CN104395967B - The electroconductive particle of tape insulation particle, conductive material and connection structural bodies - Google Patents

The electroconductive particle of tape insulation particle, conductive material and connection structural bodies Download PDF

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Publication number
CN104395967B
CN104395967B CN201380032491.1A CN201380032491A CN104395967B CN 104395967 B CN104395967 B CN 104395967B CN 201380032491 A CN201380032491 A CN 201380032491A CN 104395967 B CN104395967 B CN 104395967B
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particle
insulating properties
electroconductive
electroconductive particle
mentioned
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CN104395967A (en
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真原茂雄
上田沙织
上野山伸也
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Non-Insulated Conductors (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Powder Metallurgy (AREA)

Abstract

In the case that the present invention provides a kind between connection electrode, it is possible to increase the electroconductive particle of the tape insulation particle of both conducting reliability and insulating reliability.The electroconductive particle (1) of tape insulation particle of the invention possesses at least surface and has second insulating properties particle (4) of the first insulating properties particle (3), multiple configurations of the electroconductive particle (2), multiple configurations of conductive part (12) on electroconductive particle (2) surface on electroconductive particle (2) surface.Average grain diameter of the average grain diameter of the second insulating properties particle (4) less than the first insulating properties particle (3).The total area of the part coated by the first insulating properties particle (2) and the second insulating properties particle (4) accounts for the clad ratio of the total surface area of electroconductive particle (2) more than 50%.

Description

The electroconductive particle of tape insulation particle, conductive material and connection structural bodies
Technical field
The present invention relates to a kind of electroconductive particle of the tape insulation particle electrically connected between for example can be used for electrode.In addition, this Invention is related to the conductive material of a kind of electroconductive particle for having used above-mentioned tape insulation particle and connection structural bodies.
Background technology
It is known to the anisotropic conductive materials such as anisotropic conductive cream and anisotropic conductive film.With regard to these anisotropy For conductive material, electroconductive particle is dispersed with adhesive resin.
Above-mentioned anisotropic conductive material can be used for connection of the IC chip with flexible printed circuit substrate and IC chip and tool There is connection of the circuit substrate of ITO electrode etc..For example, anisotropic conductive material is configured into the electrode and circuit base in IC chip After between the electrode of plate, it is heated and is pressurizeed, thus these electrodes can be electrically connected.
As an example of above-mentioned electroconductive particle, in following patent documents 1, a kind of tape insulation particle is disclosed Electroconductive particle：Its particle for possessing conductive gold metal surface and the surface to above-mentioned conductive metal surface particle are entered The insulating properties particle of row cladding.Recorded in patent document 1：The insulating properties grain different by being applied in combination two or more particle diameter Son, so that during small insulating properties particle enters and carries out the gap for coating by big insulating properties particle, cladding density is improved.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-44773 publications
The content of the invention
Problems to be solved by the invention
In the electroconductive particle of the tape insulation particle described in patent document 1, the metal surface of electric conductivity is by insulating Property particle cladding, therefore, after upper and lower being conductively connected is carried out, can be to not attachable transversely adjacent interelectrode electricity Connection is suppressed.I.e., it is possible to improve the insulating reliability in the connection structural bodies being conductively connected.In addition, combination makes With the different insulating properties particle of two or more particle diameter, small insulating properties particle is set to enter the gap coated by big insulating properties particle In, thus coat density and be improved, as a result can improve insulating reliability.But, in patent document 1, only record excellent The clad ratio of insulating properties particle is set to 5~50% by choosing, and the area of the part that will be coated by insulating properties particle accounts for metal surface The surface area of particle is integrally set to 5~50%.
On the other hand, in recent years, the direction of the positive miniaturization of electronic unit is developed.Therefore, in electronic unit by leading In the distribution of conductive particles connection, the width in the width for representing the line (L) of the distribution for foring and the space (S) for not forming distribution L/S diminish.In the case where so fine distribution is formed with, if being entered using the electroconductive particle of existing tape insulation particle Row is conductively connected, then be difficult to ensure that sufficient insulating reliability.
In addition, in the case where being conductively connected using the electroconductive particle of tape insulation particle, it is desirable to fully right Insulating properties particle between electrode and electroconductive particle is excluded, and also requires that conducting reliability high.
In addition, in the electroconductive particle of existing tape insulation particle, before being conductively connected, insulating properties particle is easily non- Purpose ground departs from from the surface of electroconductive particle.For example, making the electroconductive particle of tape insulation particle be dispersed in adhesive When in resin, insulating properties particle easily departs from from the surface of electroconductive particle sometimes, exposes the surface of electroconductive particle.The knot Really, there is a problem of insulating reliability reduction.
It is an object of the invention to provide a kind in the case of being attached between electrode, conducting reliability can be improved And the tape insulation particle both insulating reliability electroconductive particle and used the electric conductivity of the tape insulation particle The conductive material and connection structural bodies of particle.
Even if limited purpose of the invention is to provide a kind and give before being conductively connected etc. to impact, insulating properties particle The electroconductive particle of the tape insulation particle for departing from from electroconductive particle surface with being difficult to non-purpose and use the band exhausted The conductive material and connection structural bodies of the electroconductive particle of edge particle.
The method of solve problem
Wide in range aspect of the invention, there is provided a kind of electroconductive particle with insulating properties particle, it has：At least Surface has the electroconductive particle of conductive part, multiple first insulating properties particles of the configuration on the electroconductive particle surface, matches somebody with somebody The multiple second insulating properties particles on the electroconductive particle surface are put, the average grain diameter of the second insulating properties particle is less than The average grain diameter of the first insulating properties particle, the portion coated by the first insulating properties particle and the second insulating properties particle The gross area for dividing accounts for the clad ratio of the electroconductive particle total surface area more than 50%.
In certain particular aspects of the electroconductive particle of tape insulation particle of the invention, the second insulating properties particle Total number in more than 20% configured in the electroconductive particle in the way of being in contact with the first insulating properties particle On surface.
In certain particular aspects of the electroconductive particle of tape insulation particle of the invention, the second insulating properties particle Total number in more than 50% configured in the electroconductive particle in the way of being in contact with the first insulating properties particle On surface.
In certain particular aspects of the electroconductive particle of tape insulation particle of the invention, the second insulating properties particle Total number in more than 10% configured in the way of not contacting the first insulating properties particle but contacting the electroconductive particle On the surface of the electroconductive particle.
In certain particular aspects of the electroconductive particle of tape insulation particle of the invention, the first insulating properties particle The surface of the electroconductive particle is attached to via chemical bond.
In certain particular aspects of the electroconductive particle of tape insulation particle of the invention, the first insulating properties particle And the second insulating properties particle is not to be configured on the electroconductive particle surface by blending together method.
In certain particular aspects of the electroconductive particle of tape insulation particle of the invention, the electroconductive particle is in institute The outer surface for stating conductive part has projection.
Wide in range aspect of the invention, there is provided a kind of conductive material, it contains the above-mentioned conduction with insulating properties particle Property particle and adhesive resin.
Wide in range aspect of the invention, a kind of connection structural bodies, it has：
Surface have first electrode the first connecting object part,
Surface have second electrode the second connecting object part,
The connecting portion of the first connecting object part and the second connecting object part is connected, the connecting portion is by upper The electroconductive particle with insulating properties particle is stated to be formed, or by containing the electroconductive particle with insulating properties particle and bonding The conductive material of agent resin is formed, and the first electrode and the second electrode are by the electric conductivity with insulating properties particle The electroconductive particle in particle realizes electrical connection.
The effect of invention
The electroconductive particle of tape insulation particle of the invention possesses at least surface and has the electroconductive particle of conductive part, matches somebody with somebody Put second of the multiple first insulating properties particles, configuration on the electroconductive particle surface on the electroconductive particle surface Insulating properties particle, and then, the average grain diameter of the average grain diameter less than the first insulating properties particle of the second insulating properties particle, It is total that the gross area of the part coated by the first insulating properties particle and the second insulating properties particle accounts for the electroconductive particle The clad ratio of surface area more than 50%, therefore, using the electroconductive particle of tape insulation particle of the invention entering between electrode In the case of row connection, conducting reliability and insulating reliability can be improved.
Brief description of the drawings
Fig. 1 is the profile of the electroconductive particle for showing tape insulation particle in first embodiment of the invention；
Fig. 2 is the profile of the electroconductive particle for showing tape insulation particle in second embodiment of the present invention；
Fig. 3 is the profile of the electroconductive particle for showing tape insulation particle in third embodiment of the present invention；
Fig. 4 is the connection structural bodies for schematically illustrating the electroconductive particle for having used the tape insulation particle shown in Fig. 1 Front cross-sectional view；
Fig. 5 is the schematic diagram illustrated for the evaluation method to clad ratio.
Description of symbols
The electroconductive particle of 1 tape insulation particle
2 electroconductive particles
3 first insulating properties particles
4 second insulating properties particles
11 substrate particles
12 conductive parts
The electroconductive particle of 21 tape insulation particles
22 electroconductive particles
26 conductive parts
27 core materials
28 is raised
The electroconductive particle of 31 tape insulation particles
32 electroconductive particles
36 conductive parts
37 is raised
81 connection structural bodies
82 first connecting object parts
82a first electrodes
83 second connecting object parts
83a second electrodes
84 connecting portions
Specific embodiment
Below, on one side referring to the drawings, while being illustrated come bright by specific embodiment of the invention and embodiment It is really of the invention.
(electroconductive particle of tape insulation particle)
Table is carried out to the electroconductive particle of tape insulation particle in first embodiment of the invention with profile in Fig. 1 Show.
The electroconductive particle 1 of the tape insulation particle shown in Fig. 1 possesses electroconductive particle 2, multiple first insulating properties particles 3rd, multiple second insulating properties particles 4.
Electroconductive particle 2 at least has conductive part 12 on surface.First insulating properties particle 3 is configured in electroconductive particle 2 On surface.Second insulating properties particle 4 is configured on the surface of electroconductive particle 2.
It is total that the total area of the part coated by the first insulating properties particle 3 and the second insulating properties particle 4 accounts for electroconductive particle 2 The clad ratio of surface area is more than 50%.
Multiple first insulating properties particles 3 are contacted with the surface of electroconductive particle 2, are attached to the surface of electroconductive particle 2.It is many Individual first insulating properties particle 3 is contacted with the outer surface of the conductive part 12 of electroconductive particle 2, is attached to the outer surface of conductive part 12. Multiple second insulating properties particles 4 are contacted with the surface of electroconductive particle 2, are attached to the surface of electroconductive particle 2.Multiple second is exhausted Edge particle 4 is contacted with the outer surface of the conductive part 12 of electroconductive particle 2, is attached to the outer surface of conductive part 12.
Electroconductive particle 2 has the conductive part 12 of substrate particle 11, configuration on the surface of substrate particle 11.Conductive part 12 It is conductive layer.Conductive part 12 covers the surface of substrate particle 11.Electroconductive particle 2 is the surface of substrate particle 11 by conductive part 12 The coating particles of cladding.Electroconductive particle 2 has conductive part 12 on surface.
First insulating properties particle 3 and the second insulating properties particle 4 are formed by the material with insulating properties respectively.Second insulating properties Average grain diameter of the average grain diameter of particle 4 less than the first insulating properties particle 3.
Table is carried out to the electroconductive particle of tape insulation particle in second embodiment of the present invention with profile in Fig. 2 Show.
The electroconductive particle 21 of the tape insulation particle shown in Fig. 2 possesses electroconductive particle 22, multiple first insulating properties grain Son 3, multiple second insulating properties particles 4.
Electroconductive particle 22 at least has conductive part 26 on surface.First insulating properties particle 3 is configured in electroconductive particle 22 Surface on.Second insulating properties particle 4 is configured on the surface of electroconductive particle 22.
The gross area of the part coated by the first insulating properties particle 3 and the second insulating properties particle 4 accounts for electroconductive particle 22 The clad ratio of whole surface area is more than 50%.
For the electroconductive particle 1 of tape insulation particle and the electroconductive particle 21 of tape insulation particle, only electric conductivity Particle 2,22 is different.Electroconductive particle 22 has the conductive part 26 of substrate particle 11, configuration on the surface of substrate particle 11.It is conductive Property particle 22 there are multiple core materials 27 on the surface of substrate particle 11.Conductive part 26 coats substrate particle 11 and core material 27.Conductive part 26 coats core material 27, thus has multiple raised 28 on the surface of electroconductive particle 22.Because core material 27 makes to lead The surface elevation in electric portion 26, is formed with multiple raised 28.
Table is carried out to the electroconductive particle of the tape insulation particle of third embodiment of the present invention with profile in Fig. 3 Show.
The electroconductive particle 31 of the tape insulation particle shown in Fig. 3 possesses electroconductive particle 32, multiple first insulating properties grain Son 3, multiple second insulating properties particles 4.
Electroconductive particle 32 at least has conductive part 36 on surface.First insulating properties particle 3 is configured in electroconductive particle 32 Surface on.Second insulating properties particle 4 is configured on the surface of electroconductive particle 32.
The total area of the part coated by the first insulating properties particle 3 and the second insulating properties particle 4 accounts for electroconductive particle 32 Total surface area clad ratio more than 50%.
For the electroconductive particle 1 of tape insulation particle and the electroconductive particle 31 of tape insulation particle, only electric conductivity Particle 2,32 is different.Electroconductive particle 32 has the conductive part 36 of substrate particle 11, configuration on the surface of substrate particle 11.Lead Conductive particles 22 have core material 27, but electroconductive particle 32 does not have core material.Conductive part 36 has Part I, thickness ratio The thick Part II of the Part I.Electroconductive particle 32 has multiple raised 37 on surface.Portion in addition to multiple raised 37 It is divided into the above-mentioned Part I of conductive part 36.Multiple raised 37 is the thicker above-mentioned Part II of the thickness of conductive part 36.
The electroconductive particle 1,21,31 of tape insulation particle is called the turn any one, the average grain of the second insulating properties particle 4 Average grain diameter of the footpath than the first insulating properties particle 3 is small, the portion coated by the first insulating properties particle 3 and the second insulating properties particle 4 The total area for dividing accounts for the total surface area i.e. clad ratio of electroconductive particle 2,22,32 more than 50%.Therefore, if using tape insulation Be electrically connected between 1,21,31 upper/lower electrodes of electroconductive particle of property particle, then can be entering between the upper/lower electrode that should be connected Row electrical connection, electrically connects between may also suppress not attachable transversely adjacent electrode.I.e., it is possible to improve conducting reliability and absolutely Edge reliability.It should be noted that generally, when being conductively connected, to the first insulating properties particle 3, the second insulating properties particle 4 Disengaging assign influence larger power, as a result, the first insulating properties particle 3, the second insulating properties particle 4 depart from, expose Electroconductive particle 2,22,32 and electrode contact.
And then, it is also possible to effectively prevent the first larger insulating properties particle before being conductively connected due to impact rather than purpose Property ground from electroconductive particle surface depart from.For example, can suppress make the electroconductive particle of tape insulation particle be dispersed in adhesive When in resin, the first insulating properties particle departs from from the surface of electroconductive particle.And then, in the electric conductivity of multiple tape insulation particles During particle contact, the impact that the first insulating properties particle is not easy to during because of contact departs from from the surface of electroconductive particle.In addition, passing through Connection structural bodies is obtained being electrically connected between upper/lower electrode using the electroconductive particle of tape insulation particle, even if being tied to connection Structure body applies impact, departs from can also suppressing the non-purpose of the first insulating properties particle, therefore, occur between adjacent electrode can be suppressed Electrical connection, it can be ensured that sufficient insulating reliability.
From the viewpoint of insulating reliability from further raising insulating reliability and for impact, insulated by above-mentioned first Property particle and above-mentioned second insulating properties particle cladding part total area account for above-mentioned electroconductive particle total surface area bag The rate Z of covering is preferably more than 51%, more preferably more than 55%, more preferably more than 60%, particularly preferably more than 70%, Most preferably more than 80%.It is above-mentioned from the viewpoint of insulating reliability from further raising insulating reliability and for impact Clad ratio Z is preferably less than 85%.Above-mentioned clad ratio Z can be less than 81%, or less than 80%.
The total area of the part coated by above-mentioned first insulating properties particle and above-mentioned second insulating properties particle accounts for above-mentioned leading The total surface area of conductive particles is that clad ratio is as described below to be obtained.
20 electroconductive particles of tape insulation particle are observed using scanning electron microscope (SEM), tape insulation is obtained The clad ratio Z (%) (also referred to as adhesive rate Z (%)) of the electroconductive particle in the electroconductive particle of property particle.Above-mentioned clad ratio is The total area (projected area) of the part coated by the first insulating properties particle, the second insulating properties particle accounts for the table of electroconductive particle The ratio of area.
Specifically, above-mentioned clad ratio refer to scanning electron microscope (SEM) from a direction to tape insulation In the case that the electroconductive particle of particle is observed, the first insulating properties in the circle of the outer peripheral edge portion on electroconductive particle surface Particle, the total area (oblique line portion of Fig. 5 (b)) of the second insulating properties particle account for leading for the tape insulation particle observed in image The gross area of (oblique line portion of Fig. 5 (a)) in the circle of the outer peripheral edge portion on the electroconductive particle surface of conductive particles.
From the viewpoint of insulating reliability from further raising conducting reliability, insulating reliability and for impact, on State the second insulating properties particle average grain diameter be preferably above-mentioned first insulating properties particle average grain diameter less than 9/10, more preferably It is less than 4/5, more preferably less than 2/3, particularly preferably less than 1/2.The average grain diameter of above-mentioned second insulating properties particle More than the 1/30 of the average grain diameter of preferably above-mentioned first insulating properties particle, more preferably more than 1/20, more preferably 1/ More than 10.
Above-mentioned first insulating properties particle, " average grain diameter " of the second insulating properties particle represent number average bead diameter respectively.Above-mentioned One insulating properties particle, the second insulating properties particle average grain diameter it is arbitrary by using electron microscope or observation by light microscope Electroconductive particle 50, calculates average value to obtain.
From from the viewpoint of further improving conducting reliability, at least a portion in preferably the second insulating properties particle is connecing The mode for touching the first insulating properties particle is configured on the surface of electroconductive particle.Examined from the viewpoint for further improving conducting reliability Consider, the number of the second insulating properties particle on electroconductive particle surface is preferably configured in the way of the first insulating properties particle of contact It is more.From further improve conducting reliability from the viewpoint of, preferably in the total number of the second insulating properties particle 10% with On by contact the first insulating properties particle in the way of configure on the surface of electroconductive particle.To contact the side of the first insulating properties particle The ratio X1 that formula configures the number of the second insulating properties particle on electroconductive particle surface is more preferably more than 20%, more excellent Elect more than 30%, more preferably more than 40% as, be still more preferably more than 50%, particularly preferably more than 50%, most Preferably greater than 80%.If the second insulating properties particle and the first insulating properties particle contact, when being conductively connected, with first The disengaging of insulating properties particle, the second insulating properties particle with the first insulating properties particle contact is also easily separated from.The result, conducting can It is further enhanced by property.It should be noted that the total number of the second insulating properties particle represents that each electroconductive particle has The number of the second insulating properties particle having.In addition, being configured on electroconductive particle surface in the way of to contact the first insulating properties particle On the second insulating properties particle number include the number of the second insulating properties particle contacted with electroconductive particle and not with lead Both numbers of the second insulating properties particle of conductive particles contact.
Method as the second insulating properties particle and the first insulating properties particle contact is made, can enumerate：To the first insulating properties Particle is surface-treated so that the method that the second insulating properties particle becomes easy attachment；Table is carried out to the second insulating properties particle Face is processed so that the method that the first insulating properties particle becomes easy attachment；And the second insulating properties particle is attached to first exhausted Behind the surface of edge particle, the first insulating properties particle for being attached with the second insulating properties particle is set to be attached to the surface of electroconductive particle Method etc..
From the viewpoint of insulating reliability from further raising insulating reliability and for impact, preferably the second insulating properties At least a portion in particle not contact the first insulating properties particle in the way of configure on the surface of electroconductive particle.From entering one Step improve insulating reliability and for the insulating reliability of impact from the viewpoint of, preferably not contacting the first insulating properties particle The number that mode configures the second insulating properties particle on electroconductive particle surface is more.It is preferred that total of the second insulating properties particle In number more than 10% not contact the first insulating properties particle in the way of configure on the surface of electroconductive particle.Not contact The mode of one insulating properties particle configures the ratio X2 of the number of the second insulating properties particle on electroconductive particle surface more preferably It is more than 20%, more preferably more than 30%, particularly preferably more than 40%, most preferably more than 50%.Need explanation , the total number of the second insulating properties particle represents the number of the second insulating properties particle that each electroconductive particle has.Separately Outward, not contact the first insulating properties particle in the way of configure the number bag of the second insulating properties particle on electroconductive particle surface The the second insulating properties particle for including the number of the second insulating properties particle contacted with electroconductive particle and not contacted with electroconductive particle Number both.
In order to improve insulating reliability and the insulating reliability for impact, preferably in the total number of the second insulating properties particle More than 10% by do not contact the first insulating properties particle and contact electroconductive particle in the way of configure on the surface of electroconductive particle On.Configure second exhausted on electroconductive particle surface in the way of not contact the first insulating properties particle and contact electroconductive particle The ratio X3 of the number of edge particle is more preferably more than 10%, more preferably more than 15%, particularly preferably 20% with On, and preferably less than 100%, more preferably less than 80%, more preferably less than 60%, especially preferably less than 50%. It should be noted that the total number of the second insulating properties particle represents the second insulating properties particle that each electroconductive particle has Number.
As make the second insulating properties particle not with the method for the first insulating properties particle contact, can enumerate：Insulated to first Property particle is surface-treated so that the second insulating properties particle is difficult adherence method；Second insulating properties particle is carried out at surface Reason so that the first insulating properties particle becomes the method for being difficult attachment；Second insulating properties particle is surface-treated so that second Insulating properties particle becomes method for being attached to electroconductive particle easier than the first insulating properties particle etc..
It is excellent from the viewpoint of insulating reliability from further raising conducting reliability, insulating reliability and for impact Select the average of above-mentioned first insulating properties particle of the configuration of each above-mentioned electroconductive particle on above-mentioned electroconductive particle surface Number Y1 be more than one, more preferably more than 2, more preferably more than 3, particularly preferably more than 5, most preferably It is more than 10, and preferably less than 100, more preferably more preferably less than 50, less than 20.Above-mentioned average Number Y1 can be less than 10.The configuration of each above-mentioned electroconductive particle is above-mentioned first exhausted on above-mentioned electroconductive particle surface The mean number of edge particle is the average value of the first insulating properties particle number that each above-mentioned electroconductive particle has.
It is excellent from the viewpoint of insulating reliability from further raising conducting reliability, insulating reliability and for impact Select the average of above-mentioned second insulating properties particle of the configuration of each above-mentioned electroconductive particle on above-mentioned electroconductive particle surface Number Y2 be more than 1, more preferably more than 4, more preferably more than 6, particularly preferably more than 10, most preferably It is more than 20, and preferably less than 1000, more preferably more preferably less than 500, less than 100.On every 1 The mean number for stating above-mentioned second insulating properties particle of the configuration of electroconductive particle on above-mentioned electroconductive particle surface is every 1 The average value of the second insulating properties particle number that above-mentioned electroconductive particle has.
In electroconductive particle of the invention, the configuration of every 1 above-mentioned electroconductive particle is on above-mentioned electroconductive particle surface On above-mentioned first insulating properties particle mean number Y1 and every 1 above-mentioned electroconductive particle configuration in above-mentioned electroconductive particle The ratio (mean number Y1/ mean number Y2) of the mean number Y2 of the above-mentioned second insulating properties particle on surface is preferably 0.001 More than, more preferably more than 0.005, more preferably more than 0.05, and preferably less than 1, more preferably less than 0.5.On Stating can be more than 0.5 than (mean number Y1/ mean number Y2).It should be noted that configuration is on above-mentioned electroconductive particle surface On above-mentioned first insulating properties particle, the second insulating properties particle number also include do not contacted with electroconductive particle above-mentioned first The number of insulating properties particle, the second insulating properties particle.
From the viewpoint of insulating reliability from further raising insulating reliability and for impact, preferably above-mentioned second is exhausted Edge particle is attached to the surface of above-mentioned electroconductive particle via chemical bond.
Departed from from the surface of electroconductive particle due to the non-purpose of impact from further the first insulating properties particle of suppression Viewpoint considers that preferably above-mentioned first insulating properties particle is attached to the surface of above-mentioned electroconductive particle via chemical bond.If in addition, on The surface that the first insulating properties particle is attached to above-mentioned electroconductive particle via chemical bond is stated, then the insulating reliability of connection structural bodies It is further enhanced.
From from the viewpoint of improving interelectrode conducting reliability, preferably above-mentioned electroconductive particle is in the outer of above-mentioned conductive part Surface has projection.Generally, for the outer surface of conductive part has raised electroconductive particle, with the bigger insulation of the projection Reliability gets over the tendency of reduction.It is exhausted due to possessing above-mentioned first for the electroconductive particle of tape insulation particle of the invention Edge particle, the second insulating properties particle, even if therefore it is raised big, also ensure that insulating reliability is abundant.
It is excellent from the viewpoint of insulating reliability from further raising conducting reliability, insulating reliability and for impact Choose state the first insulating properties particle the degree of cross linking be more than 5 weight %.The above-mentioned degree of cross linking refer to crosslinking component weight relative to The ratio of the gross weight of polymerizable monomer.
Below, it is exhausted to the electroconductive particle in the electroconductive particle of tape insulation particle, the first insulating properties particle and second The details of edge particle is illustrated.
[electroconductive particle]
As long as above-mentioned electroconductive particle at least has conductive part on surface.The conductive part is preferably conductive layer.It is conductive Property particle can have substrate particle and conductive layer of the configuration on substrate particle surface, or the generally gold of conductive part Category particle.Wherein, from reduces cost or the viewpoint of the interelectrode conducting reliability of flexible and raising for improving electroconductive particle Consider, preferably the electroconductive particle of the conductive part with substrate particle and configuration on substrate particle surface.
As above-mentioned substrate particle, can enumerate：Resin particle, the inorganic particulate in addition to metallic, organic-inorganic Stuff and other stuff and metallic etc..Above-mentioned substrate particle can be core shell particle.Wherein, above-mentioned substrate particle is preferably except metal Substrate particle beyond particle, more preferably resin particle, the inorganic particulate in addition to metallic or organic-inorganic mangcorn Son.
Above-mentioned substrate particle is preferably the resin particle formed by resin.In the electroconductive particle using tape insulation particle During being attached between electrode, after the electroconductive particle of tape insulation particle is configured between electrode, being pressed, thus being made band The electroconductive particle compression of insulating properties particle.If substrate particle is resin particle, the electroconductive particle when above-mentioned pressing is carried out It is easily deformed, electroconductive particle becomes big with the contact area of electrode.Therefore, interelectrode conducting reliability is further carried It is high.
As the resin for forming above-mentioned resin particle, various organic matters are preferably used.As above-mentioned for being formed The resin of resin particle, for example, can enumerate：Polyethylene, polypropylene, polystyrene, polyvinyl chloride, Vingon, poly- isobutyl The vistanexes such as alkene, polybutadiene；The acrylic resins such as polymethyl methacrylate, PMA；Poly- terephthaldehyde Sour alkylene ester, makrolon, polyamide, phenol formaldehyde resin, melamine resin, benzoguanamine formaldehyde resin, urine Urea formaldehyde, phenolic resin, melmac, benzene birds droppings polyimide resin, carbamide resin, epoxy resin, unsaturated polyester resin, saturation Polyester resin, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone, polyether sulfone and make a kind or 2 Polymer that the polymerization of the various polymerizable monomers with ethylenically unsaturated group more than kind is obtained etc..Due to can easily by base The hardness of material particle is controlled in preferred scope, therefore, the resin for forming above-mentioned resin particle is preferably makes a kind or 2 kinds The polymer that the polymerizable monomer with ethylenically unsaturated group above is polymerized.
In the case where making the polymerization of the monomer with ethylenically unsaturated group obtain above-mentioned resin particle, there is alkene as this Belong to the monomer of unsaturated group, the monomer of non-crosslinked property and the monomer of bridging property can be enumerated.
As the monomer of above-mentioned non-crosslinked property, for example, can enumerate：The phenylethylene list such as styrene, AMS Body；The carboxyl group-containing monomers such as (methyl) acrylic acid, maleic acid, maleic anhydride；(methyl) methyl acrylate, (methyl) acrylic acid second Ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl Ester, (methyl) acrylic acid cetyl, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, the different ice of (methyl) acrylic acid Piece ester etc. (methyl) alkyl-acrylates；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) glycerol acrylate, polyoxyethylene (methyl) acrylate, (methyl) glycidyl acrylate etc. contain oxygen atom (methyl) esters of acrylic acid；(methyl) acrylonitrile Deng containing nitrile monomer；The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether；Vinyl acetate, butyric acid The vinyl acetate class such as vinyl acetate, vinyl laurate, stearic acid vinyl ester；The insatiable hungers such as ethene, propylene, isoprene, butadiene And hydrocarbon；(methyl) acrylic acid trifluoro methyl esters, the fluorine ethyl ester of (methyl) acrylic acid five, vinyl chloride, PVF, chlorostyrene etc. contain halogen Monomer etc..
As the monomer of above-mentioned bridging property, for example, can enumerate：Tetramethylol methane four (methyl) acrylate, four hydroxyl first Methylmethane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) propylene Acid esters, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) propylene acid glycerols Ester, two (methyl) glycerol acrylates, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propane diols two (methyl) acrylic acid Multifunctional (methyl) propylene such as ester, (poly-) tetramethylene two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate Esters of gallic acid；Triallyl (different) cyanurate, triallyltrimelitate, divinylbenzene, diallyl phthalate, diene Propylacrylamide, diallyl ether, γ-(methyl) acryloxypropyl trimethoxy silane, trimethoxysilyl Silane-containing monomer such as styrene, vinyltrimethoxy silane etc..
Known method can be utilized to be obtained by making the above-mentioned polymerizable monomer with ethylenically unsaturated group be polymerized State resin particle.As the method, for example, can enumerate：The side of suspension polymerisation is carried out in the presence of radical polymerization initiator Method and the method that together makes monomer swell with radical polymerization initiator using noncrosslinking kind of particle and be polymerized etc..
In the case where above-mentioned substrate particle is inorganic particulate or organic-inorganic stuff and other stuff in addition to metal, as with In the inorganic matter for forming substrate particle, silica and carbon black etc. can be enumerated.As the particle formed by above-mentioned silica It is not particularly limited, for example, can enumerates：It is hydrolyzed by the silicon compound with the water-disintegrable alkoxy of more than 2 After forming cross-linking polymer particle, the particle obtained by being burnt till as needed.As above-mentioned organic-inorganic stuff and other stuff, example Can such as enumerate：The organic-inorganic stuff and other stuff formed by the alkoxysilyl polymer and acrylic resin of crosslinking Deng.
In the case where above-mentioned substrate particle is metallic, as the metal for forming the metallic, Ke Yiju Go out：Silver, copper, nickel, silicon, gold and titanium etc..However, it is preferred to above-mentioned substrate particle nonmetal particle.
Metal for forming above-mentioned conductive part is not particularly limited.And then, in the generally conductive part of electroconductive particle Metallic in the case of, the metal for forming the metallic is not particularly limited.As the metal, for example, can lift Go out：Gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon and their alloy Deng.In addition, as above-mentioned metal, can enumerate：Tin-doped indium oxide (ITO) and scolding tin etc..Wherein, due to interelectrode connection Resistance is further reduced, therefore preferably comprises alloy, nickel, palladium, copper or the gold of tin, preferably nickel or palladium.The fusing point of above-mentioned conductive part Preferably more than 300 DEG C, more preferably more than 450 DEG C.Above-mentioned conductive part can be the conductive part of non-scolding tin.
It should be noted that the surface of conductive part is more to have hydroxyl due to oxidation.Generally, the conductive part for being formed by nickel There is hydroxyl due to oxidation in surface.The first insulating properties particle can be made to be attached to such leading with hydroxyl via chemical bond The surface (surface of electroconductive particle) in electric portion.Alternatively, it is also possible to make the second insulating properties particle be attached to so via chemical bond The conductive part with hydroxyl surface (surface of electroconductive particle).
Above-mentioned conductive layer can be formed by one layer.Conductive layer can also be formed by multilayer.That is, conductive layer can have 2 layers Stepped construction above.In the case where conductive layer is formed by multilayer, outermost layer is preferably layer gold, nickel dam, palladium layers, layers of copper or contains There are the alloy-layer of tin and silver, more preferably layer gold.In the case where outermost layer is these preferred conductive layers, interelectrode connection Resistance is further reduced.In addition, in the case where outermost layer is layer gold, corrosion resistance is further improved.
The method for forming conductive layer on the surface of above-mentioned substrate particle is not particularly limited.As the side for forming conductive layer Method, for example, can enumerate：Using the method for plated by electroless plating, using electric plating method, the method using physical vapor deposition and general Metal dust or the cream containing metal dust and adhesive coat method on surface of substrate particle etc..Wherein, due to leading The formation of electric layer is easy, therefore preferably by the method for plated by electroless plating.As the method for above-mentioned utilization physical vapor deposition, Ke Yiju Go out：The methods such as vacuum evaporation, ion plating and ion sputtering.
The average grain diameter of above-mentioned electroconductive particle is preferably more than 0.5 μm, more preferably more than 1 μm, preferably 500 μm with Under, more preferably less than 100 μm, particularly preferably more preferably less than 50 μm, less than 20 μm.If electroconductive particle is flat Equal particle diameter is more than above-mentioned lower limit and below the above-mentioned upper limit, then in the electroconductive particle using tape insulation particle entering between electrode In the case of row connection, fully increase the contact area of electroconductive particle and electrode, and be difficult to form solidifying when conductive layer is formed Poly- electroconductive particle.In addition, will not become too much via the interelectrode interval that electroconductive particle is connected, and Conductive layer is difficult the sur-face peeling from substrate particle.
" average grain diameter " of above-mentioned electroconductive particle represents number average bead diameter.The average grain diameter of electroconductive particle can be by using Electron microscope or light microscope are observed arbitrary 50 electroconductive particles and are calculated average value and obtained.
The thickness of above-mentioned conductive layer is preferably more than 0.005 μm, more preferably more than 0.01 μm, and preferably 10 μm with Under, more preferably less than 1 μm, more preferably less than 0.3 μm.If the thickness of conductive layer be above-mentioned lower limit more than and it is above-mentioned on Limit is following, then can obtain sufficient electric conductivity, and electroconductive particle will not become really up to the mark, conductive during being attached between electrode Property particle fully deforms.
In the case where above-mentioned conductive layer is formed by multilayer, the thickness of outermost conductive layer, particularly outermost layer are gold The thickness of layer gold is preferably more than 0.001 μm in the case of layer, more preferably more than 0.01 μm, and preferably less than 0.5 μm, more Preferably less than 0.1 μm.If the thickness of above-mentioned outermost conductive layer is more than above-mentioned lower limit and below the above-mentioned upper limit, outermost The conductive layer of layer is evenly coated, and corrosion resistance is fully improved, and interelectrode connection resistance abundant step-down.In addition, above-mentioned Outermost layer is that the thickness of the layer gold in the case of layer gold is thinner, and cost is lower.
The thickness of above-mentioned conductive layer can be exhausted to electroconductive particle or band by using such as infiltration type electron microscope (TEM) The section of the electroconductive particle of edge particle is observed to measure.
It is preferred that the conductive part outer surface of electroconductive particle has projection, the projection is preferably several.By tape insulation particle Electroconductive particle connection electrode surface more form aerobicization envelope.There is raised band the surface of conductive part has been used In the case of the electroconductive particle of insulating properties particle, can be by configuring between electrode the electroconductive particle of tape insulation particle and right It carries out pressing so as to effectively exclude above-mentioned oxide film thereon using projection.Therefore, electrode and conductive part further reliably connect Touch, interelectrode connection resistance is further reduced.And then, when being attached between electrode, can be by the projection of electroconductive particle Effectively the insulating properties particle between electroconductive particle and electrode is excluded.Therefore, interelectrode conducting reliability enters one Step is improved.
Method as projection is formed on the surface of electroconductive particle, can enumerate：Core material is set to be attached to substrate particle Surface after, using plated by electroless plating formed conductive layer method；Formed on substrate particle surface using plated by electroless plating etc. After first conductive layer, core material is configured on first conductive layer, the second conductive layer is formed followed by plated by electroless plating etc. Method；And method of midway stage addition core material of conductive layer etc. is formed on the surface of substrate particle.
Method as making core material be attached to substrate particle surface, for example, can enumerate：In the dispersion liquid of substrate particle In, add core material, using such as van der waals force make core material accumulate, be attached to substrate particle surface method and By core material addition in the container equipped with substrate particle, the mechanism using the generation such as rotation of container adheres to core material Method on substrate particle surface etc..Wherein, for ease of control attachment core material amount, preferably make core material accumulate, it is attached The method for the substrate particle surface in dispersion liquid.
Above-mentioned electroconductive particle can have the first conductive layer on the surface of substrate particle, and on first conductive layer With the second conductive layer.At this point it is possible to make core material be attached to the surface of the first conductive layer.Core material is preferably by the second conductive layer Cladding.The thickness of above-mentioned first conductive layer is preferably more than 0.05 μm, and preferably less than 0.5 μm.Electroconductive particle preferably leads to Cross and the first conductive layer is formed on the surface of substrate particle, after core material is attached on the surface of first conductive layer, The second conductive layer is formed on the surface of the first conductive layer and core material to obtain.
As the material for constituting above-mentioned core material, conductive material and non-conducting material can be enumerated.Led as above-mentioned Conductive substances, for example, can enumerate：The electrically conductive, non-metallics and electric conductive polymer etc. such as metal, the oxide of metal, graphite.Make It is above-mentioned electric conductive polymer, polyacetylene etc. can be enumerated.As above-mentioned non-conducting material, can enumerate：Silica, oxygen Change aluminium and zirconium oxide etc..Wherein, because electric conductivity can be improved, therefore preferably metal.
As above-mentioned metal, for example, can enumerate：Gold, silver, copper, platinum, zinc, iron, lead, tin, aluminium, cobalt, indium, nickel, chromium, titanium, The metals such as antimony, bismuth, germanium and cadmium and tin-lead alloy, tin-copper alloy, tin-silver alloy, tin-lead-silver alloy and tungsten carbide etc. by Alloy that two or more metal is constituted etc..Wherein, preferably nickel, copper, silver or gold.The metal for constituting above-mentioned core material can be with composition The metal phase of above-mentioned conductive part (conductive layer) is same, it is also possible to different.
The shape of above-mentioned core material is not particularly limited.Core material is preferably shaped to bulk.As core material, for example may be used To enumerate：The block of particle shape, the cohesion block of multiple particulate cohesions and irregular piece etc..
The average diameter (average grain diameter) of above-mentioned core material is preferably more than 0.001 μm, more preferably more than 0.05 μm, and Preferably less than 0.9 μm, more preferably less than 0.2 μm.If the average diameter of above-mentioned core material is more than above-mentioned lower limit and the upper limit Hereinafter, then interelectrode connection resistance is effectively reduced.
" average diameter (average grain diameter) " of above-mentioned core material represents number average diameter (number average bead diameter).Core material it is average straight Footpath can calculate average value by using electron microscope or light microscope carrying out observation to arbitrary 50 core materials and ask Go out.
The above-mentioned projection of every 1 above-mentioned electroconductive particle is preferably more than 3, more preferably more than 5.Above-mentioned projection Quantity the upper limit is not particularly limited.The upper limit of raised quantity is contemplated that particle diameter of electroconductive particle etc. is suitably selected.
From the viewpoint of insulating reliability from further raising insulating reliability and for impact, above-mentioned second insulating properties The average grain diameter of particle is preferably more than 0.7 times of the average height of above-mentioned projection, more preferably more than 1 times, and preferably 5 times Hereinafter, more preferably less than 3 times.
Above-mentioned raised average height represents the average value of multiple raised height, and raised height represents connecting conductive On the center of particle and the sophisticated line (the dotted line L1 shown in Fig. 2) of projection from imagination without projection when conductive layer imagination Start (it is assumed that on outer surface of spherical electroconductive particle during without projection) on line (the dotted line L2 shown in Fig. 2) to raised The distance at tip.I.e., in fig. 2, the distance from the intersection point of dotted line L1 and dotted line L2 to raised tip is represented.
(the first insulating properties particle, the second insulating properties particle)
Above-mentioned first insulating properties particle, the second insulating properties particle are the particle with insulating properties.Above-mentioned first insulating properties grain Son, the second insulating properties particle are respectively less than electroconductive particle.If using the electroconductive particle of tape insulation particle being carried out between electrode Connection, then can prevent the short circuit between adjacent electrode by above-mentioned first insulating properties particle, the second insulating properties particle.Specifically, When the electroconductive particle of multiple tape insulation particles is contacted, due to conductive in the electroconductive particle of multiple tape insulation particles There is above-mentioned first insulating properties particle, the second insulating properties particle between property particle, therefore can prevent laterally adjacent interelectrode short Short circuit between road rather than upper/lower electrode.In addition, when being attached between electrode, can be by with 2 electrode pair tape insulations grains The electroconductive particle of son is pressurizeed easily to exclude the above-mentioned first insulating properties particle between conductive part and electrode, second exhausted Edge particle.In the case where the surface of electroconductive particle is provided with projection, further can easily exclude conductive part and electrode it Between above-mentioned first insulating properties particle, the second insulating properties particle.
As the material for forming above-mentioned first insulating properties particle, the second insulating properties particle, can enumerate insulating properties resin, And the inorganic matter of insulating properties etc..As the resin of above-mentioned insulating properties, can enumerate and can be used as substrate particle as formation The above-mentioned resin that the resin of resin particle is enumerated.As the inorganic matter of above-mentioned insulating properties, can enumerate as available for being formed Make the above-mentioned inorganic matter that the inorganic matter of the inorganic particulate of substrate particle is enumerated.
As above-mentioned first insulating properties particle, the concrete example of the insulation resistance resin of the second insulating properties particle, Ke Yiju Go out：TPO, (methyl) acrylate polymer, (methyl) acrylate copolymer, block polymer, thermoplastic resin, The cross-linking agent of thermoplastic resin, thermosetting resin and water-soluble resin etc..
As said polyolefins class, can enumerate：Polyethylene, ethene-vinyl acetate copolymer and ethylene-acrylate are total to Polymers etc..As above-mentioned (methyl) acrylate polymer, can enumerate：Poly- (methyl) methyl acrylate, poly- (methyl) propylene Acetoacetic ester and poly- (methyl) butyl acrylate etc..As above-mentioned block polymer, can enumerate：Polystyrene, styrene-propene Acid ester copolymer, SB types styrene-butadiene block copolymer and SBS types styrene-butadiene block copolymer and it Hydride etc..As above-mentioned thermoplastic resin, can enumerate：Polyvinyl and ethylenic copolymer etc..As upper Thermosetting resin is stated, can be enumerated：Epoxy resin, phenolic resin and melmac etc..As above-mentioned water-soluble resin, can To enumerate：Polyvinyl alcohol, polyacrylic acid, polyacrylamide, PVP, PEO and methylcellulose Deng.Wherein, preferably water-soluble resin, more preferably polyvinyl alcohol.
Above-mentioned first insulating properties particle, the viewpoint of the detachment of the second insulating properties particle are examined when pressing is further improved Consider, above-mentioned first insulating properties particle, the second insulating properties particle are respectively preferably inorganic particulate, preferably silicon dioxide granule.
As above-mentioned inorganic particulate, can enumerate：White sand particle, hydroxyapatite particle, magnesia particle, zirconium oxide grain Son and silicon dioxide granule etc..As above-mentioned silicon dioxide granule, can enumerate：Crush silica, spherical silicon dioxide.It is excellent Choosing uses spherical silicon dioxide.In addition, silicon dioxide granule preferably has what such as carboxyl, hydroxyl etc. were chemically bonded on surface Functional group, more preferably with hydroxyl.Inorganic particulate is harder, and particularly silicon dioxide granule is harder.Using it is such possess compared with In the case of the electroconductive particle of the tape insulation particle of hard insulating properties particle, in the electroconductive particle to tape insulation particle When being kneaded with adhesive resin, harder insulating properties particle has the tendency for easily departing from from the surface of electroconductive particle. On the other hand, in the case of using the electroconductive particle of tape insulation particle of the invention, even if exhausted using harder first Edge particle, when above-mentioned mixing is carried out, is departed from due to the second insulating properties particle such that it is able to suppress the first insulating properties particle.On The second insulating properties particle is stated for example to play a part of to assign resiliency.In addition, when above-mentioned mixing is carried out, even if the first insulating properties Particle disengaging also remains the second insulating properties particle, and its result can ensure that insulating reliability.
It is preferred that above-mentioned second insulating properties particle is attached to the surface of above-mentioned first insulating properties particle via chemical bond.It is preferred that on State the surface that the first insulating properties particle is attached to above-mentioned electroconductive particle via chemical bond.The chemical bond include covalent bond, hydrogen bond, Ionic bond and coordinate bond etc..Wherein, preferably covalently key, has preferably used the chemical bond of reactive functional groups.
As the reactive functional groups for forming above-mentioned chemical bond, for example, can enumerate：Vinyl, (methyl) acryloyl group, Silylation, silanol group, carboxyl, amino, ammonium, nitro, hydroxyl, carbonyl, mercapto, sulfonic group, sulfonium base, boronate, oxazoles Quinoline base, pyrrolidone-base, phosphate and itrile group etc..Wherein, preferred vinyl, (methyl) acryloyl group.
From the disengaging for further suppressing the first insulating properties particle, and further improve the insulating reliability of connection structural bodies Viewpoint considers that, used as above-mentioned first insulating properties particle, preferably using surface has the insulating properties particle of reactive functional groups.From entering One step suppresses the disengaging of insulating properties particle, and further from the viewpoint of the insulating reliability of raising connection structural bodies, as upper The first insulating properties particle is stated, the first insulating properties after being surface-treated with the compound with reactive functional groups is preferably used Particle.In addition, from from the viewpoint of further improving insulating reliability, as above-mentioned second insulating properties particle, preferably using table Face has the insulating properties particle of reactive functional groups.From from the viewpoint of further improving insulating reliability, as above-mentioned second Insulating properties particle, preferably uses the second insulating properties particle after being processed with the compound surface with reactive functional groups.
As the above-mentioned reactive functional groups that can be introduced to above-mentioned first insulating properties particle, the second insulating properties particle surface, Can enumerate：(methyl) acryloyl group, glycidyl, hydroxyl, vinyl and amino etc..Above-mentioned first insulating properties particle, The above-mentioned reactive functional groups that two insulating properties particle surfaces have are preferably selected from (methyl) acryloyl group, glycidyl, hydroxyl At least a kind reactive functional groups in base, vinyl and amino.
As the compound (surface treatment substance) for introducing above-mentioned reactive functional groups, can enumerate：With (first Base) compound of acryloyl group, the compound with epoxy radicals and the compound with vinyl etc..
As the compound (surface treatment substance) for introducing vinyl, can enumerate：Silanization with vinyl Compound, the titanium compound with vinyl and the phosphate cpd with vinyl etc..Above-mentioned surface treatment substance is preferably tool There is the silane compound of vinyl.As the above-mentioned silane compound with vinyl, can enumerate：Vinyl trimethoxy silicon Alkane, VTES, vinyltriacetoxy silane and vinyl silane triisopropoxide etc..
As the compound (surface treatment substance) for introducing (methyl) acryloyl group, can enumerate：With (methyl) The silane compound of acryloyl group and the titanium compound with (methyl) acryloyl group and the phosphorus with (methyl) acryloyl group Acid compound etc..Above-mentioned surface treatment substance is preferably also the silane compound with (methyl) acryloyl group.As above-mentioned tool There is the silane compound of (methyl) acryloyl group, can enumerate：(methyl) acryloxypropyl triethoxysilane, (methyl) Acryloxypropyl trimethoxy silane and the dimethoxysilane of (methyl) acryloxypropyl three etc..
Above-mentioned electroconductive particle surface and above-mentioned conduction are attached to as the first insulating properties particle, the second insulating properties particle is made The method on portion surface, can enumerate chemical method and physics or mechanical means etc..As above-mentioned chemical method, for example can be with Enumerate：Interfacial polymerization, the suspension polymerization in the presence of particle and emulsion polymerization etc..As above-mentioned physics or machinery side Method, can enumerate：Using method for being spray-dried, blending together method, electrostatic adherence method, spray-on process, dipping and vacuum evaporation etc..Its In, in the method for blending together, due to the tendency that the first insulating properties particle, the second insulating properties particle depart from is susceptible to, therefore matching somebody with somebody Put above-mentioned first insulating properties particle, the method for the second insulating properties particle and be preferably method in addition to the method for blending together.First insulating properties Particle does not preferably utilize the method that blendes together to configure on the surface of electroconductive particle.Second insulating properties particle does not preferably utilize the method for blending together to match somebody with somebody Put on the surface of electroconductive particle.Consideration is further not easily disconnected from from the first insulating properties particle, preferably by the first insulating properties grain Son configures the method on the surface of electroconductive particle via chemical bond.From the second insulating properties particle be further not easily disconnected from terms of Consider, the second insulating properties particle is preferably configured into the method on the surface of electroconductive particle via chemical bond.
As making the first insulating properties particle, the second insulating properties particle be attached to the surface of above-mentioned electroconductive particle and above-mentioned lead 1 example of the method on the surface in electric portion, can enumerate following method.
First, to electroconductive particle is added in water equal solvent 3L, while stirring, adds the first insulating properties grain at leisure on one side Son, the second insulating properties particle.After being sufficiently stirred for, the electroconductive particle to tape insulation particle is separated, using vacuum Drying machine etc. is dried, and obtains the electroconductive particle of tape insulation particle.
Above-mentioned conductive part preferably has on surface can be with the reactive functional groups of above-mentioned first insulating properties particle reaction.It is above-mentioned First insulating properties particle preferably has the reactive functional groups that can be reacted with conductive part on surface.Using these reactive functional groups Chemical bond is introduced, thus the first insulating properties particle departs from being difficult non-purpose from the surface of electroconductive particle.In addition, insulation can It is further enhanced by property and for the insulating reliability of impact.Above-mentioned conductive part preferably has on surface can be with above-mentioned second The reactive functional groups of insulating properties particle reaction.Above-mentioned second insulating properties particle preferably has what can be reacted with conductive part on surface Reactive functional groups.Chemical bond is introduced using these reactive functional groups, thus the second insulating properties particle is difficult non-purpose ground Depart from from the surface of electroconductive particle.In addition, insulating reliability and the insulating reliability for impact are further enhanced.
As above-mentioned reactive functional groups, it is contemplated that the suitable group of reaction Sexual behavior mode.As above-mentioned reactive functional groups, Can enumerate：Hydroxyl, vinyl and amino etc..Because reactivity is excellent, therefore above-mentioned reactive functional groups are preferably hydroxyl.On State electroconductive particle preferably has hydroxyl on surface.Above-mentioned conductive part preferably has hydroxyl on surface.Above-mentioned insulating properties particle is excellent Being selected in surface has hydroxyl.
In the case where the surface on the surface of insulating properties particle and electroconductive particle has hydroxyl, based on dehydration first The adhesive force of insulating properties particle, the second insulating properties particle and electroconductive particle is moderately improved.
As the compound with above-mentioned hydroxyl, can enumerate：Based compound containing P-OH and based compound containing Si-OH etc.. As the compound with hydroxyl for introducing hydroxyl to the surface of insulating properties particle, can enumerate：Based compound containing P-OH And based compound containing Si-OH etc..
As the above-mentioned concrete example containing P-OH based compounds, can enumerate：Phosphoric acid epoxide ethylmethyl acrylate, phosphoric acid Epoxide propyl methacrylate, phosphoric acid epoxide polyoxyethylene glycol monomethacrylates and phosphoric acid epoxide polyoxypropylene glycol list first Base acrylate etc..Above-mentioned based compound containing P-OH can be using only a kind, it is also possible to be applied in combination two or more.
As the above-mentioned concrete example containing Si-OH based compounds, can enumerate：Vinyl ortho-siliformic acid and 3- methyl-props Alkene acryloxypropylethoxysilane ortho-siliformic acid etc..Above-mentioned based compound containing Si-OH can be using only a kind, it is also possible to be applied in combination 2 kinds with On.
For example, the insulating properties particle that surface has hydroxyl can be processed to obtain by using silane coupler.Make It is above-mentioned silane coupler, for example, can enumerates hydroxyl trimethoxy silane etc..
(conductive material)
Conductive material of the invention includes the electroconductive particle and adhesive resin of tape insulation particle of the invention.Make When the electroconductive particle of tape insulation particle of the invention is dispersed in adhesive resin, the first insulating properties particle, the second insulation Property particle be difficult to depart from from the surface of electroconductive particle.The electroconductive particle of tape insulation particle of the invention is preferably dispersed in viscous It is used as conductive material in mixture resin.Above-mentioned conductive material is preferably anisotropic conductive material.
Above-mentioned adhesive resin is not particularly limited.As above-mentioned adhesive resin, the resin of common insulating properties is used. As above-mentioned adhesive resin, for example, can enumerate：Vinylite, thermoplastic resin, curable resin, thermoplastic block are common Polymers and elastomer etc..Above-mentioned adhesive resin can be using only a kind, it is also possible to be applied in combination two or more.
As above-mentioned vinylite, for example, can enumerate：Vinyl acetate resin, acrylic resin and styrene resin Deng.As above-mentioned thermoplastic resin, for example, can enumerate：Vistanex, ethene-vinyl acetate copolymer and polyamide Deng.As above-mentioned curable resin, for example, can enumerate：Epoxy resin, polyurethane resin, polyimide resin and unsaturation are poly- Ester resin etc..It should be noted that above-mentioned curable resin can be normal temperature cured type resin, thermosetting resin, light curable type tree Fat or moisture-curable resin.Above-mentioned curable resin can be applied in combination with curing agent.As above-mentioned thermoplastic block Thing, for example, can enumerate：SBS, styrene-isoprene-phenylethene block copolymerization The hydride and SIS of thing, SBS Hydride etc..As above-mentioned elastomer, for example, can enumerate：Styrene butadiene copolymers rubber and acrylonitrile-styrene Block copolymerization rubber etc..
Above-mentioned conductive material for example may be used in addition to the electroconductive particle and above-mentioned adhesive resin of above-mentioned tape insulation particle With steady containing filler, extender, softening agent, plasticizer, polymerization catalyst, curing catalysts, colouring agent, antioxidant, heat Determine the various additives such as agent, light stabilizer, ultra-violet absorber, lubricant, antistatic additive and fire retardant.
Use the method that the electroconductive particle of above-mentioned tape insulation particle is dispersed in above-mentioned adhesive resin existing There is known process for dispersing, be not particularly limited.Adhesive resin is dispersed in as the electroconductive particle of tape insulation particle is made In method, can for example enumerate：The electroconductive particle of tape insulation particle is added after adhesive resin, is mixed with planetary Conjunction machine etc. carries out mixing makes its scattered method；The electroconductive particle for making tape insulation particle using homogenizer etc. is uniformly dispersed After in the water or organic solvent, it is added in adhesive resin, mixing is carried out with planetary-type mixer etc. makes its scattered method； And after diluting adhesive resin water or organic solvent etc., the electroconductive particle of tape insulation particle is added, with planetary Mixer etc. carries out mixing makes its scattered method etc..
Conductive material of the invention can be used as conductive paste and conducting film etc..It is the feelings of conducting film in conductive material of the invention Under condition, the film layer that can not will contain electroconductive particle is stacked on the conducting film containing electroconductive particle.Above-mentioned conductive paste is preferred It is anisotropic conductive cream.Above-mentioned conducting film is preferably anisotropic conductive film.
Conductive material of the invention is preferably conductive paste.The operability and circuit fillibility of conductive paste are excellent.Led During electric cream, although the electroconductive particle to tape insulation particle assigns larger power, but can be by above-mentioned second insulating properties grain The presence of son suppresses insulating properties particle and departs from from the surface of electroconductive particle.
In the weight % of above-mentioned conductive material 100, the content of above-mentioned adhesive resin is preferably more than 10 weight %, more excellent Elect as more than 30 weight %, more preferably more than 50 weight %, particularly preferably more than 70 weight %, and be preferably Below 99.99 weight %, more preferably below 99.9 weight %.If the content of adhesive resin is more than above-mentioned lower limit and above-mentioned Below the upper limit, then the electroconductive particle of tape insulation particle can be effectively configured between electrode, be connected by conductive material The conducting reliability of connecting object part further improve.
In the weight % of above-mentioned conductive material 100, the content of the electroconductive particle of above-mentioned tape insulation particle is preferably More than 0.01 weight %, more preferably more than 0.1 weight %, and preferably below 40 weight %, more preferably 20 weight % with Under, more preferably below 15 weight %.If the content of the electroconductive particle of tape insulation particle be above-mentioned lower limit more than and Below the above-mentioned upper limit, then interelectrode conducting reliability is further enhanced.
(connection structural bodies)
Using the electroconductive particle of above-mentioned tape insulation particle, or use the electric conductivity grain containing the tape insulation particle The conductive material of son and adhesive resin, is attached, it is hereby achieved that connection structural bodies to connecting object part.
Above-mentioned connection structural bodies possesses the first connecting object part, the second connecting object part, the first connecting object of connection The connecting portion of part and the second connecting object part, the preferably connecting portion are by the electroconductive particle shape of above-mentioned tape insulation particle Into or conductive material (anisotropic conductive material by the electroconductive particle containing the tape insulation particle and adhesive resin Material etc.) formed connection structural bodies.Above-mentioned first connecting object part preferred surface has first electrode.Above-mentioned second connection is right As part preferred surface has second electrode.It is preferred that above-mentioned first electrode and above-mentioned second electrode are by above-mentioned tape insulation particle Above-mentioned electroconductive particle in electroconductive particle is electrically connected.In the electroconductive particle using above-mentioned tape insulation particle In the case of, connecting portion itself is formed by the electroconductive particle of tape insulation particle.That is, the first connecting object part, the second connection Object Part is electrically connected by the electroconductive particle in the electroconductive particle of tape insulation particle.
Fig. 4 is that the connection structural bodies schematically to the electroconductive particle 1 using the tape insulation particle shown in Fig. 1 is carried out The profile of expression.
Connection structural bodies 81 shown in Fig. 4 possesses the first connecting object part 82, the second connecting object part 83, connection the The connecting portion 84 of one connecting object part 82 and the second connecting object part 83.Connecting portion 84 is by leading containing tape insulation particle The conductive material of conductive particles 1 and adhesive resin is formed.In fig. 4, illustrate for convenience, schematically illustrate tape insulation The electroconductive particle 1 of particle.In addition to the electroconductive particle 1 of tape insulation particle, it is possible to use the conduction of tape insulation particle The electroconductive particle 31 of property particle 21 and tape insulation particle.
First connecting object part 82 has multiple first electrode 82a in surface (above).Second connecting object part 83 On surface, (below) has multiple second electrode 83a.First electrode 82a and second electrode 83a is by one or more tape insulations grain Electroconductive particle 2 in the electroconductive particle 1 of son is electrically connected.Therefore, the first connecting object part 82, the second connecting object Part 83 is electrically connected by the electroconductive particle 2 in the electroconductive particle 1 of tape insulation particle.
The manufacture method of above-mentioned connection structural bodies is not particularly limited.As 1 example of the manufacture method of connection structural bodies Son, can enumerate：Above-mentioned conductive material is configured between the first connecting object part and the second connecting object part, is laminated After body, method that the layered product is heated and pressurizeed etc..The pressure of above-mentioned pressurization is 9.8 × 104~4.9 × 106Pa is left It is right.The temperature of above-mentioned heating is 120~220 DEG C or so.
When above-mentioned layered product is heated and pressurizeed, can be to electroconductive particle 2 and first electrode 82a, second electrode The first insulating properties particle 3 for existing between 83a, the second insulating properties particle 4 are excluded.For example, carrying out above-mentioned heating and adding During pressure, the first insulating properties particle 3, the second insulating properties existed between electroconductive particle 2 and first electrode 82a, second electrode 83a Particle 4 is melted, or deformation, so that the surface portion ground of electroconductive particle 2 exposes.It should be noted that carry out on When stating heating and pressurizeing, due to being endowed larger power, therefore, the second of the first insulating properties particle 3, part of part is exhausted sometimes Edge particle 4 departs from from the surface of electroconductive particle 2, so that the surface portion ground of electroconductive particle 2 exposes.Can be by electric conductivity The part that the surface of particle 2 is exposed is contacted via electroconductive particle 2 to first electrode with first electrode 82a, second electrode 83a 82a, second electrode 83a are electrically connected.
As above-mentioned connecting object part, specifically, can enumerate：The electricity such as semiconductor chip, capacitor and diode The electronic units such as the circuit substrate such as subassembly and printed board, flexible printed board, glass epoxy substrate and glass substrate Deng.Above-mentioned conductive material is paste, is preferably applied on connecting object part in the state of cream.Above-mentioned tape insulation grain The electroconductive particle and conductive material of son are preferred for being attached the i.e. connecting object part of electronic unit.Above-mentioned connecting object Part is preferably electronic unit.The electroconductive particle of above-mentioned tape insulation particle is preferred for carrying out the electrode in electronic unit Electrical connection.
The electroconductive particle of tape insulation particle of the invention is particularly preferred for glass substrate and semiconductor chip The COG of connecting object part is the FOG of connecting object part with glass substrate and flexible printed board (FPC).It is of the invention The electroconductive particle of tape insulation particle can be used for COG, it is also possible to for FOG.In connection structural bodies of the invention, preferably Above-mentioned first connecting object part, the second connecting object part are glass substrate and semiconductor chip, or for glass substrate and are scratched Property printed board.Above-mentioned first connects object Part, the second connecting object part can also may be used for glass substrate and semiconductor chip Think glass substrate and flexible printed board.
It is preferred that being set on the semiconductor chip used by the COG of connecting object part with glass substrate and semiconductor chip There is projection.The size of lug is preferably 1000 μm2More than and 10000 μm2Following electrode area.It is provided with the projection (electrode) Electrode gap in semiconductor chip is preferably less than 30 μm, more preferably more preferably less than 20 μm, less than 10 μm.This The electroconductive particle of the tape insulation particle of invention is preferred for such COG purposes.With glass substrate and flexible printing base In the FPC that plate is used by the FOG of connecting object part, electrode gap is preferably less than 30 μm, more preferably less than 20 μm.
As the electrode that above-mentioned connecting object part is provided with, can enumerate：Gold electrode, nickel electrode, tin electrode, aluminium electricity The metal electrodes such as pole, copper electrode, molybdenum electrode and tungsten electrode.In the case where above-mentioned connecting object part is flexible printed board, Above-mentioned electrode is preferably gold electrode, nickel electrode, tin electrode or copper electrode.It is the situation of glass substrate in above-mentioned connecting object part Under, above-mentioned electrode is preferably aluminium electrode, copper electrode, molybdenum electrode or tungsten electrode.It should be noted that being aluminium electrode in above-mentioned electrode In the case of, can be the electrode for only being formed by aluminium, or be laminated with aluminium lamination on the surface of metal oxide layer Electrode.As the material of above-mentioned metal oxide layer, can enumerate：Indium oxide doped with the metallic element of trivalent and doped with 3 Zinc oxide of the metallic element of valency etc..As the metallic element of above-mentioned trivalent, can enumerate：Sn, Al and Ga etc..
Below, embodiment and comparative example is enumerated specifically to illustrate the present invention.The invention is not restricted to following implementation Example.
(embodiment 1)
(plated by electroless plating pretreatment process)
Alkali degreasing, acid neutralization, two using sodium hydrate aqueous solution have been carried out to resin particle (3 μm of average grain diameter) 10g Sensitization in tin chloride solution, the resin particle is to form copolymerization by tetramethylol methane tetraacrylate and divinylbenzene What resin was formed.
Above-mentioned resin particle is processed using ion adsorbent 5 minutes, then, be added in sulfuric acid aqueous palladium.Then, plus Entering dimethylamine borane carries out reduction treatment, by the resin particle for being filtered, being cleaned and obtained being attached with palladium.
(core material Composite operation)
The resin particle 10g for imparting palladium catalyst is set to be prepared for dispersion liquid in being dispersed in ion exchange water 300mL.Last The resin particle for metallic Ni particles (average grain diameter 50nm) 1g additions being prepared for being attached with metallic Ni particles in dispersion liquid in 3 minutes Son.
(process for electroless nickel plating operation)
Then, the weight % of sodium succinate 1 obtained from making sodium succinate be dissolved in ion exchange water 500mL is prepared molten Liquid.The resin particle 10g that metallic Ni particles and palladium will be attached with is added in the solution, and mixed and prepare slurry. Sulfuric acid is added in slurry, the pH of slurry is adjusted to 5.
Prepare and contain the weight % of nickel sulfate 10, the weight % of sodium hypophosphite 10, the weight % of NaOH 4 and the weight of sodium succinate 20 The early stage nickel plating bath for measuring % is electro-hydraulic as nickel.PH is adjusted to after 5 above-mentioned slurry is heated up to 80 DEG C, continuously early stage nickel is plated Drop adds in the slurry, stirs 20 minutes, thus carries out electroplating reaction.Confirm that hydrogen is no longer produced and terminates electroplating reaction.
Then, the later stage containing the weight % of nickel sulfate 20, the weight % of dimethylamine borane 5 and the weight % of NaOH 5 is prepared Nickel plating bath.Later stage nickel plating bath is continuously added dropwise the solution obtained from the electroplating reaction for finishing to be carried out using early stage nickel plating bath In, stir 1 hour, thus carry out electroplating reaction.As described above, forming nickel dam on the surface of resin particle, electric conductivity grain is obtained Sub- A.It should be noted that the thickness of nickel dam is 0.1 μm.
(production process of insulating properties particle)
Composition containing following monomers is added to and is mounted with 4 mouthfuls of detachable lids, stirring vane, triple valve, coolings In the 1000mL detachable flasks of pipe and temperature probe：Contain GMA 45mmol, methacrylic acid Methyl esters 380mmol, ethylene glycol dimethacrylate 13mmol, phosphoric acid epoxide polyoxyethylene glycol methacrylate 0.5mmol, And double { 2- [N- (2- carboxyethyls) amidino groups] propane } 1mmol of 2,2 '-azo.Addition distilled water causes the solid of the monomer composition Composition turns into 10 weight %, then, is stirred with 150rpm, and polymerization 24 hours is carried out under 60 DEG C of nitrogen atmospheres.Reaction knot Freeze-drying is carried out after beam, there is the P-OH from acid phosphate epoxide polyoxyethylene glycol methacrylate so as to obtain surface First insulating properties particle (average grain diameter 400nm) of base.
In addition, above-mentioned mixing speed is changed into 300rpm, polymerization temperature is changed to 80 DEG C, in addition, with same The method of sample obtains the second insulating properties particle (average grain diameter 180nm).
(production process of the electroconductive particle of tape insulation particle)
In insulating properties particle obtained above is dispersed in distilled water under ultrasonic irradiation respectively, insulating properties particle is obtained 10 weight % aqueous dispersions.The electroconductive particle A10g for obtaining is dispersed in distilled water 500mL, and add the first insulating properties The aqueous dispersions 3g of particle, is stirred at room temperature 30 minutes.And then, the aqueous dispersions 2g of the second insulating properties particle is added, and in room Temperature stirring 6 hours.After being filtered with 3 μm of granular membranes, again with methanol cleaning is dried, so as to obtain tape insulation The electroconductive particle of particle.
Observed using scanning electron microscope (SEM), had in the electroconductive particle of tape insulation particle The surface of raised electroconductive particle, clad is formd by insulating properties particle.
(embodiment 2~4 and comparative example 1~4)
As described in Table 1, the addition to the first insulating properties particle, the second insulating properties particle is changed, except this with Outward, the electroconductive particle of tape insulation particle is obtained similarly to Example 1.
(evaluation)
(1) the total area of the part coated by the first insulating properties particle, the second insulating properties particle accounts for electroconductive particle The clad ratio Z of total surface area
The electroconductive particle of 20 tape insulation particles is observed using SEM.Obtain by the first insulating properties particle, The total projected area of the part of two insulating properties particles cladding accounts for the clad ratio of the total surface area of electroconductive particle.By 20 claddings The average value of rate is set to clad ratio Z.
In the total number of (2) second insulating properties particles, configured in electric conductivity in the way of with the first insulating properties particle contact The ratio X1 of the number of the second electroconductive particle on particle surface
In obtaining the electroconductive particle of the tape insulation particle for obtaining, in the total number of the second insulating properties particle with lead The mode of conductive particles contact configures the ratio X1 of the number of the second insulating properties particle on the first insulating properties particle surface (%).With the ratio X1 of following standard determination numbers.
[configured in the first insulating properties in the way of with the first insulating properties particle contact in the total number of the second insulating properties particle The criterion of the ratio X1 of the number of the second insulating properties particle on particle surface]
A：The ratio X1 of number is more than 50%
B：The ratio X1 of number is more than 30% and less than 50%
C：The ratio X1 of number is more than 20% and less than 30%
D：The ratio X1 of number is less than 20%
In the total number of (3) second insulating properties particles with do not contact the first insulating properties particle and contact electroconductive particle side Formula configures the ratio X3 of the number of the second electroconductive particle on electroconductive particle surface
Obtain in the electroconductive particle of the tape insulation particle for obtaining, not connecing in the total number of the second insulating properties particle Touch the first insulating properties particle and contact the second insulating properties grain that the mode of electroconductive particle is configured on the surface of electroconductive particle The ratio X3 (%) of the number of son.With the ratio X3 of following standard determination numbers.
[in the total number of the second insulating properties particle in the way of not contacting the first insulating properties particle and contact electroconductive particle The criterion of the ratio X3 of the number of second insulating properties particle of the configuration on the surface of electroconductive particle]
A：The ratio X3 of number is more than 20% and less than 50%
B：The ratio X3 of number is more than 10% and less than 20%
C：The ratio X3 of number is less than 10%
(4) mean number of first insulating properties particle of the configuration of every 1 electroconductive particle on electroconductive particle surface Y1
Obtain in the electroconductive particle of the tape insulation particle for obtaining, the configuration of every 1 electroconductive particle is in electric conductivity The mean number Y1 of the first insulating properties particle on particle surface.With following standard determinations mean number Y1.
[the mean number of first insulating properties particle of the configuration of every 1 electroconductive particle on the surface of electroconductive particle The criterion of Y1]
A：Mean number Y1 is more than 10 and less than 100
B：Mean number Y1 is for more than 3 and less than 10
C：Mean number Y1 is less than 3
(5) mean number of second insulating properties particle of the configuration of every 1 electroconductive particle on electroconductive particle surface Y2
Obtain in the electroconductive particle of the tape insulation particle for obtaining, the configuration of every 1 electroconductive particle is in electric conductivity grain The mean number Y2 of the second insulating properties particle on sublist face.With following standard determinations mean number Y2.
[the mean number Y2 of second insulating properties particle of the configuration of every 1 electroconductive particle on electroconductive particle surface Criterion]
A：Mean number Y2 is more than 20 and less than 1000
B：Mean number Y2 is for more than 6 and less than 20
C：Mean number Y2 is less than 6
(6) mean number of first insulating properties particle of the configuration of every 1 electroconductive particle on electroconductive particle surface The ratio between the mean number Y2 of the second insulating properties particle of the configuration of Y1 and every 1 electroconductive particle on electroconductive particle surface (mean number Y1/ mean number Y2)
Obtain in the electroconductive particle of the tape insulation particle for obtaining, the configuration of every 1 electroconductive particle is in electric conductivity grain The configuration of the mean number Y1 of the first insulating properties particle on sublist face and every 1 electroconductive particle is on electroconductive particle surface The ratio between the mean number Y2 of the second insulating properties particle (mean number Y1/ mean number Y2).With following standard determinations ratio Value (mean number Y1/ mean number Y2).
[criterion of ratio (mean number Y1/ mean number Y2)]
A：Ratio than (mean number Y1/ mean number Y2) is more than 0.005 and less than 0.5
B：Ratio than (mean number Y1/ mean number Y2) is more than 0.5 and less than 1
C：Ratio than (mean number Y1/ mean number Y2) is more than 1
(7) conduction (between upper/lower electrode)
The electroconductive particle of the tape insulation particle that will be obtained is added to Mitsui Chemicals, Inc.'s system " Struct BondXN- Making the content of the electroconductive particle of the tape insulation particle for obtaining in 5A " turns into 10 weight %, disperses it, obtains anisotropy Conductive paste.
It is the transparent glass substrate of 30 μm/30 μm of ITO electrode pattern to prepare to be formed with L/S above.In addition, preparing following It is formed with the semiconductor chip of the copper electrode pattern that L/S is 30 μm/30 μm.
The anisotropic conductive cream for obtaining is coated on above-mentioned transparent glass substrate and forms anisotropic conductive Layer of paste so that its thickness is 30 μm.Then, state semiconductor chip anisotropic conductive layer of paste upper strata is stacked on so that electrode that This is opposed.Then, while the temperature of adjustment pressure head causes that the temperature of anisotropic conductive layer of paste is 185 DEG C, while in semiconductor Pressurized, heated pressure head is loaded above chip, the pressure for applying 1MPa makes anisotropic conductive layer of paste solidify at 185 DEG C, obtains Connection structural bodies.
The connection resistance between 20 upper/lower electrodes of connection structural bodies for obtaining is measured respectively using 4 terminal methods. It should be noted that can by the relation of voltage=electric current × resistance by by certain electric current when voltage be measured So as to obtain connection resistance.With following standard determination conductions.
[criterion of conduction]
○○：Resistance value is that the ratio of the number of the connection structural bodies of 5 below Ω is more than 90%
○：Resistance value is that the ratio of the number of the connection structural bodies of 5 below Ω is more than 80% and less than 90%
△：Resistance value is that the ratio of the number of the connection structural bodies of 5 below Ω is more than 60% and less than 80%
×：Resistance value is that the ratio of the number of the connection structural bodies of 5 below Ω is less than 60%
(8) insulating properties (between laterally adjacent electrode)
In 20 connection structural bodies obtained in the evaluation of above-mentioned (7) conduction, resistance is carried out by with tester Determine to evaluate whether there is leakage between adjacent electrode.Insulating properties is judged with following standards.
[criterion of insulating properties]
○：Resistance value is 108The ratio of the number of the connection structural bodies of more than Ω is more than 80%
△：Resistance value is 108The ratio of the number of the connection structural bodies of more than Ω is more than 60% and less than 80%
×：Resistance value is 108The ratio of the number of the connection structural bodies of more than Ω is less than 60%
Show the result in table 1 below.It should be noted that in embodiment 1~3, the ratio X1 of number has exceeded 50%.

Claims (8)

1. a kind of electroconductive particle with insulating properties particle, it has：
At least surface have conductive part electroconductive particle,
Configure multiple first insulating properties particles on the electroconductive particle surface,
The multiple second insulating properties particles on the electroconductive particle surface are configured,
The average grain diameter of the second insulating properties particle is less than the average grain diameter of the first insulating properties particle,
In the total number of the second insulating properties particle more than 20% in the way of being in contact with the first insulating properties particle Configure on the surface of the electroconductive particle,
The gross area of the part coated by the first insulating properties particle and the second insulating properties particle accounts for the electric conductivity grain The clad ratio of sub- total surface area is more than 50%.
2. the electroconductive particle with insulating properties particle as claimed in claim 1, wherein, the second insulating properties particle it is total In number more than 50% is configured on the surface of the electroconductive particle in the way of being in contact with the first insulating properties particle On.
3. a kind of electroconductive particle with insulating properties particle, it has：
At least surface have conductive part electroconductive particle,
Configure multiple first insulating properties particles on the electroconductive particle surface,
The multiple second insulating properties particles on the electroconductive particle surface are configured,
The average grain diameter of the second insulating properties particle is less than the average grain diameter of the first insulating properties particle,
In the total number of the second insulating properties particle more than 10% with do not contact the first insulating properties particle but contact institute The mode for stating electroconductive particle is configured on the surface of the electroconductive particle,
The gross area of the part coated by the first insulating properties particle and the second insulating properties particle accounts for the electric conductivity grain The clad ratio of sub- total surface area is more than 50%.
4. the electroconductive particle with insulating properties particle as any one of claims 1 to 3, wherein, described first is exhausted Edge particle is attached to the surface of the electroconductive particle via chemical bond.
5. the electroconductive particle with insulating properties particle as any one of claims 1 to 3, wherein, described first is exhausted Edge particle and the second insulating properties particle are not to be configured on the electroconductive particle surface by blending together method.
6. the electroconductive particle with insulating properties particle as any one of claims 1 to 3, wherein, the electric conductivity Particle has projection in the outer surface of the conductive part.
7. a kind of conductive material, it contains the electroconductive particle with insulating properties particle any one of claim 1~6 And adhesive resin.
8. a kind of connection structural bodies, it has：
Surface have first electrode the first connecting object part,
Surface have second electrode the second connecting object part,
The connecting portion of the first connecting object part and the second connecting object part is connected,
The connecting portion is formed as the electroconductive particle with insulating properties particle any one of claim 1~6, or by Contain electroconductive particle and the conduction material of adhesive resin any one of claim 1~6 with insulating properties particle Material is formed,
The first electrode and the second electrode are by the conduction in the electroconductive particle with insulating properties particle Property particle realizes electrical connection.
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