CN103765527B - Electroconductive particle, conductive material and connection structural bodies - Google Patents

Electroconductive particle, conductive material and connection structural bodies Download PDF

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Publication number
CN103765527B
CN103765527B CN201380002729.6A CN201380002729A CN103765527B CN 103765527 B CN103765527 B CN 103765527B CN 201380002729 A CN201380002729 A CN 201380002729A CN 103765527 B CN103765527 B CN 103765527B
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conductive layer
particle
mentioned
weight
nickel
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CN103765527A (en
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王晓舸
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0221—Insulating particles having an electrically conductive coating

Abstract

The present invention provides a kind of electroconductive particle that can be effectively reduced when that will be electrically connected between electrode and connect resistance.The electroconductive particle (1) of the present invention possesses：Base particle (2), it is configured on the surface of base particle (2) and the 1st conductive layer (3) containing nickel and phosphorus and is configured on the outer surface of the 1st conductive layer (3) and the 2nd conductive layer (4) containing palladium.Phosphorus content in 1st conductive layer (3) is less than 5 weight %.On the thickness direction of the 1st conductive layer (3), the phosphorus content in the 1st conductive layer (3) is high in the 2nd conductive layer (4) side in base particle (2) side ratio.

Description

Electroconductive particle, conductive material and connection structural bodies
Technical field
The present invention relates to the electroconductive particle available for for example interelectrode connection, and more specifically, being related to one kind has The electroconductive particle of base particle and the conductive layer being configured on the surface of the base particle.In addition, the present invention relates to And the conductive material and connection structural bodies of above-mentioned electroconductive particle are used.
Background technology
The anisotropic conductive material such as anisotropic conductive paste and anisotropic conductive film is well-known.It is each for this For anisotropy conductive material, electroconductive particle is dispersed with adhesive resin.
Above-mentioned anisotropic conductive material has been used for the connection and IC between IC chip and flexible printed wiring board Connection between chip and the circuit substrate with ITO electrode etc..For example, the electrode and circuit substrate in IC chip can be passed through Electrode between configure anisotropic conductive material after, heated and pressurizeed, to realize the electrical connection between these electrodes.
As one of the electroconductive particle available for above-mentioned anisotropic conductive material, disclosed in following patent documents 1 A kind of nickel dam for possessing base particle, being formed at the base particle surface and the palladium for being formed at the nickel dam surface The electroconductive particle of layer.For the electroconductive particle, in above-mentioned nickel dam the containing ratio of phosphorus in the range of 5~15 weight %, and on The containing ratio for stating palladium in palladium layers is more than 96 weight %.
Prior art literature
Patent document
Patent document 1：(Japan) JP 2010-73578 publications
The content of the invention
Problems to be solved by the invention
In the electroconductive particle described in patent document 1, due to formed with specific conductive layer, therefore, for using Connection structural bodies obtained from electroconductive particle described in patent document 1 will electrically connect between electrode, can be to a certain extent Reduce connection resistance.
But in recent years, thirst for that the electroconductive particle that can further reduce connection resistance can be developed.
It is an object of the invention to provide a kind of for can will effectively reduce connection resistance when being electrically connected between electrode Electroconductive particle and the conductive material and connection structural bodies using the electroconductive particle.
The limited purpose of the present invention is to provide a kind of rupture and conduction for being not likely to produce conductive layer when applying and loading Electroconductive particle of the layer from the stripping on base particle surface and the conductive material using the electroconductive particle and connection knot Structure body.
The method solved the problems, such as
According to the wide in range aspect of the present invention, it is possible to provide a kind of electroconductive particle, it possesses：Base particle, configuration In on the surface of the base particle and the 1st conductive layer containing nickel and phosphorus and the outer surface for being configured at the 1st conductive layer Upper and the 2nd conductive layer containing palladium, the content of phosphorus is less than 5 weight % in the 1st conductive layer, and in the thickness of the 1st conductive layer Spend on direction, the phosphorus content in the 1st conductive layer is high in the 2nd conductive layer side in described matrix material particles side ratio.
It is described on the thickness direction of the 1st conductive layer in some particular aspects of the electroconductive particle of the present invention Phosphorus content in 1st conductive layer is in described matrix material particles side ratio in high more than the 0.5 weight % in the 2nd conductive layer side.
In some particular aspects of the electroconductive particle of the present invention, the phosphorus content in the 1st conductive layer is 0.1 weight % is measured less than 5 weight %.
In some particular aspects of the electroconductive particle of the present invention, the phosphorus content in the 1st conductive layer is 3 weight % Less than 5 weight %.
In some particular aspects of the electroconductive particle of the present invention, the electroconductive particle has prominent on the surface of electric conductivity Rise.
In another particular aspects of the electroconductive particle of the present invention, it possesses the appearance for being configured at the 2nd conductive layer Megohmite insulant on face.
The conductive material of the present invention contains above-mentioned electroconductive particle and adhesive resin.
The connection structural bodies of the present invention possesses：1st connecting object part, the 2nd connecting object part and connect the 1st, The connecting portion of 2nd connecting object part, wherein, the connecting portion is formed by above-mentioned electroconductive particle or by containing the electric conductivity grain The conductive material of son and adhesive resin is formed.
The effect of invention
The electroconductive particle of the present invention possesses：Base particle, it is configured on the surface of the base particle and contains There is the 1st conductive layer of nickel and phosphorus and be configured on the outer surface of the 1st conductive layer and the 2nd conductive layer containing palladium, also, Phosphorus content in above-mentioned 1st conductive layer is less than 5 weight %, and on the thickness direction of above-mentioned 1st conductive layer, above-mentioned 1st conductive layer In phosphorus content it is high in above-mentioned 2nd conductive layer side in above-mentioned base particle side ratio, therefore, in the feelings that will be electrically connected between electrode Under condition, connection resistance can be effectively reduced.
Brief description of the drawings
Fig. 1 is the sectional view for the electroconductive particle for schematically showing first embodiment of the invention；
Fig. 2 is the sectional view for the electroconductive particle for schematically showing second embodiment of the invention；
Fig. 3 is front section view, it is schematically shown that has used the electroconductive particle of first embodiment of the invention Connection structural bodies；
Fig. 4 is illustrated on the substrate used in the evaluation of the insulaion resistance of embodiment, comparative example and reference example Comb electrodes copper pattern shape top view.
Symbol description
1 ... electroconductive particle
1a ... projections
2 ... base particles
3 ... the 1st conductive layers
3a ... projections
4 ... the 2nd conductive layers
4a ... projections
5 ... core materials
6 ... megohmite insulants
11 ... electroconductive particles
12 ... the 1st conductive layers
13 ... the 2nd conductive layers
51 ... connection structural bodies
52 ... the 1st connecting object parts
52a ... upper surfaces
52b ... electrodes
53 ... the 2nd connecting object parts
53a ... lower surfaces
53b ... electrodes
54 ... connecting portions
Embodiment
Hereinafter, the present invention is described in detail.
The electroconductive particle of the present invention possesses：Base particle, the 1st conductive layer and the 2nd conductive layer.Above-mentioned 1st is conductive Layer is configured on the surface of above-mentioned base particle, and contains nickel and phosphorus.It is conductive that above-mentioned 2nd conductive layer is configured at the above-mentioned 1st On the outer surface of layer, and contain palladium.In the electroconductive particle of the present invention, the phosphorus content in above-mentioned 1st conductive layer is less than 5 weights Measure %.On the thickness direction of above-mentioned 1st conductive layer, the phosphorus content in above-mentioned 1st conductive layer is in base particle side ratio 2 conductive layer sides are high.On the thickness direction of above-mentioned 1st conductive layer, phosphorus in above-mentioned 1st conductive layer in base particle side and The skewness of 2nd conductive layer side, its amount in base particle side are higher than the amount in the 2nd conductive layer side.
Because the electroconductive particle of the present invention possesses above-mentioned composition, therefore, using the electroconductive particle will between electrode it is electric In the case of connection, connection resistance can be effectively reduced.With the feelings that the phosphorus content in above-mentioned 1st conductive layer is more than 5 weight % Condition is compared, and by making the phosphorus content in above-mentioned 1st conductive layer be less than 5 weight %, connection resistance is effectively reduced.
In order to further reduce connection resistance, the phosphorus content in the 1st conductive layer is more few better.Phosphorus in 1st conductive layer Content is less than 5 weight %, preferably shorter than 3 weight %, more preferably below 2.9 weight %.Phosphorus content in 1st conductive layer can also For more than 0.1 weight %, or more than 0.5 weight %, can also be more than 2.9 weight %, or more than 3 weight %.
From the rupture that conductive layer is more not likely to produce during load and conductive layer is applied to electroconductive particle from matrix material grain From the viewpoint of the stripping in sublist face, preferably on the thickness direction of above-mentioned 1st conductive layer, the phosphorus in above-mentioned 1st conductive layer contains Amount in base particle side ratio in high more than the 0.5 weight % in the 2nd conductive layer side, more preferably high more than 2.0 weight %, it is further excellent High more than 4.0 weight % is selected, particularly preferred high more than 8.0 weight %.The maximum of phosphorus content in above-mentioned 1st conductive layer and minimum The poor absolute value of value is preferably more than 0.5 weight %, more preferably more than 2.0 weight %, more preferably 4.0 weight % with On, particularly preferably more than 8.0 weight %.Compared to the relatively small number of 2nd conductive layer side of nickel content in above-mentioned 1st conductive layer Region, the region of the relatively large number of base particle side of nickel content is located at inner side in above-mentioned 1st conductive layer.Thus, can be effective Ground suppresses the rupture of conductive layer and the stripping of conductive layer.The relatively large number of base particle of nickel content in above-mentioned 1st conductive layer The region of side be preferably from the inner surface of the 1st conductive layer towards outside 10% thickness region (region A).Above-mentioned 1st is conductive The region of the relatively small number of 2nd conductive layer side of nickel content is preferably towards the 10% of inner side from the outer surface of the 2nd conductive layer in layer The region (region B) of thickness.The poor absolute value of phosphorus content and the phosphorus content in above-mentioned zone B in above-mentioned zone A is preferably More than 0.5 weight %, more preferably more than 2.0 weight %, more preferably more than 4.0 weight %, particularly preferably 8.0 weight % More than.
From the rupture that conductive layer is more not likely to produce during load and conductive layer is applied to electroconductive particle from matrix material grain From the viewpoint of the stripping in sublist face, preferably on the thickness direction of above-mentioned 1st conductive layer, the phosphorus in above-mentioned 1st conductive layer contains Amount continuously or periodically increases from the lateral 2nd conductive layer side of base particle.
In the connection structural bodies for having used the electroconductive particle of the present invention, from further reducing interelectrode connection resistance From the viewpoint of, the nickel content in above-mentioned 1st conductive layer is The more the better.Nickel content in above-mentioned 1st conductive layer is preferably 50 weights Measure more than %, more preferably more than 60 weight %, more preferably more than 70 weight %, still more preferably for 80 weight % with On, particularly preferably more than 90 weight %.Nickel content in above-mentioned 1st conductive layer can also be more than 97 weight %, or More than 97.5 weight %, or more than 98 weight %.Nickel content in the above-mentioned weight % of 1st conductive layer 100 is preferably 99.85 Below weight %, more preferably below 99.7 weight %, more preferably below 99.5 weight %.
In the present invention, the upper limit of the palladium content in above-mentioned 2nd conductive layer is not particularly limited.In above-mentioned 2nd conductive layer Palladium content can also be 100 weight %, 99 weight % can also be less than, 98 weight % can also be less than, 96 weights can also be less than Measure %.In addition, phosphorus content in above-mentioned 1st conductive layer for more than 3 weight %, less than 5 weight % in the case of, the above-mentioned 2nd is conductive Palladium content in layer can also be 100 weight %, can also be less than 99 weight %, can also be less than 98 weight %, can also be less than 96 Weight %.
In the connection structural bodies of electroconductive particle of the present invention has been used, from the further viewpoint for reducing connection resistance From the point of view of, the palladium content in above-mentioned 2nd conductive layer is The more the better.Palladium content in above-mentioned 2nd conductive layer be preferably 80 weight % with On, more preferably more than 90 weight %, more preferably more than 96 weight %, particularly preferably more than 97 weight %, it is most preferably More than 98 weight %.
It should be noted that each content of the phosphorus and nickel in above-mentioned 1st conductive layer is represented in above-mentioned 1st conductive layer entirety Average content.Palladium content in above-mentioned 2nd conductive layer represents the average content of the palladium in above-mentioned 2nd conductive layer entirety.It is above-mentioned Phosphorus content in region A and above-mentioned zone B represents the average content of the phosphorus in above-mentioned zone A entirety and above-mentioned zone B entirety.
As the method for the content of the phosphorus and nickel controlled in above-mentioned 1st conductive layer, can enumerate for example：Passing through electroless plating The pH of nickel-plating liquid method is controlled when nickel forms 1 conductive layer and is controlled when forming 1 conductive layer by process for electroless nickel plating Method of the concentration of phosphorous reducing agent etc..In addition, in order that the phosphorus content in the 1st conductive layer is partly different, can also plate Using two-stage or the multistage plating for plating Ni and the high phosphorus composition plating Ni reached and low-phosphorous composition by separation of solid and liquid in Ni processes Coating method.
As the method for controlling the palladium content in above-mentioned 2nd conductive layer, such as can enumerate：Formed by electroless plating palladium Control plates the pH of palladium liquid method and controls reducing agent when forming 2 conductive layer by electroless plating palladium during 2 conductive layer The method of concentration etc..
Above-mentioned 1st, the assay method of each content of the nickel in the 2nd conductive layer, phosphorus and palladium can use known various points Analysis method, is not particularly limited.
Above-mentioned 1st, the assay method of each content of the nickel in the 2nd conductive layer, phosphorus and palladium is not particularly limited, for example, can Enumerate following method：Using focused ion beam, the obtained cut film of electroconductive particle is made, and use transmission electron microscopy Mirror FE-TEM (Japan Electronics Corporation's system " JEM-2010FEF "), nickel, phosphorus are determined by energy dispersion type x-ray analysis equipment (EDS) And each content of palladium.
As other assay methods of each content of the nickel in the above-mentioned 1st, the 2nd conductive layer, phosphorus and palladium, extinction can be enumerated Analytic approach or spectra methods etc..In above-mentioned absorptiometric analysis, flame extinction photometer and electric furnace absorption photometric can be used Meter etc..As above-mentioned spectra methods, luminescence of plasma analytic approach and plasma ion source mass spectrometry etc. can be enumerated.
In each content of the nickel in determining the above-mentioned 1st, the 2nd conductive layer, phosphorus and palladium, ICP luminesceence analyses can also be used Device.As the commercially available product of ICP apparatus for analyzing luminosity, ICP apparatus for analyzing luminosity of HORIBA company systems etc. can be enumerated.
In each content of the nickel on the thickness direction for determining above-mentioned 1st conductive layer and phosphorus, preferably using FE-TEM devices. As the commercially available product of FE-TEM devices, Japan Electronics Corporation's system " JEM-2010FEF " etc. can be enumerated.
Hereinafter, specific embodiment of the present invention and embodiment are illustrated with reference to accompanying drawing, thus illustrates the present invention.
Fig. 1 is the sectional view for the electroconductive particle for showing first embodiment of the invention.
As shown in figure 1, electroconductive particle 1 possesses：Base particle 2, the 1st conductive layer 3, the 2nd conductive layer 4, Duo Gexin Material 5 and multiple megohmite insulants 6.
1st conductive layer 3 is configured on the surface of base particle 2.1st conductive layer 3 coats the table of base particle 2 Face.2nd conductive layer 4 is configured on the outer surface of the 1st conductive layer 3.2nd conductive layer 4 coats the outer surface of the 1st conductive layer 3.It is conductive Property particle 1 be the surface of base particle 2 by the coating particles that form of the 1st, the 2nd conductive layer 3,4 cladding.
Electroconductive particle 1 has multiple projection 1a on the surface of electric conductivity.1st, the 2nd conductive layer 3,4 has in outer surface Multiple projections 3a, 4a.Multiple core materials 5 are configured on the surface of base particle 2.Multiple embedments of core material 5 the 1st, the 2nd are led In electric layer 3,4.Multiple core materials 5 are configured between the conductive layer 3 of base particle 2 and the 1st and base particle 2 and the 2nd Between conductive layer 4.Core material 5 is configured at projection 1a, 3a, 4a inner side.1st conductive layer 3 coats multiple core materials 5.Due to more The presence of individual core material 5, the outer surface protuberance of the 1st, the 2nd conductive layer 3,4, forms projection 1a, 3a, 4a.
Electroconductive particle 1 has the megohmite insulant 6 being configured on the outer surface of the 2nd conductive layer 4.The appearance of 2nd conductive layer 4 At least a portion region in face is coated by megohmite insulant 6.Megohmite insulant 6 is formed by the material with insulating properties, is insulating properties grain Son.So, electroconductive particle of the invention can also have the megohmite insulant being configured on the outer surface of the 2nd conductive layer.But The electroconductive particle of the present invention can also need not have megohmite insulant.
Fig. 2 is the sectional view for the electroconductive particle for showing second embodiment of the invention.
Electroconductive particle 11 shown in Fig. 2 possesses base particle 2, the 1st conductive layer 12 and the 2nd conductive layer 13.
Electroconductive particle 11 does not have core material.Electroconductive particle 11 does not have projection in conductive surface.Electric conductivity grain Son 11 is spherical.1st, the 2nd conductive layer 12,13 does not have projection on surface.So, electroconductive particle of the invention can not also Conductive projection, can be spherical.In addition, electroconductive particle 11 does not have megohmite insulant.But electroconductive particle 11 There can also be the megohmite insulant being configured on the surface of the 2nd conductive layer 13.
As above-mentioned base particle, can enumerate：Resin particle, the inorganic particulate in addition to metallic, You Jiwu Machine hybrid particle and metallic etc..Above-mentioned base particle is preferably the base particle in addition to metallic, more Preferably resin particle, the inorganic particulate in addition to metallic or organic inorganic hybridization particle.
Above-mentioned base particle is preferably the resin particle formed by resin.When by being connected between electrode, by electric conductivity After particle is configured between electrode, generally compress electroconductive particle.If base particle is resin particle, pass through pressure Contracting, electroconductive particle easily deform, the contact area increase of electroconductive particle and electrode.Thus, interelectrode conducting is reliable Property uprises.
As the resin for forming above-mentioned resin particle, various organic matters can be suitably used.As above-mentioned for being formed The resin of resin particle, it can enumerate for example：Polyethylene, polypropylene, polystyrene, polyvinyl chloride, Vingon, poly- isobutyl The vistanexes such as alkene, polybutadiene；The acrylic resin such as polymethyl methacrylate and PMA；Poly- terephthaldehyde Sour alkylene ester, polysulfones, makrolon, polyamide, phenol formaldehyde resin, melamine resin, benzoguanamine formaldehyde tree Fat, urea-formaldehyde resin, phenolic resin, melmac, benzoguanamine resin, Lauxite, epoxy resin, unsaturation are poly- Ester resin, saturated polyester resin, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone, polyether sulfone, And polymer etc. as obtained from one or more kinds of various polymerizable monomers with ethylenically unsaturated group are aggregated. In addition, by polymerizeing one or more kinds of various polymerizable monomers with ethylenically unsaturated group, it can design and close Into any resin particle with physical property when compressing for going out to be suitable to conductive material.Further, since it can design and synthesize out suitable In any resin particle with physical property when compressing of conductive material, and easily the hardness of base particle can be controlled In suitable scope, therefore, the resin for forming above-mentioned resin particle is preferably to have multiple alkene by one or more The polymer that the polymerizable monomer of category unsaturated group is polymerized.
In the case of being polymerize in the monomer for making there is ethylenically unsaturated group and obtaining above-mentioned resin particle, this is used as Monomer with ethylenically 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, such as can enumerate：The styrene monomers such as styrene, α-methylstyrene； The carboxyl group-containing monomers such as (methyl) acrylic acid, maleic acid, maleic anhydride；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) aliphatic acrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, the different ice of (methyl) acrylic acid Piece ester etc. (methyl) alkyl-acrylates；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) glycerol acrylate, polyoxyethylene (methyl) esters of acrylic acid containing oxygen atom such as (methyl) acrylate, (methyl) glycidyl acrylate；(methyl) third Alkene nitrile etc. contains nitrile monomer；The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether；Vinyl acetate, The vinyl acetate class such as vinyl butyrate, vinyl laurate, stearic acid vinyl ester；Ethene, propylene, isoprene, butadiene etc. Unsaturated hydrocarbons；(methyl) acrylic acid trifluoromethyl ester, the fluorine ethyl ester of (methyl) acrylic acid five, vinyl chloride, PVF, chlorostyrene etc. contain Halogen monomer etc..
As the monomer of above-mentioned bridging property, such as can enumerate：Tetramethylol methane four (methyl) acrylate, tetra methylol Methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid Ester, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine three (methyl) acrylic acid Ester, glycerine two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propane diols two (methyl) acrylic acid Multifunctional (methyl) propylene such as ester, (poly-) tetramethylene two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate Esters of gallic acid；(different) triallyl cyanurate, triallyltrimelitate, divinylbenzene, dially phthalate, two allyls Base acrylamide, diallyl ether, γ-(methyl) acryloxypropyl trimethoxy silane, trimethoxysilyl benzene Silane-containing monomer such as ethene, vinyltrimethoxy silane etc..
It polymerize the above-mentioned polymerizable monomer with ethylenically unsaturated group by using known method, can obtains State resin particle.As this method, for example, can enumerate in the presence of radical polymerization initiator carry out suspension polymerisation method, And method for making monomer swell together with radical polymerization initiator using noncrosslinking kind of particle and polymerizeing etc..
In the case that above-mentioned base particle is the inorganic particulate or organic inorganic hybridization particle in addition to metallic, As the inorganic matter for forming base particle, silica and carbon black etc. can be enumerated.As by above-mentioned silica shape Into particle, be not particularly limited, such as can enumerate by the way that the silicon compound with more than 2 water-disintegrable alkoxies is entered into water-filling After solving and forming cross-linking polymer particle, particle obtained from being fired as needed.As above-mentioned organic inorganic hybridization grain Son, such as the organic inorganic hybridization particle formed by the alkoxysilyl polymer and acrylic resin being crosslinked can be enumerated Deng.
, can as the metal for forming the metallic in the case where above-mentioned base particle is metallic Silver, copper, nickel, silicon, gold and titanium etc. are enumerated, but preferred substrate material particles are not metallics.
The average grain diameter of above-mentioned base particle is preferably more than 0.1 μm, more preferably more than 0.5 μm, further Preferably more than 1 μm, more preferably more than 1.5 μm, particularly preferably more than 2 μm, preferably less than 1000 μm, more preferably Less than 500 μm, be still more preferably less than 300 μm, more preferably less than 100 μm, more preferably less than 50 μm, Still more preferably it is less than 30 μm, particularly preferably less than 5 μm, most preferably less than 3 μm.If base particle is flat Equal particle diameter is more than above-mentioned lower limit, then the contact area of electroconductive particle and electrode becomes big, therefore, can further improve electrode Between conducting reliability, further reduce via electroconductive particle connect interelectrode connection resistance.In addition, by non- When electrolysis is plated in base particle surface formation conductive layer, it is not susceptible to condense, is not easy to form the electroconductive particle of cohesion.Such as The average grain diameter of fruit base particle is that then electroconductive particle is easily sufficiently compressed, interelectrode company below the above-mentioned upper limit Connecting resistance further reduces, and can further reduce interelectrode interval.
The average grain diameter of above-mentioned base particle is particularly preferably more than 0.1 μm and less than 5 μm.Above-mentioned matrix material grain When in the range of 0.1~5 μm, interelectrode interval reduces the average grain diameter of son, and even if the thickness of increase conductive layer, It can obtain less electroconductive particle.From can further reduce it is interelectrode interval, even in increase conductive layer thickness when Also from the viewpoint of can obtain smaller electroconductive particle, the average grain diameter of above-mentioned base particle is preferably more than 0.5 μm, More preferably more than 2 μm, preferably less than 3 μm.
Above-mentioned average grain diameter represents number average bead diameter.The average grain diameter can use such as Coulter-counter (Beckman Coulter company systems) it is measured.
The gross thickness of above-mentioned 1st conductive layer and above-mentioned 2nd conductive layer (the overall thickness of conductive layer) is preferably more than 5nm, More preferably more than 10nm, more preferably more than 20nm, particularly preferably more than 50nm, preferably below 1000nm, more Preferably below 800nm, more preferably below 500nm, particularly preferably below 400nm, most preferably below 300nm. If the overall thickness of conductive layer is more than above-mentioned lower limit, the electric conductivity of electroconductive particle becomes more good.It is if conductive The overall thickness of layer is below the above-mentioned upper limit, then the difference of the thermal coefficient of expansion of base particle and metal level diminishes, metal level It is not easy to peel off from base particle.
As the method that the 1st, the 2nd conductive layer is formed on the surface of above-mentioned base particle, it can enumerate and pass through non-electrical Solution plating forms the method for the 1st, the 2nd conductive layer and by electroplating method for forming the 1st, the 2nd conductive layer etc..
Above-mentioned 1st conductive layer can also contain other gold beyond nickel and phosphorus in the range of not hindering the purpose of the present invention Category.Above-mentioned 2nd conductive layer can also contain other metals beyond palladium in the range of the purpose of the present invention is not hindered.As upper Other metals are stated, such as can be enumerated：Au Ag Pt Pd, zinc, iron, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, Tungsten, molybdenum, silicon and tin-doped indium oxide (ITO) etc..In addition, above-mentioned 1st conductive layer can also contain palladium.Above-mentioned 2nd conductive layer Phosphorus can be contained.
In the case where the above-mentioned 1st, the 2nd conductive layer contain above-mentioned other metals, above-mentioned other metals in the 1st conductive layer Content and the contents of above-mentioned other metals in the 2nd conductive layer be respectively preferably below 20 weight %, more preferably 10 weight % Hereinafter, more preferably below 5 weight %, particularly preferably below 1 weight %.
Such as electroconductive particle 1, electroconductive particle of the invention preferably has projection on the surface of electric conductivity.Above-mentioned projection is excellent Elect as multiple.By the way that above-mentioned core material is embedded in above-mentioned conductive layer, it can make above-mentioned conductive layer that there is projection in outer surface. By the electrode surface of electroconductive particle connection mostly formed with oxide film thereon.There is the electroconductive particle of projection in use Under, by configuring electroconductive particle between electrode and being pressed, above-mentioned oxide film thereon is effectively excluded using projection.By This, can be such that the conductive layer of electrode and electroconductive particle more effectively contacts, and interelectrode connection resistance further reduces.Enter one Step, in the case where electroconductive particle possesses megohmite insulant on surface or using electroconductive particle be scattered in resin and as leading In the case of electric material (anisotropic conductive material etc.) use, using the projection of electroconductive particle, conduction can be effectively excluded Resin component between property particle and electrode.Thus, interelectrode conducting reliability uprises.
As the method for forming projection on the surface of above-mentioned electroconductive particle, can enumerate：On the surface of base particle After adhering to core material, pass through the method for electroless plating formation conductive layer；And by electroless plating base particle table After face forms conductive layer, adhere to core material, and method that conductive layer is further formed by electroless plating etc..As in formation Other methods of projection are stated, can be enumerated after forming the 1st conductive layer on the surface of base particle, on the 1st conductive layer Core material is configured, the method for then forming the 2nd conductive layer；And formed on the surface in base particle in conductive layer Between stage addition core material method etc..
As the method for the surface attachment core material in above-mentioned base particle, such as can enumerate：To matrix material grain Core material is added in the dispersion liquid of son, core material is attached to the surface of base particle for example, by Van der Waals force collection coalescence Method；And core material is added into the container for add base particle, made by machinery caused by container rotation etc. With the method on surface etc. for making core material be attached to base particle.Wherein, due to easily controllable accompanying core material Amount, it is therefore preferable that making the method on the surface for the base particle that core material collection coalescence is attached in dispersion liquid.
As the material for forming above-mentioned core material, conductive material and non-conducting material can be enumerated.As above-mentioned conduction Property material, such as can enumerate：The electrically conductive, non-metallics such as metal, metal oxide, graphite and electric conductive polymer etc..As upper Electric conductive polymer is stated, polyacetylene etc. can be enumerated.As above-mentioned non-conducting material, can enumerate：Silica, aluminum oxide and Zirconium oxide etc..Wherein, due to that can improve electric conductivity and then connection resistance can be effectively reduced, it is therefore preferable that metal.It is excellent It is metallic to choose and state core material.
As above-mentioned metal, such as can enumerate：Gold, silver, copper, platinum, zinc, iron, lead, tin, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, The metals such as bismuth, germanium and cadmium and tin-lead alloy, tin-copper alloy, tin-silver alloy, tin-lead-silver alloy and tungsten carbide etc. are by two Alloy that the metal of the kind above is formed etc..Wherein, preferably nickel, copper, silver or gold.The metal of above-mentioned composition core material and above-mentioned composition The metal of conductive layer can be with identical, can also be different.The metal of above-mentioned composition core material preferably comprises nickel.In addition, as above-mentioned Metal oxide, it can enumerate：Aluminum oxide, silica and zirconium oxide etc..
The shape of above-mentioned core material is not particularly limited.Core material is preferably shaped to bulk.As core material, such as can To enumerate：The block of particle shape, multiple fine particles condense the cohesion block formed and unbodied 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, excellent Elect less than 0.9 μm, more preferably less than 0.2 μm as.If the average diameter of above-mentioned core material is more than above-mentioned lower limit and above-mentioned Below the upper limit, then interelectrode connection resistance can be effectively reduced.
" average diameter (average grain diameter) " of above-mentioned core material represents number average diameter (number average bead diameter).Being averaged for core material is straight Footpath by using any 50 core materials of electron microscope or observation by light microscope and can calculate average value to try to achieve.
Inorganic particulate can also be configured on the surface of above-mentioned core material.The inorganic particulate being configured on core material surface is excellent Elect as multiple.Inorganic particulate can also be adhered on the surface of core material.Can also use possess such inorganic particulate and core The compound particle of material.It is preferred that the size (average diameter) of inorganic particulate is smaller than the size (average diameter) of core material, preferably on It is inorganic particles to state inorganic particulate.
As the material for the above-mentioned inorganic particulate being configured on above-mentioned core material surface, can enumerate：Barium titanate (Mohs' hardness 4.5), silica (silica, Mohs' hardness 6~7), zirconium oxide (Mohs' hardness 8~9), aluminum oxide (Mohs' hardness 9), Tungsten carbide (Mohs' hardness 9) and diamond (Mohs' hardness 10) etc..Above-mentioned inorganic particulate is preferably silica, zirconium oxide, oxygen Change aluminium, tungsten carbide or diamond, preferably also silica, zirconium oxide, aluminum oxide or diamond.The Mohs of above-mentioned inorganic particulate Hardness is preferably more than 5, and more preferably more than 6.It is preferred that the Mohs' hardness of above-mentioned inorganic particulate is more than the Mohs of above-mentioned conductive layer Hardness.It is preferred that the Mohs' hardness of above-mentioned inorganic particulate is more than the Mohs' hardness of above-mentioned 2nd conductive layer.The Mohs of above-mentioned inorganic particulate The poor absolute value of hardness and the Mohs' hardness of above-mentioned conductive layer and the Mohs' hardness of above-mentioned inorganic particulate are led with the above-mentioned 2nd The poor absolute value of the Mohs' hardness of electric layer is preferably more than 0.1, more preferably more than 0.2, more preferably more than 0.5, Particularly preferably more than 1.In addition, when inorganic particulate is harder than the whole metals for forming first, second layer, can more effectively send out Wave the reducing effect of connection resistance.
The average grain diameter of above-mentioned inorganic particulate is preferably more than 0.0001 μm, more preferably more than 0.005 μm, is preferably Less than 0.5 μm, more preferably less than 0.1 μm.If the average grain diameter of above-mentioned inorganic particulate be above-mentioned lower limit more than and it is above-mentioned on Limit is following, then can be effectively reduced interelectrode connection resistance.
" average grain diameter " of above-mentioned inorganic particulate represents number average bead diameter.The average grain diameter of inorganic particulate can be by using electronics Microscope or any 50 inorganic particulates of observation by light microscope simultaneously calculate average value to try to achieve.
In the case of the compound particle of inorganic particulate being configured with the surface using above-mentioned core material, above-mentioned compound particle Average diameter (average grain diameter) be preferably more than 0.0012 μm, more preferably more than 0.0502 μm, preferably less than 1.9 μm, More preferably less than 1.2 μm.If the average diameter of above-mentioned compound particle is more than above-mentioned lower limit and below the above-mentioned upper limit, can Enough it is effectively reduced interelectrode connection resistance.
" average diameter (average grain diameter) " of above-mentioned compound particle represents number average diameter (number average bead diameter).Above-mentioned compound particle Average diameter by using any 50 compound particles of electron microscope or observation by light microscope and average value can be calculated Try to achieve.
Such as electroconductive particle 1, electroconductive particle of the invention is preferably provided with being configured on the outer surface of above-mentioned 2nd conductive layer Megohmite insulant.In this case, if electroconductive particle is used for into interelectrode connection, it is not likely to produce between adjacent electrode Short circuit.Specifically, when multiple electroconductive particles contact, due to megohmite insulant between multiple electrodes be present, therefore, it is not susceptible to Short circuit in transverse direction between adjacent electrode rather than between upper/lower electrode.It should be noted that when carrying out interelectrode connection, lead to Cross and pressurizeed using two electrode pair electroconductive particles, easily can be excluded between the conductive layer of electroconductive particle and electrode Megohmite insulant.In the case that electroconductive particle has projection on the surface of the 2nd conductive layer, electroconductive particle can be more easily excluded Conductive layer and electrode between megohmite insulant.Above-mentioned megohmite insulant is preferably insulative resin layer or insulating properties particle, more excellent Elect insulating properties particle as.The insulating properties particle is preferably insulative resin particle.
As the concrete example of above-mentioned megohmite insulant, TPO, (methyl) acrylate polymer, (methyl) third can be enumerated Olefin(e) acid ester copolymer, block polymer, thermoplastic resin, the cross-linking agent of thermoplastic resin, thermosetting resin and water-soluble resin Deng.
As said polyolefins class, polyethylene, vinyl-vinyl acetate copolymer and ethylene-acrylate can be enumerated and be total to Polymers etc..As above-mentioned (methyl) acrylate polymer, poly- (methyl) methyl acrylate, poly- (methyl) acrylic acid second can be enumerated Ester and poly- (methyl) butyl acrylate etc..As above-mentioned block polymer, it is common that polystyrene, cinnamic acrylic ester can be enumerated Polymers, SB types styrene-butadiene block copolymer and SBS types styrene-butadiene block copolymer and these polymer Hydrogenation products etc..As above-mentioned thermoplastic resin, polyvinyl and ethylenic copolymer etc. can be enumerated.As above-mentioned heat Thermosetting resin, epoxy resin, phenolic resin and melmac etc. can be enumerated.As above-mentioned water-soluble resin, can enumerate poly- Vinyl alcohol, polyacrylic acid, polyacrylamide, PVP, polyoxyethylene and methylcellulose etc..Above-mentioned electric conductivity Particle more preferably possesses the insulating properties particle for being attached to above-mentioned conductive layer surface.In this case, if electroconductive particle used In interelectrode connection, then interelectrode short circuit adjacent in transverse direction is not only more not likely to produce, moreover, the upper/lower electrode of connection Between connection resistance further reduce.
As make insulating properties particle be attached to above-mentioned conductive layer surface method, chemical method and physics or machine can be enumerated Tool method etc..As above-mentioned chemical method, can enumerate：Pass through the different cohesion (ヘ テ ロ aggegations) based on Van der Waals force or electrostatic force Method adheres to insulating properties particle and the method being chemically bonded as needed on the conductive layer of metal surface particle.As above-mentioned Physically or mechanically, spray drying process, hydridization method, electrostatic adherence method, spray-on process, infusion process can be enumerated and utilize vacuum evaporation Method etc..Wherein, because megohmite insulant is not easily disconnected from, therefore preferably megohmite insulant is made to be attached to above-mentioned conduction by chemical bond The method on the surface of layer.
The particle diameter of above-mentioned insulating properties particle is preferably less than the 1/5 of the particle diameter of electroconductive particle.In this case, insulating properties The particle diameter of particle is not excessive, more can effectively realize the electrical connection using conductive layer.It is to lead in the particle diameter of insulating properties particle In the case of less than the 1/5 of the particle diameter of conductive particles, when adhering to insulating properties particle by different coacervation, insulating properties grain can be made Son is efficiently adsorbed on the surface of electroconductive particle.In addition, the average diameter of above-mentioned megohmite insulant (above-mentioned insulating properties particle) (average grain diameter) is preferably more than 5nm, more preferably more than 10nm, preferably below 1000nm, more preferably below 500nm. If the average diameter (average grain diameter) of above-mentioned megohmite insulant (above-mentioned insulating properties particle) is more than above-mentioned lower limit, adjacent leads Distance between conductive particles is more than the transition distance of electronics, is not susceptible to leak electricity.If above-mentioned megohmite insulant (above-mentioned insulating properties grain Son) average diameter (average grain diameter) for below the above-mentioned upper limit, then the pressure required when carrying out hot pressing and heat diminish.
" average diameter (average grain diameter) " of above-mentioned megohmite insulant represents number average diameter (number average bead diameter).Megohmite insulant is put down Equal diameter can utilize particle size distribution device etc. to try to achieve.
The CV values of the particle diameter of above-mentioned insulating properties particle are preferably less than 20%.If CV values are less than 20%, by insulating properties The thickness for the clad that particle is formed is uniform, and easy uniformly applied pressure during hot pressing is carried out between electrode, is not susceptible to lead It is logical bad.It should be noted that the CV values of above-mentioned particle diameter can be calculated using following formula.
Standard deviation/average grain diameter × 100 of CV values (%)=particle diameter of particle diameter
Particle diameter distribution can utilize particles distribution instrument etc. to be measured before metal surface particle is coated, after cladding It can be measured by graphical analysis of SEM photograph etc..
It should be noted that in order that the conductive layer of electroconductive particle exposes, the clad ratio of megohmite insulant be preferably 5% with On, preferably less than 70%.The clad ratio of above-mentioned megohmite insulant is the part by megohmite insulant cladding in conductive layer (or metal watch Face particle) surface area entirety in shared area.If above-mentioned clad ratio is more than 5%, between adjacent electroconductive particle More can effectively it be insulated by megohmite insulant.If above-mentioned clad ratio is less than 70%, need not be applied in connection electrode Add the heat and pressure more than necessary, can suppress the performance of the adhesive resin as caused by the megohmite insulant excluded reduces.
As above-mentioned insulating properties particle, it is not particularly limited, known inorganic particulate and organic polymer particle can be used. As above-mentioned inorganic particulate, the insulating properties inorganic particulate such as aluminum oxide, silica and zirconium oxide can be enumerated.
Above-mentioned organic polymer particle is preferably aggregated (altogether by one or more kinds of monomers with unsaturated double-bond It is poly-) obtained from resin particle.As the above-mentioned monomer with unsaturated double-bond, can enumerate：(methyl) acrylic acid；(methyl) third E pioic acid methyl ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid 2- second The own ester of base, (methyl) glycidyl acrylate, tetramethylol methane four (methyl) acrylate, trimethylolpropane tris (first Base) acrylate, glycerine three (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (the first of (poly-) propane diols two Base) (methyl) esters of acrylic acid such as acrylate, 1,4- butanediols two (methyl) acrylate；Vinyl ethers；Vinyl chloride；Benzene Ethene；The styrene compounds such as divinylbenzene, acrylonitrile etc..Wherein, (methyl) esters of acrylic acid is preferably used.
In order that above-mentioned insulating properties particle is attached to the conductive layer of electroconductive particle, above-mentioned insulating properties particle by different cohesion It is preferred that there is polar functional group.As the polar functional group, such as ammonium, sulfonium base, phosphate and hydroxyl silicyl can be enumerated Deng.Above-mentioned polar functional group can be imported by making to have the monomer copolymerization of above-mentioned polar functional group and unsaturated double-bond.
As the monomer with above-mentioned ammonium, can enumerate：Methacrylic acid N, N- dimethylaminoethyl, N, N- dimethylaminos Propylacrylamide and N, N, N- trimethyl-N-2- methylacryoyloxyethyl ammonium chlorides etc..As the list with above-mentioned sulfonium base Body, it can enumerate：Methacrylic acid pheiiyldimetliyl sulfonium Methylsulfate etc..As the monomer with above-mentioned phosphate, can enumerate： Methacrylic acid (acid phosphinylidyne epoxide) ethyl ester (acid phosphoxy ethyl methacrylate), methacrylic acid (acid Formula phosphinylidyne epoxide) propyl ester (acid phosphoxy propyl methacrylate), (acid phosphinylidyne epoxide) polyoxygenated Asia second Base monomethacryiate (acid phosphoxy polyoxyethylene glycol monomethacrylate) And (acid phosphinylidyne epoxide) oxide glycols monomethacrylates (acid phosphoxy Polyoxypropylene glycol monomethacrylate) etc.., can as the monomer with above-mentioned hydroxyl silicyl Enumerate：Vinyl ortho-siliformic acid and 3- methacryloxypropyl ortho-siliformic acids etc..
As other methods that polar functional group is imported to above-mentioned insulating properties particle surface, can enumerate to use has polar group Method of the radical initiator of group as initiator when polymerizeing above-mentioned monomer with unsaturated double-bond.As it is above-mentioned from By base initiator, such as can enumerate：2,2 '-azo double { 2- methyl-N- [2- (1- hydroxybutyls)]-propionamide }, 2,2 '-azos Double [2- (2- imidazoline -2- bases) propane] and 2,2 '-azo double (2- amidine propanes) and their salt etc..
(conductive material)
The conductive material of the present invention contains above-mentioned electroconductive particle and adhesive resin.Above-mentioned electroconductive particle is preferably scattered Conductive material use is made in adhesive resin.Above-mentioned conductive material is preferably anisotropic conductive material.This is respectively to different Property conductive material include and be used to turn on conductive material between upper/lower electrode.
Above-mentioned adhesive resin is not particularly limited.As above-mentioned adhesive resin, the resin of generally usable insulating properties. As above-mentioned adhesive resin, such as can enumerate：Vinylite, thermoplastic resin, curable resin, thermoplastic block Thing and elastomer etc..Above-mentioned adhesive resin can be used only a kind, can also be applied in combination two or more.
As above-mentioned vinylite, such as can enumerate：Vinyl acetate resin, acrylic resin and styrene resin Deng.As above-mentioned thermoplastic resin, such as can enumerate：Vistanex, vinyl-vinyl acetate copolymer and polyamide resin Fat etc..As above-mentioned curable resin, such as can enumerate：Epoxy resin, polyurethane resin, polyimide resin and unsaturation Polyester resin etc..In addition, above-mentioned curable resin can be normal temperature cured type resin, thermohardening type resin, photocurable resin Or wet-cured type resin.Above-mentioned curable resin can be applied in combination with curing agent.As above-mentioned thermoplastic block copolymers, example It can such as enumerate：SBS, SIS, benzene The hydrogenation products of ethylene-butadiene-styrene block copolymer and adding for SIS Hydrogen product etc..As above-mentioned elastomer, such as can enumerate：Styrene butadiene copolymers rubber and acrylonitrile-styrene are embedding Section copolymer rubber etc..
In above-mentioned conductive material in addition to above-mentioned electroconductive particle and above-mentioned adhesive resin, it can also contain and for example fill Agent, extender, softening agent, plasticizer, polymerization catalyst, curing catalysts, colouring agent, antioxidant, heat stabilizer, light are stable The various additives such as agent, ultra-violet absorber, lubricant, antistatic additive and fire retardant.
The method that above-mentioned electroconductive particle is scattered in above-mentioned adhesive resin is set to use existing known scattered side Method, it is not particularly limited.As the method for making above-mentioned electroconductive particle be scattered in above-mentioned adhesive resin, example can be enumerated Such as：After above-mentioned electroconductive particle is made an addition in above-mentioned adhesive resin, be kneaded with planetary mixer etc. so that its Scattered method；Above-mentioned electroconductive particle is evenly dispersed in water or organic solvent using homogenizer etc., then add In above-mentioned adhesive resin, it is kneaded with planetary mixer etc. so that its scattered method；And by above-mentioned adhesive resin After being diluted with water or organic solvent etc., above-mentioned electroconductive particle is added, is kneaded with planetary mixer etc. so that its point Scattered method etc..
The conductive material of the present invention can be made into electroconductive paste or conducting film uses.It is conducting film in the conductive material of the present invention In the case of, the film without electroconductive particle can also be laminated on the conducting film containing electroconductive particle.Above-mentioned electroconductive paste is preferred Pasted for anisotropic conductive.Above-mentioned conducting film is preferably anisotropic conductive film.
From the viewpoint of the connecting portion suppressed in connection structural bodies produces space, further improves conducting reliability, on It is preferably electroconductive paste to state conductive material.It is preferred that above-mentioned conductive material is electroconductive paste and is to be coated on connection pair with the state of pasty state As the conductive material of the upper surface of part.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned adhesive resin is preferably more than 10 weight %, more preferably More than 30 weight %, more preferably more than 50 weight %, preferably below 90.99 weight %.If above-mentioned adhesive resin Content is that then electroconductive particle is efficiently configured between electrode, interelectrode conducting more than above-mentioned lower limit and below the above-mentioned upper limit Reliability further improves.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned electroconductive particle is preferably more than 0.01 weight %, more excellent Elect as more than 0.1 weight %, preferably below 80 weight %, more preferably below 40 weight %, more preferably 20 weight % with Under, particularly preferably below 10 weight %.If the content of above-mentioned electroconductive particle be above-mentioned lower limit more than and the above-mentioned upper limit with Under, then interelectrode conducting reliability further improves.
(connection structural bodies)
By using electroconductive particle of the invention or use the conduction containing the electroconductive particle and adhesive resin Material is attached to connecting object part, can obtain connection structural bodies.
Above-mentioned connection structural bodies possesses the 1st connecting object part, the 2nd connecting object part and connects the 1st, the 2nd company Connect the connecting portion of object Part, the connecting portion be preferably by the present invention the connection structural bodies that is formed of electroconductive particle or by The connection structural bodies that conductive material (anisotropic conductive material etc.) containing the electroconductive particle and adhesive resin is formed. In the case of using electroconductive particle, connecting portion sheet is as electroconductive particle.That is, the 1st, the 2nd connecting object part is by electric conductivity Particle connects.
Fig. 3 schematically shows the company for the electroconductive particle for having used first embodiment of the invention with front section view Connect structure.
Connection structural bodies 51 shown in Fig. 3 possesses the 1st connecting object part 52, the 2nd connecting object part 53 and connection The connecting portion 54 of 1st, the 2nd connecting object part 52,53.Connecting portion 54 is by consolidating the conductive material containing electroconductive particle 1 Change and formed.It should be noted that in figure 3, in order to illustrate conveniently, electroconductive particle 1 is shown with sketch.It can also use The grade of electroconductive particle 11 replaces electroconductive particle 1.
1st connecting object part 52 has multiple electrodes 52b in upper surface 52a (surface).2nd connecting object part 53 exists Lower surface 53a (surface) has multiple electrodes 53b.Electrode 52b and electrode 53b is electrically connected by one or more electroconductive particles 1 Connect.Thus, the 1st, the 2nd connecting object part 52,53 is electrically connected by electroconductive particle 1.
The manufacture method of above-mentioned connection structural bodies is not particularly limited.An example as the manufacture method of connection structural bodies Son, it can enumerate：Above-mentioned conductive material is configured between the 1st connecting object part and the 2nd connecting object part and obtains layered product Afterwards, method for the layered product being heated and being pressurizeed etc..The pressure of above-mentioned pressurization is 9.8 × 104~4.9 × 106Pa or so. The temperature of above-mentioned heating is 120~220 DEG C or so.
As above-mentioned connecting object part, can specifically enumerate：The electronic units such as semiconductor chip, capacitor and diode, And electronic unit such as circuit substrate such as printed base plate, flexible printing substrate and glass substrate etc..Above-mentioned connecting object part is excellent Elect electronic unit as.Above-mentioned electroconductive particle is preferred for the electrical connection of the electrode of electronic unit.
As the electrode for being arranged at above-mentioned connecting object part, 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 printing substrate, It is preferred that above-mentioned electrode is gold electrode, nickel electrode, tin electrode or copper electrode.In the situation that above-mentioned connecting object part is glass substrate Under, preferably above-mentioned electrode is aluminium electrode, copper electrode, molybdenum electrode or tungsten electrode.It should be noted that it is aluminium electrode in above-mentioned electrode In the case of, can be the electrode only formed by aluminium, or the electricity that stacking aluminium lamination forms on the surface of metal oxide layer Pole.As the material of above-mentioned metal oxide layer, can enumerate doped with the indium oxide of trivalent metallic element and doped with trivalent gold Belong to zinc oxide of element etc..As above-mentioned trivalent metallic element, can enumerate：Sn, Al and Ga etc..
As other occupation modes of the electroconductive particle of the present invention, can enumerate：Using electroconductive particle as inciting somebody to action Form the conductive material electrically connected between the upper and lower base plate of liquid crystal display cells.Including electroconductive particle is mixed and is scattered in thermosetting Property resin or hot UV and with curable resin, are coated on the substrate of side with point-like, and the method being bonded with counter substrate；With And electroconductive particle is mixed and is scattered in perimeter seal, wire is coated into, so as to not only be used to seal but also be used for upper and lower base Method of the electrical connection of plate etc..Above-mentioned any occupation mode is applied to the electroconductive particle of the present invention.In addition, the present invention's leads Conductive particles are configured with the 1st, the 2nd conductive layer on the surface of base particle, therefore, using the excellent of base particle Different elasticity is realized in the case where not damaging transparency carrier etc. to be conductively connected.
Hereinafter, in conjunction with the embodiments and comparative example further illustrates the present invention.The present invention is not limited to following reality Apply example.
(embodiment 1)
(1) process for electroless nickel plating process
Prepare divinylbenzene resin particle (4 μm of average grain diameter, CV values 5%, ponding chemical industrial company system “Micropearl SP-204”).After 10 weight % solution of the resin particle ion adsorbent are handled 5 minutes, sulphur is used The 0.01 weight % aqueous solution of sour palladium is handled 5 minutes, is then added dimethylamino borine and is carried out reduction treatment, is then filtered And washing, thus, obtain being attached with the resin particle of palladium.
Then, the solution of the sodium succinate containing 1 weight % and 500mL ion exchange water is prepared.Added into the solution 10g is attached with the resin particle of palladium and mixed, and is prepared for slurry, further adds sulfuric acid, and the pH of slurry is adjusted into 5.
Prepare the nickel sulfate containing 10 weight %, 10 weight % sodium hypophosphite, 4 weight % sodium hydroxide and 20 weight % Nickel liquid 52mL early stage of sodium succinate.PH5 slurry is reached 80 DEG C, and continuously dripped with 5mL/ minutes into 80 DEG C of slurry Add resulting nickel liquid early stage, stir 20 minutes, thus carry out plating reaction.Confirm not coagulate significantly in plating reaction After poly- and hydrogen-free produces, terminate plating reaction.
Then, after the sodium hydroxide for preparing the nickel sulfate containing 30 weight %, 10 weight % sodium hypophosphite and 5 weight % Phase nickel liquid 100mL.Then, the pH of the solution after terminating using the plating reaction that early stage, nickel liquid was carried out is adjusted to 9.0, for anti- The purpose only condensed, the temperature of solution is reduced to 30 DEG C from 80 DEG C.Continuously it is added dropwise with 5mL/ minutes into 30 DEG C of solution Later stage nickel liquid, and stir 55 minutes, thus carry out plating reaction.Then, separation of solid and liquid is carried out, has obtained middle nickel particles.
Then, the solution of the sodium succinate containing 1 weight % and 500mL ion exchange water is prepared.Added into the solution Middle nickel particles through whole amount obtained from separation of solid and liquid are simultaneously mixed, and are prepared for slurry.Then, it is molten using sodium hydroxide The pH of slurry is adjusted to 9.0 by liquid, and liquid temperature is held in into 30 DEG C.
Then, the whole nickel of the sodium hydroxide of the nickel sulfate containing 50 weight %, 5 weight % sodium hypophosphite and 5 weight % is prepared Liquid 20mL.Then, whole nickel liquid is continuously added dropwise with 5mL/ minutes into 30 DEG C of pulp solution, and stirred 5 minutes, thus make plating Reaction is applied to carry out.
Thus, obtained on the surface of resin particle formed with the particle containing nickel and the 1st conductive layer of phosphorus.Gained grain The thickness of 1st conductive layer of son is 0.1 μm.
(2) electroless plating palladium process
Obtained particle 10g is scattered in 500mL ion exchange water using ultrasonic processor, obtains suspension. Prepare the ethylenediamine 0.04mol/L containing palladium sulfate 0.02mol/L, as complexant, the sodium formate as reducing agent The pH of 0.06mol/L and crystallization modifier is 10.0 plating solution.Gained is slowly added while in 50 DEG C of stirring gained suspension The plating solution arrived, electroless plating palladium is carried out, forms the 2nd conductive layer.Terminate at the time of the thickness of the 2nd conductive layer reaches 0.04 μm Electroless plating palladium.Then, washed, be dried in vacuo, be resulting on the outer surface containing nickel and the 1st conductive layer of phosphorus Form the electroconductive particle of the 2nd conductive layer containing palladium.
(embodiment 2)
(1) process for electroless nickel plating process (in the process that the surface of the 1st conductive layer forms projection)
1-1) palladium attachment process
Prepare divinylbenzene resin particle (4 μm of average grain diameter, CV values 5%, ponding chemical industrial company system “Micropearl SP-204”).The resin particle is etched, washed.Then, to containing 8 weight % palladium catalysts Resin particle is added in 100mL palladium catalyst liquid, is stirred.Then, filtered, washed.To pH6 0.5 weight % bis- Resin particle is added in methylamino borine liquid, has obtained being attached with the resin particle of palladium.
1-2) core material attachment process
The resin particle 10g for being attached with palladium is stirred 3 minutes in 300mL ion exchange water, is allowed to scattered, is divided Dispersion liquid.Then, 1g metallic Ni particles slurry (Mitsui Metal Co., Ltd.'s company system " 2020SUS ", average grain diameter 200nm) was added through 3 minutes It is added in above-mentioned dispersion liquid, has obtained being attached with the resin particle of core material.
1-3) process for electroless nickel plating process
By process for electroless nickel plating process similarly to Example 1, obtained on the surface of resin particle formed with containing 1st conductive layer of nickel and phosphorus and there is the particle of projection on surface.The thickness of 1st conductive layer of gained particle is 0.1 μm.
(2) electroless plating palladium process
Via electroless plating palladium process in the same manner as in Example 1, obtain in the outer surface containing nickel and the 1st conductive layer of phosphorus On form the electroconductive particle of the 2nd conductive layer containing palladium.
(embodiment 3)
(1) making of insulating properties particle
Four neck removable lids (4 Star mouth セ パ ラ Block Le カ バ ー), agitating paddle, triple valve, condenser pipe and temperature are being installed In the 1000mL of sensor removable flask, weigh containing methyl methacrylate 100mmol, N, N, N- trimethyls-N-2- Double (2- amidine propanes) the dihydrochloride 1mmol of methylacryoyloxyethyl ammonium chloride 1mmol and 2,2 '-azo monomer composition In ion exchange water and make the solid constituent point rate of the monomer composition be 5 weight %, then, stirred with 200rpm Mix, carried out polymerizeing for 24 hours in nitrogen atmosphere, at 70 DEG C.After reaction terminates, it is freeze-dried, having obtained surface has Ammonium, average grain diameter are the insulating properties particle (insulative resin particle) that 220nm and CV values are 10%.
Insulating properties particle is dispersed under ultrasonic activation in ion exchange water, obtain 10 weights of insulating properties particle Measure % aqueous dispersions.
The electroconductive particle 10g obtained in embodiment 1 is scattered in ion exchange water 500mL, add insulating properties particle Aqueous dispersions 4g, and be stirred at room temperature 6 hours.After 3 μm of granular membrane filtering, further washed with methanol Wash, dry, obtained being attached with the electroconductive particle of insulating properties particle.
Observed using SEM (SEM), 1 layer is as a result only formd on the surface of electroconductive particle by exhausted The clad that edge particle is formed.Cladding area (the i.e. particle diameter of insulating properties particle of insulating properties particle is calculated using image analysis Projected area) relative to the ratio of areas of 2.5 μm away from electroconductive particle center, as a result, clad ratio 30%.
(embodiment 4)
In addition to the electroconductive particle for being altered to obtain in embodiment 2 by the electroconductive particle obtained in embodiment 1, with Embodiment 3 is similarly implemented, and has obtained being attached with the electroconductive particle of insulating properties particle.Clad ratio is 30%.
(embodiment 5)
(1) process for electroless nickel plating process
Prepare divinylbenzene resin particle (4 μm of average grain diameter, CV values 5%, ponding chemical industrial company system “Micropearl SP-204”).After 10 weight % solution of the resin particle ion adsorbent are handled 5 minutes, sulphur is used The 0.01 weight % aqueous solution of sour palladium is handled 5 minutes, is then added dimethylamino borine and is carried out reduction treatment, is then filtered And washing, thus, obtain being attached with the resin particle of palladium.
Then, the solution of the sodium succinate containing 1 weight % and 500mL ion exchange water is prepared.Added into the solution 10g is attached with the resin particle of palladium and mixed, and is prepared for slurry, further adds sulfuric acid, and the pH of slurry is adjusted to 6.5。
Prepare the nickel sulfate containing 10 weight %, 10 weight % sodium hypophosphite, 4 weight % sodium hydroxide and 20 weight % Nickel liquid 52mL early stage of sodium succinate.PH6.5 slurry is set to reach 80 DEG C, and into 80 DEG C of slurry with the flow of 5mL/ minutes Resulting nickel liquid early stage is continuously added dropwise, stirs 20 minutes, thus carries out plating reaction.Confirm do not have in plating reaction After significant cohesion and hydrogen-free produce, terminate plating reaction.
Then, after the sodium hydroxide for preparing the nickel sulfate containing 30 weight %, 10 weight % sodium hypophosphite and 5 weight % Phase nickel liquid 100mL.Then, the pH of the solution after terminating using the plating reaction that early stage, nickel liquid was carried out is adjusted to 9.0, for anti- The purpose only condensed, the temperature of solution is reduced to 30 DEG C from 80 DEG C.It is continuous with the flow of 5mL/ minutes into 30 DEG C of solution Later stage nickel liquid is added dropwise in ground, and stirs 55 minutes, thus carries out plating reaction, then, carries out separation of solid and liquid, has obtained middle Nickel particle Son.
Then, the solution of the sodium succinate containing 1 weight % and 500mL ion exchange water is prepared.Added into the solution Middle nickel particles through whole amount obtained from separation of solid and liquid are simultaneously mixed, and are prepared for slurry, then, molten using sodium hydroxide The pH of slurry is adjusted to 9.5 by liquid, and liquid temperature is held in into 30 DEG C.
Then, the whole nickel of the sodium hydroxide of the nickel sulfate containing 60 weight %, 5 weight % sodium hypophosphite and 5 weight % is prepared Liquid 20mL.Then, whole nickel liquid is continuously added dropwise into 30 DEG C of pulp solution, and stirs 5 minutes, thus carries out plating reaction.
So, obtained on the surface of resin particle formed with the particle containing nickel and the 1st conductive layer of phosphorus.Gained grain The thickness of 1st conductive layer of son is 0.1 μm.
(2) electroless plating palladium process
In addition to being altered to above-mentioned process for electroless nickel plating process, implement similarly to Example 2, obtained containing nickel and The 2nd conductive layer containing palladium is formd on the outer surface of 1st conductive layer of phosphorus and there is the electroconductive particle of projection on surface.
(embodiment 6)
(1) process for electroless nickel plating process
Prepare divinylbenzene resin particle (4 μm of average grain diameter, CV values 5%, ponding chemical industrial company system “Micropearl SP-204”).After 10 weight % solution of the resin particle ion adsorbent are handled 5 minutes, sulphur is used The 0.01 weight % aqueous solution of sour palladium is handled 5 minutes, is then added dimethylamino borine and is carried out reduction treatment, is then filtered And washing, thus, obtain being attached with the resin particle of palladium.
Then, the solution of the sodium succinate containing 1 weight % and 500mL ion exchange water is prepared.Added into the solution 10g is attached with the resin particle of palladium and mixed, and is prepared for slurry, further adds sulfuric acid, and the pH of slurry is adjusted to 3.5。
Prepare the nickel sulfate containing 10 weight %, 10 weight % sodium hypophosphite, 4 weight % sodium hydroxide and 20 weight % Nickel liquid 52mL early stage of sodium succinate.PH3.5 slurry is reached 80 DEG C, and into 80 DEG C of slurry with 5mL/ minutes continuously Nickel liquid early stage obtained by being added dropwise, stir 20 minutes, thus carry out plating reaction.Confirm in plating reaction without significant After cohesion and hydrogen-free produce, terminate plating reaction.
Then, after the sodium hydroxide for preparing the nickel sulfate containing 30 weight %, 10 weight % sodium hypophosphite and 5 weight % Phase nickel liquid 100mL.Then, the pH of the solution after terminating using the plating reaction that early stage, nickel liquid was carried out is adjusted to 6.0, for anti- The purpose only condensed, the temperature of solution is reduced to 30 DEG C from 80 DEG C.Continuously it is added dropwise with 5mL/ minutes into 30 DEG C of solution Later stage nickel liquid, and stir 55 minutes, plating reaction is thus carried out, then, separation of solid and liquid is carried out, has obtained middle nickel particles.
Then, the solution of the sodium succinate containing 1 weight % and 500mL ion exchange water is prepared.Added into the solution Middle nickel particles through whole amount obtained from separation of solid and liquid are simultaneously mixed, and are prepared for slurry.Then, it is molten using sodium hydroxide The pH of slurry is adjusted to 10.5 by liquid, and liquid temperature is held in into 30 DEG C.
Then, the whole nickel of the sodium hydroxide of the nickel sulfate containing 50 weight %, 5 weight % sodium hypophosphite and 5 weight % is prepared Liquid 20mL.Then, whole nickel liquid is continuously added dropwise with 5mL/ minutes into 30 DEG C of pulp solution, and stirred 5 minutes, thus carried out Plating reacts.
So, obtained on the surface of resin particle formed with the particle containing nickel and the 1st conductive layer of phosphorus.Gained grain The thickness of 1st conductive layer of son is 0.1 μm.
(2) electroless plating palladium process
In addition to being changed to above-mentioned process for electroless nickel plating process, implement similarly to Example 1, obtained containing nickel and The electroconductive particle of the 2nd conductive layer containing palladium is formd on the outer surface of 1st conductive layer of phosphorus.
(embodiment 7)
In electroless plating palladium process, by the pH of plating solution be altered to 5.5 and will add plating solution suspension temperature become More into 80 DEG C, in addition, implement similarly to Example 1, obtained electroconductive particle.
In process for electroless nickel plating process, the pH for the slurry for adding nickel liquid early stage is altered to 10.5, later stage nickel liquid will be added The pH of solution be altered to 10.5, the content of the nickel sulfate in later stage nickel liquid be altered to 45 weight %, the dropwise addition by later stage nickel liquid Speed is altered to 10mL/ minutes (mixing time 27 minutes), the pH for the slurry for adding whole nickel liquid is altered to 10.5 and by eventually The rate of addition of nickel liquid is altered to 10mL/ minutes (mixing time 2.5 minutes), in addition, implements similarly to Example 1, Electroconductive particle is obtained.
(embodiment 8)
Except the pH that the slurry of nickel liquid early stage is added in process for electroless nickel plating process is altered into 10.5, addition later stage nickel liquid The pH of solution is altered to 10.5, the content of the nickel sulfate in later stage nickel liquid is altered to 45 weight %, the dropwise addition speed by later stage nickel liquid Degree is altered to 10mL/ minutes (mixing time 27 minutes), the pH for the slurry for adding whole nickel liquid is altered to 10.5 and by whole nickel The rate of addition of liquid was altered to beyond 10mL/ minutes (mixing time 2.5 minutes), is implemented similarly to Example 1, is led Conductive particles.
(reference example 1)
(1) process for electroless nickel plating process
Prepare divinylbenzene resin particle (4 μm of average grain diameter, CV values 5%, ponding chemical industrial company system “Micropearl SP-204”).After 10 weight % solution of the resin particle ion adsorbent are handled 5 minutes, sulfuric acid is used The 0.01 weight % aqueous solution of palladium is handled 5 minutes.Then, add dimethylamino borine and carry out reduction treatment, and filtered, washed Wash, resulting in the resin particle for being attached with palladium.
Then, prepare and the weight % solution of sodium succinate 1 that sodium succinate forms is dissolved in 500mL ion exchange water.To 10g is added in the solution to be attached with the resin particle of palladium and mixed, and is prepared for slurry.The pH of slurry is adjusted to 6.5.
Prepare the nickel sulfate containing 10 weight %, 10 weight % sodium hypophosphite, 4 weight % sodium hydroxide and 20 weight % Nickel liquid early stage of sodium succinate.By pH be adjusted to 6.5 above-mentioned slurry be heated up to 80 DEG C after, with the flow of 5mL/ minutes through 10 points Nickel liquid early stage is continuously added dropwise in clockwise slurry, stirs 20 minutes, thus carries out plating reaction.Confirm that hydrogen-free produces, terminate Plating reacts.
Then, after the sodium hydroxide for preparing the nickel sulfate containing 20 weight %, 20 weight % sodium hypophosphite and 5 weight % Phase nickel liquid.Into the solution after being terminated using the plating reaction that early stage, nickel liquid was carried out, with the flow of 10mL/ minutes through 20 minutes companies Later stage nickel liquid is added dropwise continuously, and is stirred, thus carries out plating reaction.So, nickel is contained on resin particle surface Terminate plating reaction at the time of reaching 0.1 μm with the thickness of the 1st conductive layer of phosphorus, obtain plating particle.The 1st of gained particle The thickness of conductive layer is 0.1 μm.
(2) electroless plating palladium process
Obtained particle 10g is scattered in ion exchange water 500mL using ultrasonic processor, obtains suspension.Side The suspension side is stirred in 50 DEG C and slowly adds ethylenediamine 0.04mol/ containing palladium sulfate 0.02mol/L, as complexant L, as reducing agent sodium formate 0.06mol/L and crystallization modifier pH10.0 plating solution, carry out electroless plating palladium, form 2nd conductive layer.Terminate electroless plating palladium at the time of the thickness of the 2nd conductive layer reaches 0.04 μm.Then, washed, vacuum Dry, resulting in the conduction that the 2nd conductive layer containing palladium is formd on the outer surface containing nickel and the 1st conductive layer of phosphorus Property particle.
(reference example 2)
(1) process for electroless nickel plating process
Prepare divinylbenzene resin particle (4 μm of average grain diameter, CV values 5%, ponding chemical industrial company system “Micropearl SP-204”).10 weight % solution of the resin particle ion adsorbent are handled 5 minutes, then use sulphur The sour weight % aqueous solution of palladium 0.01 is handled 5 minutes.Then, add dimethylamino borine and carry out reduction treatment, and filtered, washed Wash, resulting in the resin particle for being attached with palladium.
Then, prepare and the weight % solution of sodium succinate 1 that sodium succinate forms is dissolved in 500mL ion exchange water.To 10g is added in the solution to be attached with the resin particle of palladium and mixed, and prepares slurry.The pH of slurry is adjusted to 7.5.
Prepare the nickel sulfate containing 10 weight %, 6 weight % sodium hypophosphite, 4 weight % sodium hydroxide and 20 weight % Nickel liquid early stage of sodium succinate.By pH be adjusted to 7.5 above-mentioned slurry be heated up to 80 DEG C after, with the flow of 5mL/ minutes through 10 points Nickel liquid early stage is continuously added dropwise in clockwise slurry, stirs 20 minutes, thus carries out plating reaction.Confirm that hydrogen-free produces, terminate Plating reacts.
Then, after the sodium hydroxide for preparing the nickel sulfate containing 20 weight %, 20 weight % sodium hypophosphite and 5 weight % Phase nickel liquid.Into the solution after being terminated using the plating reaction that early stage, nickel liquid was carried out, with the flow of 10mL/ minutes through 20 minutes companies Later stage nickel liquid is added dropwise continuously, and is stirred, thus carries out plating reaction, forms the 1st conductive layer.On resin particle surface On the thickness of the 1st conductive layer containing nickel and phosphorus terminate plating reaction at the time of reach 0.1 μm, obtained plating particle.Institute The thickness for obtaining the 1st conductive layer of particle is 0.1 μm.
(2) electroless plating palladium process
In addition to being altered to above-mentioned process for electroless nickel plating process, implement in the same manner as reference example 1, obtained containing nickel and The electroconductive particle of the 2nd conductive layer containing palladium is formd on the outer surface of 1st conductive layer of phosphorus.
(reference example 3)
(1) process for electroless nickel plating process
Prepare the nickel sulfate hexahydrate compound containing 80g/L, 40g/L sodium hypophosphite monohydrate and 60g/L citric acid PH8.0 nickel-plating liquid 600mL.500mL distillations are added in being attached with the resin particle of core material for being obtained into embodiment 2 Water, and 600mL nickel-plating liquid is added with 10mL/ minutes, the pH of suspension is remained 8.0, while be stirred non-to carry out Electrolytic ni plating.In nickel plating, for the purpose for preventing cohesion, the temperature of suspension is reduced to 30 DEG C.In the thickness of the 1st conductive layer Degree terminates plating at the time of reaching 0.1 μm, has obtained plating particle.
(2) electroless plating palladium process
In addition to being altered to above-mentioned process for electroless nickel plating process, implement similarly to Example 2, obtained containing nickel and The 2nd conductive layer containing palladium is formd on the outer surface of 1st conductive layer of phosphorus and there is the electroconductive particle of projection on surface.
(reference example 4)
In addition to the pH of process for electroless nickel plating process is altered into 8.8, implement in the same manner as reference example 3, obtained containing The outer surface for having the 1st conductive layer of nickel and phosphorus forms the 2nd conductive layer containing palladium and has the electric conductivity grain of projection on surface Son.
(comparative example 1)
(1) process for electroless nickel plating process
Prepare divinylbenzene resin particle (4 μm of average grain diameter, CV values 5%, ponding chemical industrial company system “Micropearl SP-204”).10 weight % solution of the resin particle ion adsorbent are handled 5 minutes, then use sulphur The sour weight % aqueous solution of palladium 0.01 is handled 5 minutes.Then, add dimethylamino borine and carry out reduction treatment, and filtered, washed Wash, resulting in the resin particle for being attached with palladium.
Then, prepare and the weight % solution of sodium succinate 1 that sodium succinate forms is dissolved in 500mL ion exchange water.To 10g is added in the solution to be attached with the resin particle of palladium and mixed, and prepares slurry.The pH of slurry is adjusted to 7.5.
Prepare the nickel sulfate containing 10 weight %, 6 weight % sodium hypophosphite, 4 weight % sodium hydroxide and 20 weight % Nickel liquid early stage of sodium succinate.By pH be adjusted to 10.0 above-mentioned slurry be heated up to 80 DEG C after, with the flow of 5mL/ minutes through 10 Minute, nickel liquid early stage was continuously added dropwise into slurry, stirred 20 minutes, thus carried out plating reaction.Confirm that hydrogen-free produces, knot Beam plating reacts.
Then, after the sodium hydroxide for preparing the nickel sulfate containing 20 weight %, 20 weight % sodium hypophosphite and 5 weight % Phase nickel liquid.Into the solution after being terminated using the plating reaction that early stage, nickel liquid was carried out, with the flow of 10mL/ minutes through 20 minutes companies Later stage nickel liquid is added dropwise continuously, pH is held in 7.5 and stirred 55 minutes, has thus carried out plating reaction, then, carries out solid-liquid point From having obtained the middle nickel particles Jing Guo nickel plating.
Then, the solution of the sodium succinate containing 1 weight % and 500mL ion exchange water is prepared.Added into the solution Middle nickel particles through whole amount obtained from separation of solid and liquid are simultaneously mixed, and are prepared for slurry, then, molten using sodium hydroxide The pH of slurry is adjusted to 5.5 by liquid, and liquid temperature is held in into 50 DEG C.
Then, the whole nickel of the sodium hydroxide of the nickel sulfate containing 50 weight %, 5 weight % sodium hypophosphite and 5 weight % is prepared Liquid 20mL.Then, whole nickel liquid is continuously added dropwise with 5mL/ minutes into 50 DEG C of pulp solution, and stirred 5 minutes, thus make plating Reaction is applied to carry out.
Thus, obtained on the surface of resin particle formed with the particle containing nickel and the 1st conductive layer of phosphorus.Gained grain The thickness of 1st conductive layer of son is 0.1 μm.
(2) electroless plating palladium process
In addition to being altered to above-mentioned process for electroless nickel plating process, implement in the same manner as reference example 1, obtained containing nickel and The electroconductive particle of the 2nd conductive layer containing palladium is formd on the outer surface of 1st conductive layer of phosphorus.
(comparative example 2)
(1) process for electroless nickel plating process
Prepare divinylbenzene resin particle (4 μm of average grain diameter, CV values 5%, ponding chemical industrial company system “Micropearl SP-204”).10 weight % solution of the resin particle ion adsorbent are handled 5 minutes, then use sulphur The sour weight % aqueous solution of palladium 0.01 is handled 5 minutes.Then, add dimethylamino borine and carry out reduction treatment, and filtered, washed Wash, resulting in the resin particle for being attached with palladium.
Then, prepare and the weight % solution of sodium succinate 1 that sodium succinate forms is dissolved in 500mL ion exchange water.To 10g is added in the solution to be attached with the resin particle of palladium and mixed, and prepares slurry.The pH of slurry is adjusted to 7.5.
Prepare the nickel sulfate containing 10 weight %, 12 weight % sodium hypophosphite, 4 weight % sodium hydroxide and 20 weight % Nickel liquid early stage of sodium succinate.By pH be adjusted to 7.5 above-mentioned slurry be heated up to 80 DEG C after, with the flow of 5mL/ minutes through 10 points Nickel liquid early stage is continuously added dropwise in clockwise slurry, stirs 20 minutes, thus carries out plating reaction.Confirm that hydrogen-free produces, terminate Plating reacts.
Then, after the sodium hydroxide for preparing the nickel sulfate containing 20 weight %, 20 weight % sodium hypophosphite and 5 weight % Phase nickel liquid.Into the solution after being terminated using the plating reaction that early stage, nickel liquid was carried out, with the flow of 10mL/ minutes through 20 minutes companies Later stage nickel liquid is added dropwise continuously, pH is held in 6.0 and stirred 55 minutes, has thus carried out plating reaction, then, carries out solid-liquid point From having obtained middle nickel particles.
Then, the solution of the sodium succinate containing 1 weight % and 500mL ion exchange water is prepared.Added into the solution Middle nickel particles through whole amount obtained from separation of solid and liquid are simultaneously mixed, and are prepared for slurry.Then, it is molten using sodium hydroxide The pH of slurry is adjusted to 9.5 by liquid, and liquid temperature is held in into 30 DEG C.
Then, the whole nickel of the sodium hydroxide of the nickel sulfate containing 50 weight %, 5 weight % sodium hypophosphite and 5 weight % is prepared Liquid 20mL.Then, whole nickel liquid is continuously added dropwise with 5mL/ minutes into 30 DEG C of pulp solution, and stirred 5 minutes, thus make plating Reaction is applied to carry out.
Thus, obtained on the surface of resin particle formed with the particle containing nickel and the 1st conductive layer of phosphorus.Gained grain The thickness of 1st conductive layer of son is 0.1 μm.
(2) electroless plating palladium process
In addition to being altered to above-mentioned process for electroless nickel plating process, implement in the same manner as reference example 1, obtained containing nickel and The electroconductive particle of the 2nd conductive layer containing palladium is formd on the outer surface of 1st conductive layer of phosphorus.
(comparative example 3)
The particle 10g obtained in the process for electroless nickel plating process of embodiment 1 is scattered in ion using ultrasonic processor In exchanged water 500mL, suspension is obtained.Prepare ethylenediamine 0.08mol/L containing palladium sulfate 0.04mol/L, as complexant, As reducing agent hydrazine sulfate 0.10mol/L and crystallization modifier pH10.0 plating solution.While in 50 DEG C of stirring gained suspension Resulting plating solution is slowly added on side, has carried out electroless plating palladium, has terminated at the time of the thickness of conductive layer reaches 0.04 μm Electroless plating palladium, thus, electroconductive particle is obtained.It should be noted that in comparative example 3, the 1st conductive layer is not formed, The 2nd conductive layer is formd on the surface of base particle.
(comparative example 4)
In addition to not carrying out electroless palladium process, implement similarly to Example 1, obtained electroconductive particle.Need Illustrate, in comparative example 4, do not form the 2nd conductive layer, the 1st conductive layer is only formd on the surface of base particle.
(comparative example 5)
(1) process for electroless nickel plating process
Implement similarly to Example 1, obtained being attached with the resin particle of palladium.
Then, the solution of the sodium succinate containing 1 weight % and 500mL ion exchange water is prepared.Added into the solution 10g is attached with the resin particle of palladium and mixed, and is prepared for slurry, further adds sulfuric acid, and the pH of slurry is adjusted into 8.
Prepare the nickel sulfate containing 10 weight %, 15% hydrazine sulfate, 4 weight % sodium hydroxide and 20 weight % butanedioic acid Nickel liquid 52mL early stage of sodium.PH8 slurry is reached 80 DEG C, and gained is continuously added dropwise with 5mL/ minutes into 80 DEG C of slurry Nickel liquid early stage arrived, stir 20 minutes, thus carry out plating reaction.Confirm in plating reaction without significantly cohesion and nothing After hydrogen produces, terminate plating reaction.
Then, the later stage of the sodium hydroxide of the nickel sulfate containing 45 weight %, 15 weight % hydrazine sulfate and 5 weight % is prepared Nickel liquid 120mL.Then, the pH of the solution after terminating using the reaction of plating that early stage, nickel liquid was carried out is adjusted to 9.0, for preventing The purpose of cohesion, the temperature of solution is reduced to 60 DEG C from 80 DEG C.After being continuously added dropwise with 5mL/ minutes into 30 DEG C of solution Phase nickel liquid, and stir 55 minutes, thus carry out plating reaction.Then, separation of solid and liquid is carried out.
Thus, the particle of the 1st not phosphorous but nickeliferous conductive layer has been obtained foring on the surface of resin particle.Gained The thickness of 1st conductive layer of particle is 0.1 μm.
Then, by carrying out electroless plating palladium process similarly to Example 1, electroconductive particle has been obtained.Need to illustrate , it is not phosphorous in the 1st conductive layer in comparative example 5.
(evaluation)
Each content of phosphorus and nickel in (1) the 1st conductive layer
The cut film of gained electroconductive particle has been made using focused ion beam.Slice position is set to：From electric conductivity grain The position of the distance of center advance electroconductive particle half mass runoff of the surface of son to electroconductive particle.Use transmission electron microscope FE-TEM (Japan Electronics Corporation's system " JEM-2010FEF "), determines the 1st by energy dispersion type x-ray analysis equipment (EDS) and leads Each content of phosphorus and nickel in electric layer.Similarly, the phosphorus and nickel in the 1st conductive layer entirety of any 10 electroconductive particles are determined Each average content, and calculated the average value of 10 measured values.In addition, on the thickness direction of above-mentioned 1st conductive layer, The average content of phosphorus is (towards the thickness of outside 10% from the inner surface of the 1st conductive layer in above-mentioned 1st conductive layer of resin particle side Region A entirety in phosphorus average content) and above-mentioned 1st conductive layer of the 2nd conductive layer side in the average content of phosphorus (led from the 1st Play the average content towards phosphorus in the region B entirety of the thickness of inner side 10% in the outer surface of electric layer) evaluated.1st conductive layer Thickness is evaluated also by the above method.
The content of palladium in (2) the 2nd conductive layers
The cut film of gained electroconductive particle has been made using focused ion beam.Slice position is set to：From electric conductivity grain The position of the distance of center advance electroconductive particle half mass runoff of the surface of son to electroconductive particle.Use transmission electron microscope FE-TEM (Japan Electronics Corporation's system " JEM-2010FEF "), it is conductive to determine the 2nd by energy dispersion X-ray analysis device (EDS) The content of palladium in layer.Similarly, palladium and being averaged for phosphorus in the 2nd conductive layer entirety of any 10 electroconductive particles is determined to contain Amount, and calculated the average value of 10 measured values.The thickness of 2nd conductive layer is evaluated also by the above method.
(3) corrosion test 1 (connection resistance) of conductive layer
Two plate bases formed with the copper electrode that L/S is 100 μm/100 μm are prepared.In addition, prepare to lead containing gained The parts by weight of conductive particles 10, the epoxy resin (Mitsui Chemicals, Inc.'s system " Struct.Bond XN-5A ") as adhesive resin The anisotropic conductive of 85 parts by weight and the parts by weight of imidazole type curing agent 5 is pasted.
After anisotropic conductive paste is coated with a manner of electroconductive particle is contacted with copper electrode in the upper surface of substrate, with The mode for making copper electrode be contacted with electroconductive particle is laminated other substrates, and is pressed, and has obtained layered product.Then, in 180 DEG C to layered product heat 1 minute, thus make anisotropic conductive paste solidification, obtained connection structural bodies.
Connection resistance between the comparative electrode of connection structural bodies as obtained by determining four-end method, and gained measured value is made Resistance is connected for initial stage.
Then, 85 DEG C and 85% it is hot and humid under the conditions of place obtained by connection structural bodies.Determined and placed by four-end method The interelectrode connection resistance of connection structural bodies afterwards, and using gained measured value as the connection resistance after corrosion test.
(4) corrosion test 2 (insulaion resistance) of conductive layer
As shown in figure 4, having prepared to have sequentially formed nickel coating and Gold plated Layer on the surface of copper electrode and formd L/S and being The substrate of 20 μm/20 μm of comb electrodes copper pattern.In addition, prepare containing the parts by weight of gained electroconductive particle 10, as viscous Epoxy resin (Mitsui Chemicals, Inc.'s system " Struct.Bond XN-5A ") 85 parts by weight and imidazole type curing agent 5 of mixture resin The anisotropic conductive paste of parts by weight.
After the upper surface coating anisotropic conductive paste of the copper pattern of substrate, it is laminated alkali-free glass plate and is pressed, Electroconductive particle is set to be contacted with copper pattern.In the state of alkali-free glass plate is laminated with, heat 1 minute, thus make each in 180 DEG C Anisotropy electroconductive paste solidifies, and has obtained connection structural bodies.
The interelectrode insulaion resistance of the adjoining of connection structural bodies as obtained by determining four-end method, and by gained measured value As insulaion resistance at initial stage.
Then, 85 DEG C and 85% it is hot and humid under the conditions of place obtained by connection structural bodies.Determined and placed by four-end method The interelectrode insulaion resistance of the adjoining of connection structural bodies afterwards, and using gained measured value as the insulated electro after corrosion test Resistance.
(5) load test
Electroconductive particle obtained by use, with 1g electroconductive particles in 300cc glass system beaker:45g zirconia balls are (straight Footpath 1.0mm):The ratio of 17g toluene mixes each material, and utilizes diameter 30mm stainless steel blade with 400rpm/2 minutes Electroconductive particle is applied under conditions of being stirred and loaded.Then, confirm to whether there is conductive layer rupture and conductive layer from matrix The stripping on material particles surface.Load test is judged with following standards.
[criterion of load test]
○：Conductive layer does not produce rupture, and conductive layer is not from base particle sur-face peeling
△：Although conductive layer only generates slight rupture, at least a portion of conductive layer is from base particle surface Peel off
×：Conductive layer generates rupture, and at least a portion of conductive layer is from base particle sur-face peeling
As a result as shown in table 1 below, 2.

Claims (8)

1. a kind of electroconductive particle, it possesses：
Base particle,
Be configured on the surface of described matrix material particles and the 1st conductive layer containing nickel and phosphorus and
It is configured on the outer surface of the 1st conductive layer and the 2nd conductive layer containing palladium,
Wherein,
Phosphorus content in 1st conductive layer is less than 5 weight %,
On the thickness direction of the 1st conductive layer, the phosphorus content in the 1st conductive layer is in described matrix material particles side ratio It is high in the 2nd conductive layer side,
The region of described matrix material particles side for from the inner surface of the 1st conductive layer towards outside 10% thickness region, The region of the 2nd conductive layer side for from the outer surface of the 2nd conductive layer towards inner side 10% thickness region.
2. electroconductive particle according to claim 1, wherein,
On the thickness direction of the 1st conductive layer, the phosphorus content in the 1st conductive layer is in described matrix material particles side ratio In high more than the 0.5 weight % in the 2nd conductive layer side.
3. electroconductive particle according to claim 1 or 2, wherein,
Phosphorus content in 1st conductive layer is 0.1 weight % less than 5 weight %.
4. electroconductive particle according to claim 3, wherein,
Phosphorus content in 1st conductive layer is 3 weight % less than 5 weight %.
5. electroconductive particle according to claim 1 or 2, it has projection on the surface of electric conductivity.
6. electroconductive particle according to claim 1 or 2, it, which possesses, is configured on the outer surface of the 2nd conductive layer Megohmite insulant.
7. a kind of conductive material, it contains adhesive resin and electroconductive particle according to any one of claims 1 to 6.
8. a kind of connection structural bodies, it possesses：
1st connecting object part,
2nd connecting object part and
The the described 1st, connecting portion of the 2nd connecting object part is connected,
Wherein, the connecting portion is formed by electroconductive particle according to any one of claims 1 to 6 or by being led containing described The conductive material of conductive particles and adhesive resin is formed.
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JP6696721B2 (en) * 2013-09-09 2020-05-20 積水化学工業株式会社 Base particle, conductive particle, conductive material, and connection structure
JP6507552B2 (en) * 2014-10-03 2019-05-08 日立化成株式会社 Conductive particles
CN112863732B (en) * 2014-10-29 2023-01-17 迪睿合株式会社 Method for manufacturing connection structure, and conductive material
KR102410478B1 (en) 2015-09-14 2022-06-17 삼성디스플레이 주식회사 Display device
CN107851482B (en) * 2016-02-08 2020-03-20 积水化学工业株式会社 Conductive particle, conductive material, and connection structure
US10510821B2 (en) 2016-06-10 2019-12-17 Innovation Counsel Llp Display device
WO2021206201A1 (en) * 2020-04-10 2021-10-14 주식회사 씨앤씨머티리얼즈 Conductive polymer particles containing nickel metal layer
WO2021206202A1 (en) * 2020-04-10 2021-10-14 주식회사 씨앤씨머티리얼즈 Conductive polymer particles containing silver metal layer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906705A (en) * 2004-01-30 2007-01-31 积水化学工业株式会社 Conductive fine particle and anisotropic conductive material
CN101996696A (en) * 2009-08-06 2011-03-30 日立化成工业株式会社 Conductive fine particles and anisotropic conductive material
CN102047347A (en) * 2008-07-01 2011-05-04 日立化成工业株式会社 Circuit connection material and circuit connection structure
WO2011111152A1 (en) * 2010-03-08 2011-09-15 積水化学工業株式会社 Electroconductive particle, anisotropic electroconductive material and connecting structure
JP2012004034A (en) * 2010-06-18 2012-01-05 Sekisui Chem Co Ltd Conductive particles, anisotropic conductive material and connection structure

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4860163B2 (en) * 2005-02-15 2012-01-25 積水化学工業株式会社 Method for producing conductive fine particles
JP4991666B2 (en) * 2008-09-19 2012-08-01 積水化学工業株式会社 Conductive particles, anisotropic conductive materials, and connection structures
JP2012004033A (en) * 2010-06-18 2012-01-05 Sekisui Chem Co Ltd Conductive particles, anisotropic conductive material and connection structure
JP5703836B2 (en) * 2011-02-25 2015-04-22 日立化成株式会社 Conductive particles, adhesive composition, circuit connection material, and connection structure
JP6165625B2 (en) * 2012-01-20 2017-07-19 積水化学工業株式会社 Conductive particles, conductive materials, and connection structures

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906705A (en) * 2004-01-30 2007-01-31 积水化学工业株式会社 Conductive fine particle and anisotropic conductive material
CN102047347A (en) * 2008-07-01 2011-05-04 日立化成工业株式会社 Circuit connection material and circuit connection structure
CN101996696A (en) * 2009-08-06 2011-03-30 日立化成工业株式会社 Conductive fine particles and anisotropic conductive material
WO2011111152A1 (en) * 2010-03-08 2011-09-15 積水化学工業株式会社 Electroconductive particle, anisotropic electroconductive material and connecting structure
JP2012004034A (en) * 2010-06-18 2012-01-05 Sekisui Chem Co Ltd Conductive particles, anisotropic conductive material and connection structure

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