that preferably forms above-mentioned core material comprises nickel.
The shape of above-mentioned core material is not particularly limited.The shape of core material is preferably bulk.As core material, can enumerate such as: the cohesion piece that emboliform, a plurality of fine particle cohesion form and atypic etc.
The average diameter of above-mentioned core material (average grain diameter) be preferably 0.001 μ m above, more preferably more than 0.05 μ m, be preferably 0.9 μ m following, more preferably below 0.2 μ m.The average diameter of above-mentioned core material, more than above-mentioned lower limit and when the above-mentioned upper limit is following, 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 any 50 core materials of electron microscope or observation by light microscope, and calculate mean value.
[megohmite insulant]
Electroconductive particle of the present invention preferably possesses the megohmite insulant being arranged on above-mentioned conductive layer surface.In this case, when electroconductive particle is used for to interelectrode connection, can prevent the short circuit between adjacent electrode.Particularly, when the contact of a plurality of electroconductive particles, owing to having megohmite insulant between a plurality of electrodes, therefore can prevent between transversely adjacent electrode but not short circuit between upper/lower electrode.It should be noted that, when connecting between electrode, by utilizing 2 electrode pair electroconductive particles to pressurize, can easily get rid of the conductive layer of electroconductive particle and the megohmite insulant between electrode.Because electroconductive particle has a plurality of projections at the outer surface of conductive layer, therefore can easily get rid of the conductive layer of electroconductive particle and the megohmite insulant between electrode.
Owing to can more easily above-mentioned megohmite insulant being got rid of when carrying out interelectrode pressing, therefore preferred above-mentioned megohmite insulant is insulating properties particle.
As the material of above-mentioned megohmite insulant, be the concrete example of insulative resin, can enumerate: cross-linking agent, thermosetting resin and the water-soluble resin etc. of TPO, (methyl) acrylate polymer, (methyl) acrylate copolymer, block polymer, thermoplastic resin, thermoplastic resin.
As said polyolefins class, can enumerate: polyethylene, vinyl-vinyl acetate copolymer and vinyl-acrylate copolymer etc.As above-mentioned (methyl) acrylate polymer, can enumerate poly-(methyl) methyl acrylate, poly-(methyl) ethyl acrylate and poly-(methyl) butyl acrylate etc.As above-mentioned block polymer, can enumerate polystyrene, copolymer in cinnamic acrylic ester, SB type styrene-butadiene block copolymer and SBS type styrene-butadiene block copolymer and their hydrogenation products etc.As above-mentioned thermoplastic resin, can enumerate polyvinyl and ethylenic copolymer etc.As above-mentioned thermosetting resin, can enumerate epoxy resin, phenolic resins and melmac etc.As above-mentioned water-soluble resin, can enumerate polyvinyl alcohol, polyacrylic acid, polyacrylamide, PVP, polyoxyethylene and methylcellulose etc.Wherein, preferred water soluble resin, more preferably polyvinyl alcohol.
As the method for megohmite insulant is set 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 suspension polymerization under existing such as: interfacial polymerization, particle and emulsion polymerization etc.As above-mentioned physics or mechanical means, can enumerate: spray drying process, hydridization method, electrostatic adherence method, spray-on process, infusion process and utilize method of vacuum evaporation etc.Wherein, because megohmite insulant is difficult for departing from, therefore the method for above-mentioned megohmite insulant is preferably set at above-mentioned conductive layer surface by chemical bond.
The average diameter of above-mentioned megohmite insulant (average grain diameter) can suitably be selected according to the purposes of the particle diameter of electroconductive particle and electroconductive particle etc.The average diameter of above-mentioned megohmite insulant (average grain diameter) be preferably 0.005 μ m above, more preferably more than 0.01 μ m, be preferably 1 μ m following, more preferably below 0.5 μ m.The average diameter of megohmite insulant, when above-mentioned lower limit is above, when electroconductive particle is scattered in adhesive resin, is difficult for coming in contact between the conductive layer of a plurality of electroconductive particles.The average diameter of insulating properties particle when the above-mentioned upper limit is following, when connecting between electrode, need to be for the megohmite insulant between electrode and electroconductive particle is got rid of and excessively improved pressure, without 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, 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, can use known insulative resin.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 be used a kind, also two or more can be used in combination.
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, light-cured type resin or wet-cured type resin.Above-mentioned curable resin can also be used in combination with curing agent.As above-mentioned thermoplastic block copolymers, can enumerate such as the hydrogenation products of SBS, SIS, SBS and the hydrogenation products of SIS etc.As above-mentioned elastomer, can enumerate such as styrene-butadiene copolymer 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 various additives 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.
Make above-mentioned electroconductive particle be scattered in the process for dispersing that method in above-mentioned adhesive resin can adopt conventional known, be not particularly limited.As making above-mentioned electroconductive particle be scattered in the method in above-mentioned adhesive resin, for example can enumerate: add above-mentioned electroconductive particle in above-mentioned adhesive resin after, utilize planet mixer etc. to carry out mixing so that the method for its dispersion; Use homogenizer etc. to make after above-mentioned electroconductive particle is dispersed in water or organic solvent, to be added in above-mentioned adhesive resin, utilize planet mixer etc. to carry out mixing so that the method for its dispersion; And by after the dilution such as above-mentioned adhesive resin water or organic solvent, add above-mentioned electroconductive particle, utilize planet mixer etc. to carry out mixing so that the method for its dispersion; Etc..
Electric conducting material of the present invention can be made into the uses such as electroconductive paste and conducting film.In the situation that electric conducting material of the present invention being made to the film-like adhesive uses such as conducting film, also can not contain the film-like adhesive of electroconductive particle at the film-like adhesive superimposed layer that comprises this 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 be preferably 10 % by weight above, more preferably 30 % by weight above, more preferably 50 % by weight above, be particularly preferably 70 % by weight more than, be preferably 99.99 % by weight following, more preferably below 99.9 % by weight.The content of above-mentioned adhesive resin, more than above-mentioned lower limit and when the above-mentioned upper limit is following, can effectively arrange electroconductive particle between electrode, and the connection reliability of the connecting object parts that connected by electric conducting material further improves.
In above-mentioned electric conducting material 100 % by weight, the content of above-mentioned electroconductive particle be preferably 0.01 % by weight above, more preferably 0.1 % by weight above, be preferably 40 % by weight following, more preferably 20 % by weight following, more preferably below 10 % by weight.The content of above-mentioned electroconductive particle is more than above-mentioned lower limit and when the above-mentioned upper limit is following, and interelectrode conducting reliability further improves.
(syndeton body)
The electric conducting material that the electroconductive particle of the application of the invention or use comprise this electroconductive particle and adhesive resin is connected connecting object parts, can obtain syndeton body.
Above-mentioned syndeton body be preferably possess the 1st connecting object parts, the 2nd connecting object parts and connect the 1st, the connecting portion of the 2nd connecting object parts, and this connecting portion syndeton body of being formed by electroconductive particle of the present invention or being formed by the electric conducting material that comprises this electroconductive particle and adhesive resin.In the situation that using electroconductive particle, connecting portion is originally as electroconductive particle.That is, the 1st, the 2nd connecting object parts are connected by electroconductive particle.In order to obtain the above-mentioned electric conducting material of above-mentioned syndeton body, be preferably anisotropic conductive material.
Fig. 4 schematically shows the syndeton body of the electroconductive particle that has used the present invention's the 1st execution mode with front cross-sectional view.
Syndeton body 51 shown in Fig. 4 possesses: the connecting portion 54 of the 1st connecting object parts the 52, the 2nd connecting object parts 53 and connection the 1st, the 2nd connecting object parts 52,53.Connecting portion 54 is by being solidified to form the electric conducting material that comprises electroconductive particle 1.It should be noted that, in Fig. 4, for the ease of diagram, electroconductive particle 1 represents with sketch map.
The 1st connecting object parts 52 in the above 52a (surface) have a plurality of electrode 52b.The 2nd connecting object parts 53 below 53a (surface) have a plurality of electrode 53b.Electrode 52b is electrically connected to by one or more electroconductive particles 1 with electrode 53b.Therefore, the 1st, the 2nd connecting object parts 52,53 are electrically connected to by electroconductive particle 1.
The manufacture method of above-mentioned syndeton body is not particularly limited.As an example of the manufacture method of syndeton body, can 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, this laminated body is heated and the method for pressurizeing etc.The pressure of above-mentioned pressurization is 9.8 * 10 4～4.9 * 10 6pa left and right.The temperature of above-mentioned heating is 120～220 ℃ of left and right.
As above-mentioned connecting object parts, specifically can enumerate: the circuit substrates such as the electronic units such as semiconductor chip, capacitor and diode and printed base plate, flexible printing substrate and glass substrate etc.Preferred above-mentioned electric conducting material is the electric conducting material in order to connecting electronic parts.The electroconductive paste that preferred above-mentioned electric conducting material is pasty state is also coated on connecting object parts with the state of pasty state.
As the electrode arranging on above-mentioned connecting object parts, can enumerate the metal electrodes such as gold electrode, nickel electrode, tin electrode, aluminium electrode, copper electrode, molybdenum electrode and tungsten electrode.Above-mentioned connecting object parts are in the situation of flexible printing substrate, and preferred above-mentioned electrode is gold electrode, nickel electrode, tin electrode or copper electrode.In the situation that above-mentioned connecting object parts are glass substrate, preferred above-mentioned electrode is aluminium electrode, copper electrode, molybdenum electrode or tungsten electrode.It should be noted that, above-mentioned electrode is in the situation of aluminium electrode, can be the electrode only being formed by aluminium, the electrode that also can form for the surperficial lamination aluminium lamination at metal oxide layer.As the material of above-mentioned metal oxide layer, can enumerate doped with the indium oxide of 3 valency metallic elements and doped with zinc oxide of 3 valency metallic elements etc.As above-mentioned 3 valency metallic elements, can enumerate Sn, Al and Ga etc.
Below, in conjunction with the embodiments and comparative example the present invention is specifically described.The present invention is not only defined in following embodiment.
(embodiment 1)
Having prepared particle diameter is the divinyl benzene copolymer resin particle (ponding chemical industrial company system " Micropearl SP-203 ") of 3.0 μ m.
Utilize ultrasonic disperser that above-mentioned resin particle 10 weight portions are dispersed in aqueous slkali 100 weight portions that comprise 5 % by weight palladium catalyst liquid, then solution is filtered, isolate thus resin particle.Then, resin particle is added in dimethylamino borine 1 % by weight solution 100 weight portions, 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 portions it is disperseed, and has obtained thus suspension.
In addition, prepared the nickel-plating liquid (pH8.5) that comprises nickelous sulfate 0.23mol/L, dimethylamino borine 0.92mol/L, natrium citricum 0.5mol/L and sodium tungstate 0.01mol/L.
When stirring gained suspension for 60 ℃, above-mentioned nickel-plating liquid is slowly added drop-wise in suspension, carried out process for electroless nickel plating.Then, by suspension is filtered and isolates particle, and wash, be dried, obtained being thus provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 2)
Except concentration of sodium tungstate being changed to 0.12mol/L, operate similarly to Example 1, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 3)
Except concentration of sodium tungstate being changed to 0.23mol/L, operate similarly to Example 1, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 4)
Except concentration of sodium tungstate being changed to 0.35mol/L, operate similarly to Example 1, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 5)
Except dimethylamino borane concentration being changed to 2.76mol/L and concentration of sodium tungstate being changed to 0.35mol/L, operate similarly to Example 1, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 6)
(1) palladium adheres to operation
Having prepared particle diameter is the divinylbenzene resin particle (ponding chemical industrial company system " Micropearl SP-205 ") of 5.0 μ m.This resin particle has been carried out to etching, washing.Then, resin particle added in the palladium catalyst liquid 100mL that comprises 8 % by weight palladium catalysts and stir.Then, filter, wash.Resin particle is added in the 0.5 % by weight dimethylamino borine liquid of pH6, obtained being attached with the resin particle of palladium.
(2) core material adheres to operation
The resin particle that is attached with palladium is stirred 3 minutes in ion exchange water 300mL, it is disperseed, obtained dispersion liquid.Then, metallic nickel particle slurry (average grain diameter 100nm) 1g was added in above-mentioned dispersion liquid through 3 minutes, obtained being attached with the resin particle of core material.
(3) process for electroless nickel plating operation
Operate similarly to Example 1, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 7)
Except concentration of sodium tungstate being changed to 0.35mol/L, operate similarly to Example 6, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 8)
(1) making of insulating properties particle
The separable lid of four-hole is 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) monomer composition of 1mmol joining in ion exchange water, the fraction solids that makes this monomer composition is 5 % by weight, then, with 200rpm, stir, and in nitrogen atmosphere, at 70 ℃, carried out polymerization in 24 hours.After reaction finishes, carry out freeze drying, obtained the surperficial insulating properties particle with ammonium, average grain diameter 220nm and CV value 10%.
Under ultrasonic irradiation, make insulating properties particle be scattered in ion exchange water, obtained 10 % by weight aqueous dispersions of insulating properties particle.
The electroconductive particle 10g obtaining in embodiment 6 is scattered in ion exchange water 500mL, adds the aqueous dispersions 4g of insulating properties particle, under room temperature, carried out stirring for 6 hours.After utilizing the granular membrane of 3 μ m to filter, then wash with methyl alcohol, dry, obtained being attached with the electroconductive particle of insulating properties particle.
Utilize scanning electron microscopy (SEM) to observe following result: on the surface of electroconductive particle, only to form 1 layer of coating layer that comes from insulating properties particle.By image analysis, the coated area of the insulating properties particle of the area with respect to apart from electroconductive particle center 2.5 μ m (being the particle diameter projected area of insulating properties particle) is calculated, result, clad ratio is 30%.
(embodiment 9)
Except concentration of sodium tungstate being changed to 0.46mol/L, operate similarly to Example 1, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 10)
Except dimethylamino borane concentration being changed to 4.60mol/L and concentration of sodium tungstate being changed to 0.23mol/L, operate similarly to Example 1, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(comparative example 1)
Except the dimethylamino borine 0.92mol/L in nickel-plating liquid being changed to sodium hypophosphite 0.5mol/L, operate similarly to Example 1, obtained being provided with on the surface of resin particle the electroconductive particle of the conductive layer (thick 0.1 μ m) that comprises nickel, tungsten and phosphorus.In whole 100 % by weight of conductive layer, 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, obtained being provided with on the surface of resin particle the electroconductive particle of the conductive layer (thick 0.1 μ m) that comprises nickel and boron.
(embodiment 11)
Having prepared particle diameter is the divinyl benzene copolymer resin particle (ponding chemical industrial company system " Micropearl SP-203 ") of 3.0 μ m.
Utilize ultrasonic disperser that above-mentioned resin particle 10 weight portions are dispersed in aqueous slkali 100 weight portions that comprise 5 % by weight palladium catalyst liquid, then solution is filtered, isolate thus resin particle.Then, resin particle is added in dimethylamino borine 1 % by weight solution 100 weight portions, 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 portions it is disperseed, and has obtained thus suspension.
In addition, prepared the nickel-plating liquid (pH8.5) that comprises nickelous sulfate 0.23mol/L, dimethylamino borine 0.92mol/L, natrium citricum 0.5mol/L and sodium molybdate 0.01mol/L.
When stirring gained suspension for 60 ℃, above-mentioned nickel-plating liquid is slowly added drop-wise in suspension, carried out process for electroless nickel plating.Then, by suspension is filtered and isolates particle, and wash, be dried, obtained being thus provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 12)
Except sodium molybdate concentration being changed to 0.12mol/L, operate similarly to Example 11, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 13)
Except sodium molybdate concentration being changed to 0.23mol/L, operate similarly to Example 11, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 14)
Except sodium molybdate concentration being changed to 0.35mol/L, operate similarly to Example 11, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 15)
Except dimethylamino borane concentration being changed to 2.76mol/L and sodium molybdate concentration being changed to 0.35mol/L, operate similarly to Example 11, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 16)
(1) palladium adheres to operation
Having prepared particle diameter is the divinylbenzene resin particle (ponding chemical industrial company system " Micropearl SP-205 ") of 5.0 μ m.This resin particle has been carried out to etching, washing.Then, resin particle added in the palladium catalyst liquid 100mL that comprises 8 % by weight palladium catalysts and stir.Then, filter, wash.Resin particle is added in the 0.5 % by weight dimethylamino borine liquid of pH6, obtained being attached with the resin particle of palladium.
(2) core material adheres to operation
The resin particle that is attached with palladium is stirred 3 minutes in ion exchange water 300mL, it is disperseed, obtained dispersion liquid.Then, metallic nickel particle slurry (average grain diameter 100nm) 1g was added in above-mentioned dispersion liquid through 3 minutes, obtained being attached with the resin particle of core material.
(3) process for electroless nickel plating operation
Operate similarly to Example 11, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 17)
Except sodium molybdate concentration being changed to 0.35mol/L, operate similarly to Example 16, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 18)
(1) making of insulating properties particle
In the detachable flask of 1000mL of the separable lid of four-hole, paddle, triple valve, condenser pipe and temp probe is installed, 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 that makes this monomer composition is 5 % by weight, then, with 200rpm, stir, and carried out polymerization in 24 hours in nitrogen atmosphere, at 70 ℃.After reaction finishes, carry out freeze drying, obtained the surperficial insulating properties particle with ammonium, average grain diameter 220nm and CV value 10%.
Under ultrasonic irradiation, make insulating properties particle be scattered in ion exchange water, obtained 10 % by weight aqueous dispersions of insulating properties particle.
The electroconductive particle 10g obtaining in embodiment 16 is scattered in ion exchange water 500mL, adds the aqueous dispersions 4g of insulating properties particle, under room temperature, carried out stirring for 6 hours.After utilizing the granular membrane of 3 μ m to filter, then wash with methyl alcohol, dry, obtained being attached with the electroconductive particle of insulating properties particle.
Utilize scanning electron microscopy (SEM) to observe following result: on the surface of electroconductive particle, only to form 1 layer of coating layer that comes from insulating properties particle.By image analysis, the coated area of the insulating properties particle of the area with respect to apart from electroconductive particle center 2.5 μ m (being the particle diameter projected area of insulating properties particle) is calculated, result, clad ratio is 30%.
(embodiment 19)
Except sodium molybdate concentration being changed to 0.46mol/L, operate similarly to Example 11, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 20)
Except dimethylamino borane concentration being changed to 4.60mol/L and sodium molybdate concentration being changed to 0.23mol/L, operate similarly to Example 11, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(comparative example 3)
Except the dimethylamino borine 0.92mol/L in nickel-plating liquid being changed to sodium hypophosphite 0.5mol/L, operate similarly to Example 11, obtained being provided with on the surface of resin particle the electroconductive particle of the conductive layer (thick 0.1 μ m) that comprises nickel, molybdenum and phosphorus.In whole 100 % by weight of conductive layer, 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 of electroconductive particle (5%K value)
Use slight compression testing machine (Fischer company system " Fischer Scope H-100 ") to measure the modulus of elasticity in comperssion of gained electroconductive particle (5%K value).
(2) breaking of conductive layer tested
Electroconductive particle is placed on stand.Use slight compression testing machine (Fischer company system " Fischer Scope H-100 ") under the condition of compression speed 0.33mN/ second and maximum test load 10mN, the cylinder (diameter 50 μ m, Buddha's warrior attendant made of stones) of usining, as compression member, makes the level and smooth end face of this compression member decline towards electroconductive particle.Utilize level and smooth end face to compress electroconductive particle.Compress until the conductive layer of electroconductive particle breaks.With respect to the particle diameter of electroconductive particle before the compression on compression direction, conductive layer has produced the above-mentioned compression displacement of the electroconductive particle breaking as shown in following table 1,2.About the evaluation result of above-mentioned compression displacement, 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 the molybdenum in whole 100 % by weight of conductive layer X
In the mixed liquor of 60% nitric acid 5mL and 37% hydrochloric acid 10mL, add electroconductive particle 5g, conductive layer is dissolved completely, obtained solution.Use gained solution, utilize ICP-MS analyzer (Hitachi company system) 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
Utilize scanning electron microscope to observe the plating state of 50 of gained electroconductive particles.For plating, break or plating the having or not of plating inequality such as is peeled off and observed.There are 4 following situations to be judged to be " well ", to have 5 above situations to be judged to be " bad " electroconductive particle that confirms plating inequality the electroconductive particle that confirms 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 approximately 800,000) 40 weight portions, methyl ethyl ketone 200 weight portions, microcapsule-type curing agent (Asahi Kasei Chemicals company's system " HX3941HP ") 50 weight portions and silane coupler (Dow Coring Toray company's system " SH6040 ") 2 weight portions are mixed, add electroconductive particle and make its content reach 3 % by weight, disperse, obtained anisotropic conductive material.
Gained anisotropic conductive material is preserved 72 hours at 25 ℃.After preservation, for whether having there is the sedimentation of electroconductive particle after cohesion in anisotropic conductive material, evaluate.The situation that the sedimentation of the rear electroconductive particle of cohesion does not occur is judged to be to " well ", the situation that the sedimentation of electroconductive particle after cohesion has occurred is judged to be to " bad ".
(6) contact resistance
The making of syndeton body:
Bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " Epikote1009 ") 10 weight portions, acrylic rubber (weight average molecular weight approximately 800,000) 40 weight portions, methyl ethyl ketone 200 weight portions, microcapsule-type curing agent (Asahi Kasei Chemicals company's system " HX3941HP ") 50 weight portions and silane coupler (Dow Coring Toray company's system " SH6040 ") 2 weight portions are mixed, add electroconductive particle and make its content reach 3 % by weight, disperse, obtained resin combination.
Gained resin combination is coated to PET (PETG) film that one side has passed through the thick 50 μ m that the demoulding processes, utilize the heated-air drying 5 minutes of 70 ℃, made anisotropic conductive film.The thickness of gained anisotropic conductive film is 12 μ m.
Gained anisotropic conductive film is cut into the size of 5mm * 5mm.By cutting the anisotropic conductive film obtaining, be fitted in and there is the substantial middle that a side has the aluminium electrode side of the glass substrate (wide 3cm, long 3cm) of the aluminium electrode (high 0.2 μ m, L/S=20 μ m/20 μ m) of lead-in wire (draw I and return Line) for resistance measurement.Then, will have identical aluminium electrode two-layer flexible printed base plate (wide 2cm, long 1cm) so that the mode overlapping each other between electrode after positioning, fit.Under the pressing condition in 10N, 180 ℃ and 20 seconds, the laminated body of this glass substrate and two-layer flexible printed base plate is carried out to hot pressing, obtained syndeton body.Wherein, used the two-layer flexible printed base plate that is directly formed with aluminium electrode on polyimide film.
The mensuration of contact resistance:
Utilize four-terminal method to measure the relative interelectrode contact resistance of gained syndeton body.In addition, according to following standard, contact resistance is judged.
[criterion of contact resistance]
00: contact resistance is below 2.0 Ω
Zero: contact resistance surpasses 2.0 Ω and is below 3.0 Ω
△: contact resistance surpasses 3.0 Ω and is below 5.0 Ω
*: contact resistance surpasses 5.0 Ω
(7) resistance to impact
The syndeton body obtaining in the evaluation of above-mentioned (6) contact resistance is fallen from the position of high 70cm, by confirmation conducting, resistance to impact is evaluated.By the resistance value climbing with respect to initial stage resistance value, be that situation below 50% is judged to be " well ", the resistance value climbing with respect to initial stage resistance value is surpassed to 50% situation is judged to be " bad ".
(8) have or not formation impression
Use differential interference microscope, the glass substrate side of the syndeton body obtaining from the evaluation at above-mentioned (6) contact resistance is observed the electrode being arranged on glass substrate, and on electrode electroconductive particle being contacted according to following standard, has or not formation impression to judge.It should be noted that, about having or not formation impression on electrode, so that electrode area is 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, calculated the every 0.02mm of electrode 2on the mean value of impression number.
[having or not the criterion that forms impression]
00: the every 0.02mm of electrode 2on impression be more than 25
Zero: the every 0.02mm of electrode 2on impression be 20 above and be less than 25
△: the every 0.02mm of electrode 2on impression be 5 above 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.
Figure BDA0000453941260000351
Figure BDA0000453941260000361
It should be noted that, the electroconductive particle of the electroconductive particle of embodiment 21～40 and comparative example 4～6 and embodiment 1～20 and comparative example 1～3 is made respectively.
(embodiment 21)
Having prepared particle diameter is the divinyl benzene copolymer resin particle (ponding chemical industrial company system " Micropearl SP-203 ") of 3.0 μ m.
Utilize ultrasonic disperser that above-mentioned resin particle 10 weight portions are dispersed in aqueous slkali 100 weight portions that comprise 5 % by weight palladium catalyst liquid, then solution is filtered, isolate thus resin particle.Then, resin particle is added in dimethylamino borine 1 % by weight solution 100 weight portions, 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 portions it is disperseed, and has obtained thus suspension.
In addition, prepared the nickel-plating liquid (pH8.5) that comprises nickelous sulfate 0.23mol/L, dimethylamino borine 0.92mol/L, natrium citricum 0.5mol/L and sodium tungstate 0.01mol/L.
When stirring gained suspension for 60 ℃, above-mentioned nickel-plating liquid is slowly added drop-wise in suspension, carried out process for electroless nickel plating.Then, by suspension is filtered and isolates particle, and wash, be dried, obtained being thus provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 22)
Except concentration of sodium tungstate being changed to 0.12mol/L, operate similarly to Example 21, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 23)
Except concentration of sodium tungstate being changed to 0.23mol/L, operate similarly to Example 21, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 24)
Except concentration of sodium tungstate being changed to 0.35mol/L, operate similarly to Example 21, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 25)
Except dimethylamino borane concentration being changed to 2.76mol/L and concentration of sodium tungstate being changed to 0.35mol/L, operate similarly to Example 21, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 26)
(1) palladium adheres to operation
Having prepared particle diameter is the divinylbenzene resin particle (ponding chemical industrial company system " Micropearl SP-205 ") of 5.0 μ m.This resin particle has been carried out to etching, washing.Then, resin particle added in the palladium catalyst liquid 100mL that comprises 8 % by weight palladium catalysts and stir.Then, filter, wash.Resin particle is added in the 0.5 % by weight dimethylamino borine liquid of pH6, obtained being attached with the resin particle of palladium.
(2) core material adheres to operation
The resin particle that is attached with palladium is stirred 3 minutes in ion exchange water 300mL, it is disperseed, obtained dispersion liquid.Then, metallic nickel particle slurry (average grain diameter 100nm) 1g was added in above-mentioned dispersion liquid through 3 minutes, obtained being attached with the resin particle of core material.
(3) process for electroless nickel plating operation
Operate similarly to Example 21, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 27)
Except concentration of sodium tungstate being changed to 0.35mol/L, operate similarly to Example 26, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 28)
(1) making of insulating properties particle
In the detachable flask of 1000mL of the separable lid of four-hole, paddle, triple valve, condenser pipe and temp probe is installed, 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 that makes this monomer composition is 5 % by weight, then, with 200rpm, stir, and carried out polymerization in 24 hours in nitrogen atmosphere, at 70 ℃.After reaction finishes, carry out freeze drying, obtained the surperficial insulating properties particle with ammonium, average grain diameter 220nm and CV value 10%.
Under ultrasonic irradiation, make insulating properties particle be scattered in ion exchange water, obtained 10 % by weight aqueous dispersions of insulating properties particle.
The electroconductive particle 10g obtaining in embodiment 26 is scattered in ion exchange water 500mL, adds the aqueous dispersions 4g of insulating properties particle, under room temperature, carried out stirring for 6 hours.After utilizing the granular membrane of 3 μ m to filter, then wash with methyl alcohol, dry, obtained being attached with the electroconductive particle of insulating properties particle.
Utilize scanning electron microscopy (SEM) to observe following result: on the surface of electroconductive particle, only to form 1 layer of coating layer that comes from insulating properties particle.By image analysis, the coated area of the insulating properties particle of the area with respect to apart from electroconductive particle center 2.5 μ m (being the particle diameter projected area of insulating properties particle) is calculated, result, clad ratio is 30%.
(embodiment 29)
Except concentration of sodium tungstate being changed to 0.46mol/L, operate similarly to Example 21, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(embodiment 30)
Except dimethylamino borane concentration being changed to 4.60mol/L and concentration of sodium tungstate being changed to 0.23mol/L, operate similarly to Example 21, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-tungsten conductive layer (thick 0.1 μ m).
(comparative example 4)
Except the dimethylamino borine 0.92mol/L in nickel-plating liquid being changed to sodium hypophosphite 0.5mol/L, operate similarly to Example 21, obtained being provided with on the surface of resin particle the electroconductive particle of the conductive layer (thick 0.1 μ m) that comprises nickel, tungsten and phosphorus.In whole 100 % by weight of conductive layer, 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, obtained being provided with on the surface of resin particle the electroconductive particle of the conductive layer (thick 0.1 μ m) that comprises nickel and boron.
(embodiment 31)
Having prepared particle diameter is the divinyl benzene copolymer resin particle (ponding chemical industrial company system " Micropearl SP-203 ") of 3.0 μ m.
Utilize ultrasonic disperser that above-mentioned resin particle 10 weight portions are dispersed in aqueous slkali 100 weight portions that comprise 5 % by weight palladium catalyst liquid, then solution is filtered, isolate thus resin particle.Then, resin particle is added in dimethylamino borine 1 % by weight solution 100 weight portions, 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 portions it is disperseed, and has obtained thus suspension.
In addition, prepared the nickel-plating liquid (pH8.5) that comprises nickelous sulfate 0.23mol/L, dimethylamino borine 0.92mol/L, natrium citricum 0.5mol/L and sodium molybdate 0.01mol/L.
When stirring gained suspension for 60 ℃, above-mentioned nickel-plating liquid is slowly added drop-wise in suspension, carried out process for electroless nickel plating.Then, by suspension is filtered and isolates particle, and wash, be dried, obtained being thus provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 32)
Except sodium molybdate concentration being changed to 0.12mol/L, similarly operate with embodiment 31, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 33)
Except sodium molybdate concentration being changed to 0.23mol/L, similarly operate with embodiment 31, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 34)
Except sodium molybdate concentration being changed to 0.35mol/L, similarly operate with embodiment 31, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 35)
Except dimethylamino borane concentration being changed to 2.76mol/L and sodium molybdate concentration being changed to 0.35mol/L, similarly operate with embodiment 31, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 36)
(1) palladium adheres to operation
Having prepared particle diameter is the divinylbenzene resin particle (ponding chemical industrial company system " Micropearl SP-205 ") of 5.0 μ m.This resin particle has been carried out to etching, washing.Then, resin particle added in the palladium catalyst liquid 100mL that comprises 8 % by weight palladium catalysts and stir.Then, filter, wash.Resin particle is added in the 0.5 % by weight dimethylamino borine liquid of pH6, obtained being attached with the resin particle of palladium.
(2) core material adheres to operation
The resin particle that is attached with palladium is stirred 3 minutes in ion exchange water 300mL, it is disperseed, obtained dispersion liquid.Then, metallic nickel particle slurry (average grain diameter 100nm) 1g was added in above-mentioned dispersion liquid through 3 minutes, obtained being attached with the resin particle of core material.
(3) process for electroless nickel plating operation
Similarly operate with embodiment 31, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 37)
Except sodium molybdate concentration being changed to 0.35mol/L, similarly operate with embodiment 36, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 38)
(1) making of insulating properties particle
In the detachable flask of 1000mL of the separable lid of four-hole, paddle, triple valve, condenser pipe and temp probe is installed, 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 that makes this monomer composition is 5 % by weight, then, with 200rpm, stir, and carried out polymerization in 24 hours in nitrogen atmosphere, at 70 ℃.After reaction finishes, carry out freeze drying, obtained the surperficial insulating properties particle with ammonium, average grain diameter 220nm and CV value 10%.
Under ultrasonic irradiation, make insulating properties particle be scattered in ion exchange water, obtained 10 % by weight aqueous dispersions of insulating properties particle.
The electroconductive particle 10g obtaining in embodiment 36 is scattered in ion exchange water 500mL, adds the aqueous dispersions 4g of insulating properties particle, under room temperature, carried out stirring for 6 hours.After utilizing the granular membrane of 3 μ m to filter, then wash with methyl alcohol, dry, obtained being attached with the electroconductive particle of insulating properties particle.
Utilize scanning electron microscopy (SEM) to observe following result: on the surface of electroconductive particle, only to form 1 layer of coating layer that comes from insulating properties particle.By image analysis, the coated area of the insulating properties particle of the area with respect to apart from electroconductive particle center 2.5 μ m (being the particle diameter projected area of insulating properties particle) is calculated, result, clad ratio is 30%.
(embodiment 39)
Except sodium molybdate concentration being changed to 0.46mol/L, similarly operate with embodiment 31, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(embodiment 40)
Except dimethylamino borane concentration being changed to 4.60mol/L and sodium molybdate concentration being changed to 0.23mol/L, similarly operate with embodiment 31, obtained being provided with on the surface of resin particle the electroconductive particle of nickel-boron-molybdenum conductive layer (thick 0.1 μ m).
(comparative example 6)
Except the dimethylamino borine 0.92mol/L in nickel-plating liquid being changed to sodium hypophosphite 0.5mol/L, similarly operate with embodiment 31, obtained being provided with on the surface of resin particle the electroconductive particle of the conductive layer (thick 0.1 μ m) that comprises nickel, molybdenum and phosphorus.In whole 100 % by weight of conductive layer, 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 of electroconductive particle (10%K value)
Use slight compression testing machine (Fischer company system " Fischer Scope H-100 ") to measure the modulus of elasticity in comperssion of gained electroconductive particle (10%K value).
(2) compressive recovery rate of electroconductive particle
Use the compressive recovery rate of slight compression testing machine (Fischer company system " Fischer Scope H-100 ") when gained electroconductive particle is compressed to 30% to measure.
(3) content of nickel, boron, phosphorus, tungsten and the molybdenum in whole 100 % by weight of conductive layer
In the mixed liquor of 60% nitric acid 5mL and 37% hydrochloric acid 10mL, add electroconductive particle 5g, conductive layer is dissolved completely, obtained solution.Use gained solution, utilize ICP-MS analyzer (Hitachi company system) 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
Utilize scanning electron microscope to observe the plating state of 50 of gained electroconductive particles.For plating, break or plating the having or not of plating inequality such as is peeled off and observed.There are 4 following situations to be judged to be " well ", to have 5 above situations to be judged to be " bad " electroconductive particle that confirms plating inequality the electroconductive particle that confirms 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 approximately 800,000) 40 weight portions, methyl ethyl ketone 200 weight portions, microcapsule-type curing agent (Asahi Kasei Chemicals company's system " HX3941HP ") 50 weight portions and silane coupler (Dow Coring Toray company's system " SH6040 ") 2 weight portions are mixed, add electroconductive particle and make its content reach 3 % by weight, disperse, obtained anisotropic conductive material.
Gained anisotropic conductive material is preserved 72 hours at 25 ℃.After preservation, for whether having there is the sedimentation of electroconductive particle after cohesion in anisotropic conductive material, evaluate.The situation that the sedimentation of the rear electroconductive particle of cohesion does not occur is judged to be to " well ", the situation that the sedimentation of electroconductive particle after cohesion has occurred is judged to be to " bad ".
(6) contact resistance at initial stage
The making of syndeton body:
Bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " Epikote1009 ") 10 weight portions, acrylic rubber (weight average molecular weight approximately 800,000) 40 weight portions, methyl ethyl ketone 200 weight portions, microcapsule-type curing agent (Asahi Kasei Chemicals company's system " HX3941HP ") 50 weight portions and silane coupler (Dow Coring Toray company's system " SH6040 ") 2 weight portions are mixed, add electroconductive particle and make its content reach 3 % by weight, disperse, obtained resin combination.
Gained resin combination is coated to PET (PETG) film that one side has passed through the thick 50 μ m that the demoulding processes, utilize the heated-air drying 5 minutes of 70 ℃, made anisotropic conductive film.The thickness of gained anisotropic conductive film is 12 μ m.
Gained anisotropic conductive film is cut into the size of 5mm * 5mm.By cutting the anisotropic conductive film obtaining, be fitted in and there is a side and there is the substantial middle of aluminium electrode side of the glass substrate (wide 3cm, long 3cm) of the aluminium electrode (high 0.2 μ m, L/S=20 μ m/20 μ m) of lead-in wire for resistance measurement.Then, will have identical aluminium electrode two-layer flexible printed base plate (wide 2cm, long 1cm) so that the mode overlapping each other between electrode after positioning, fit.Under the pressing condition in 10N, 180 ℃ and 20 seconds, the laminated body of this glass substrate and two-layer flexible printed base plate is carried out to hot pressing, obtained syndeton body.Wherein, used the two-layer flexible printed base plate that is directly formed with aluminium electrode on polyimide film.
The mensuration of contact resistance:
Utilize four-terminal method to measure the relative interelectrode contact resistance of gained syndeton body.In addition, according to following standard, the contact resistance at initial stage is judged.
[criterion of contact resistance]
00: contact resistance is below 2.0 Ω
Zero: contact resistance surpasses 2.0 Ω and is below 3.0 Ω
△: contact resistance surpasses 3.0 Ω and is below 4.0 Ω
△ △: contact resistance surpasses 4.0 Ω and is below 5.0 Ω
*: contact resistance surpasses 5.0 Ω
(7) contact resistance after high temperature and humidity test
The syndeton body obtaining in making at above-mentioned (6) syndeton body has been placed 100 hours under the condition of 85 ℃ and humidity 85%.Utilize four-terminal method to measure the interelectrode contact resistance of the syndeton body after placing, and using gained measured value the contact resistance after high temperature and humidity test.In addition, according to following standard, the contact resistance after to high temperature and humidity test is judged.
[criterion of contact resistance]
00: contact resistance is below 2.0 Ω
Zero: contact resistance surpasses 2.0 Ω and is below 3.0 Ω
△: contact resistance surpasses 3.0 Ω and is below 4.0 Ω
△ △: contact resistance surpasses 4.0 Ω and is below 5.0 Ω
*: contact resistance surpasses 5.0 Ω
(8) resistance to impact
The syndeton body obtaining in the making of above-mentioned (6) syndeton body is fallen from the position of high 70cm, by confirmation conducting, resistance to impact is evaluated.By the resistance value climbing with respect to initial stage resistance value, be that situation below 50% is judged to be " well ", the resistance value climbing with respect to initial stage resistance value is surpassed to 50% situation is judged to be " bad ".
(9) have or not formation impression
Use differential interference microscope, the glass substrate side of the syndeton body obtaining from the making at above-mentioned (6) syndeton body is observed the electrode being arranged on glass substrate, and on electrode electroconductive particle being contacted according to following standard, has or not formation impression to judge.It should be noted that, about having or not formation impression on electrode, so that electrode area is 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, calculated the every 0.02mm of electrode 2on the mean value of impression number.
[having or not the criterion that forms impression]
00: the every 0.02mm of electrode 2on impression be more than 25
Zero: the every 0.02mm of electrode 2on impression be 20 above and be less than 25
△: the every 0.02mm of electrode 2on impression be 5 above and be less than 20
*: the every 0.02mm of electrode 2on impression be 1 above and be less than 5
The every 0.02mm of * *: electrode 2on impression be 0
Result is as shown in following table 3,4.
Figure BDA0000453941260000451
Figure BDA0000453941260000461

Claims (14)

1. an electroconductive particle, it has:
Basis material particle; With
Conductive layer, this conductive layer is arranged on the surface of described basis material particle, and comprises at least one metal ingredient in tungsten and molybdenum and nickel, boron.
2. electroconductive particle according to claim 1, wherein, in whole 100 % by weight of described conductive layer, the content of described boron is that 0.05 % by weight is above and below 4 % by weight.
3. electroconductive particle according to claim 1 and 2, wherein, in whole 100 % by weight of described conductive layer, the content of described metal ingredient is that 0.1 % by weight is above and below 30 % by weight.
4. electroconductive particle according to claim 1 and 2, wherein, in whole 100 % by weight of described conductive layer, the content of described metal ingredient is greater than 5 % by weight and below 30 % by weight.
5. according to the electroconductive particle described in any one in claim 1～4, wherein, described metal ingredient comprises tungsten.
6. according to the electroconductive particle described in any one in claim 1～5, its modulus of elasticity in comperssion when compression 10% is 5000N/mm 2above and 15000N/mm 2below.
7. according to the electroconductive particle described in any one in claim 1～6, its compressive recovery rate is more than 5% and below 70%.
8. according to the electroconductive particle described in any one in claim 1～7, wherein, described metal ingredient comprises molybdenum.
9. according to the electroconductive particle described in any one in claim 1～8, wherein,
Described conductive layer comprises nickel and molybdenum,
In whole 100 % by weight of described conductive layer, the content of nickel is that 70 % by weight are above and 99.9 % by weight are following, content molybdenum is more than 0.1 % by weight and below 30 % by weight.
10. according to the electroconductive particle described in any one in claim 1～9, its modulus of elasticity in comperssion compressed 5% time is 7000N/mm 2above, and, electroconductive particle on compression direction, take be greater than electroconductive particle before compression particle diameter 10% and when compressing particle diameter compressed below 25% of front electroconductive particle, described conductive layer breaks.
11. according to the electroconductive particle described in any one in claim 1～10, and wherein, the thickness of described conductive layer is more than 0.05 μ m and below 0.5 μ m.
12. according to the electroconductive particle described in any one in claim 1～11, and wherein, the outer surface of described conductive layer has projection.
13. 1 kinds of electric conducting materials, it comprises the electroconductive particle described in any one in adhesive resin and claim 1～12.
14. 1 kinds of syndeton bodies, it possesses the 1st connecting object parts, the 2nd connecting object parts and connects connecting portions described the 1st, the 2nd connecting object parts,
Described connecting portion is formed by the electroconductive particle described in any one in claim 1～12 or is formed by the electric conducting material that comprises described electroconductive particle and adhesive resin.
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KR20210114596A (en) * 2020-03-10 2021-09-24 삼성디스플레이 주식회사 Display device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002075057A (en) * 2000-08-30 2002-03-15 Mitsui Mining & Smelting Co Ltd Coated copper powder
CN1737072A (en) * 2004-08-18 2006-02-22 播磨化成株式会社 Conductive adhesive agent and process for manufacturing article using the conductive adhesive agent
CN1906705A (en) * 2004-01-30 2007-01-31 积水化学工业株式会社 Conductive fine particle and anisotropic conductive material
JP2008041671A (en) * 2007-09-07 2008-02-21 Sekisui Chem Co Ltd Manufacturing method of conductive particulate
CN101724361A (en) * 2008-12-30 2010-06-09 四川虹欧显示器件有限公司 Aeolotropic conductive adhesive and conductive film and electric connection method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3696429B2 (en) 1999-02-22 2005-09-21 日本化学工業株式会社 Conductive electroless plating powder, method for producing the same, and conductive material comprising the plating powder
JP2003313304A (en) 2002-04-22 2003-11-06 Sekisui Chem Co Ltd Conductive fine particle, its manufacturing method and bonding material for electronic component
KR101626266B1 (en) * 2011-07-28 2016-05-31 세키스이가가쿠 고교가부시키가이샤 Conductive particles, conductive material and connection structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002075057A (en) * 2000-08-30 2002-03-15 Mitsui Mining & Smelting Co Ltd Coated copper powder
CN1906705A (en) * 2004-01-30 2007-01-31 积水化学工业株式会社 Conductive fine particle and anisotropic conductive material
CN1737072A (en) * 2004-08-18 2006-02-22 播磨化成株式会社 Conductive adhesive agent and process for manufacturing article using the conductive adhesive agent
JP2008041671A (en) * 2007-09-07 2008-02-21 Sekisui Chem Co Ltd Manufacturing method of conductive particulate
CN101724361A (en) * 2008-12-30 2010-06-09 四川虹欧显示器件有限公司 Aeolotropic conductive adhesive and conductive film and electric connection method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106233396A (en) * 2014-05-12 2016-12-14 积水化学工业株式会社 Electroconductive particle, conductive material and connection structural bodies
CN106233396B (en) * 2014-05-12 2018-05-04 积水化学工业株式会社 Electroconductive particle, conductive material and connection structural bodies
CN104117685A (en) * 2014-07-30 2014-10-29 金堆城钼业股份有限公司 Method for preparing sodium molybdate doped molybdenum powder
CN108780677A (en) * 2016-05-19 2018-11-09 积水化学工业株式会社 Electroconductive particle, conductive material and connection structural bodies
CN111886657A (en) * 2018-03-30 2020-11-03 迪睿合株式会社 Conductive material and method for producing connector
CN111383793A (en) * 2018-12-31 2020-07-07 德山金属株式会社 Conductive particle, conductive material, and contact structure
CN111383793B (en) * 2018-12-31 2021-10-26 德山金属株式会社 Conductive particle, conductive material, and contact structure

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