CN104704579B - Substrate particle, electroconductive particle, conductive material and connection structural bodies - Google Patents

Substrate particle, electroconductive particle, conductive material and connection structural bodies Download PDF

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CN104704579B
CN104704579B CN201380051449.4A CN201380051449A CN104704579B CN 104704579 B CN104704579 B CN 104704579B CN 201380051449 A CN201380051449 A CN 201380051449A CN 104704579 B CN104704579 B CN 104704579B
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particle
mentioned
substrate
substrate particle
load value
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CN104704579A (en
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永井康彦
上野山伸也
王晓舸
山田恭幸
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Non-Insulated Conductors (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provides a kind of in the case where the electroconductive particle for being formed with conductive layer on using surface is electrically connected between electrode, connection resistance can be reduced, and can be to the bad connection as caused by the crackle in electrode or to bad connection is inhibited caused by rebound substrate particle.The substrate particle 11 of the present invention is used to obtain the electroconductive particle 1 for forming conductive layer 2 on surface and having the conductive layer 2.Substrate particle 11 is core shell particle, the shell 13 for having core 12 and being configured on 12 surface of core.The compression recovery of substrate particle 11 is less than 50%.The modulus of elasticity in comperssion when compression of substrate particle 11 10% is 3000N/mm2Above and less than 6000N/mm2.The load value when compression of substrate particle 1 30% and the ratio between load value when compression 10% are 3 or less.

Description

Substrate particle, electroconductive particle, conductive material and connection structural bodies
Technical field
The present invention relates to for obtaining the base material for forming conductive layer on the surface and having the electroconductive particle of the conductive layer Particle.In addition, the invention further relates to the electroconductive particles, conductive material and connection structural bodies that have used above-mentioned substrate particle.
Background technology
The anisotropic conductive materials such as anisotropic conductive cream and anisotropic conductive film are well known.Above-mentioned each In anisotropy conductive material, electroconductive particle is dispersed in adhesive resin.
Above-mentioned anisotropic conductive material be used for flexible printing substrate (FPC), glass substrate, glass epoxy substrate and It is electrically connected between the electrode of the various connecting object components such as semiconductor chip and obtains connection structural bodies.In addition, can make sometimes Use the electroconductive particle with substrate particle and the conductive layer being configured on the substrate particle surface as above-mentioned electric conductivity grain Son.
As an example of substrate particle used in above-mentioned electroconductive particle, the following patent document 1 discloses： Shell be inorganic compound (A), core be organic polymer (b), and shell core is coated made of organic polymer particle (B) (substrate particle).In addition, being also disclosed that in patent document 1：To organic polymer particle, (B is carried out conductive metal (C) Electroconductive particle made of cladding.
In addition, organic mineral complex particle (substrate particle) is disclosed in following patent documents 2, by interface In the presence of activating agent, make to have the multi-functional silane compound of polymerism unsaturated group that hydrolysis and polycondensation occurs and obtains .In patent document 2, above-mentioned multi-functional silane compound is selected from following formula (X) compounds represented and its derivative In at least containing 1 radically polymerizable group group the first silicon compound.
[chemical formula 1]
In above-mentioned formula (X), R1 indicates that hydrogen atom or methyl, R2 indicate can be with the carbon atom number 1~20 of substituent group 2 Valence organic group, R3 indicate that the alkyl or phenyl of carbon atom number 1~5, R4 indicate the alkane selected from hydrogen atom, carbon atom number 1~5 1 valence group of at least one of base and the acyl group of carbon atom number 2~5.
In addition, the following Patent Document 3 discloses carried out to hard particles surface using soft polymer polymeric layer Core shell particle made of cladding.As the preference of above-mentioned hard particles, can enumerate：The metallics such as nickel；Glass fibre, oxygen Change the inorganic particles such as aluminium, silica；Cure the resin cured matters particles such as benzoguanamine.It is recorded in patent document 3：It is logical Setting soft polymer polymeric layer is crossed, contact area can be increased, to improve reliability.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-156068 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2000-204119 bulletins
Patent document 3：Japanese Unexamined Patent Publication 7-140481 bulletins
Invention content
Problem to be solved by the invention
In recent years, there are the narrower intervals of the electrode connected by electroconductive particle and electrode area becomes smaller trend, thus want Seek the electroconductive particle that can be attached with lower resistance.In addition, for baseplate material, in order to improve flexibility, in addition to Other than glass substrate, also begin to use softer resin film substrate, therefore, it is necessary to will not be to flexible substrate and electrode Cause the electroconductive particle of damage.
If using electroconductive particle obtained from being coated to flexible substrate particle surface by conductive layer, electricity The contact area of pole and electroconductive particle becomes larger, and electroconductive particle is not easy to cause to damage to electrode.But it if uses merely soft Soft substrate particle, then there are the following problems：When being attached between electrode, electrode and electric conductivity cannot be fully excluded Adhesive resin between particle, resin are sandwiched between electrode and electroconductive particle, or cannot fully penetrate through conductive layer and The oxidation film of electrode surface, as a result, connection resistance is got higher.It is to compare that the problem has carried out cladding and shell by shell in use to core Soft also will produce when having the core shell particle of casing as substrate particle.
On the other hand, it is obtained using cladding has been carried out by the conductive layer substrate particle surface harder to silica etc. When the electroconductive particle arrived, the connectivity of the removing property and conductive layer of adhesive resin and the oxidation film of electrode surface becomes Well.But the non-fully deformed of electroconductive particle, accordingly, there exist following problems：The contact area of electrode and electroconductive particle Do not become larger fully, therefore, connection resistance will not be reduced fully.In addition, according to crimping condition when being attached between electrode Difference, sometimes electroconductive particle can lesion electrode, crack on electrode.
In addition, in previous electroconductive particle, after being attached between electrode, make compressed electroconductive particle The bounce for returning original form is very big, will produce the phenomenon that referred to as springing back sometimes.Accordingly, there exist electroconductive particles and electrode The tendency that becomes smaller of contact area, also, when connection structural bodies is exposed under hot conditions and super-humid conditions, be easy to happen back Bullet, connection reliability reduction, is unable to maintain that lower connection resistance sometimes.
The object of the present invention is to provide a kind of using foring the electroconductive particle of conductive layer on surface between electrode When being electrically connected, connection resistance can be reduced, and can in electrode caused by cracking bad connection or right The substrate particle that bad connection is inhibited caused by rebound.The present invention also aims to provide a kind of use Electroconductive particle, conductive material and the connection structural bodies of the substrate particle.
Technical teaching for solving the problem was
According to the wide in range aspect of the present invention, a kind of substrate particle is provided, is used to form conductive layer on the surface and obtain Electroconductive particle with the conductive layer, wherein
The compression recovery of the substrate particle is less than 50%,
The substrate particle is core shell particle, and with core and the shell that is set on the surface of the core,
Modulus of elasticity in comperssion when compressing 10% is 3000N/mm2Less than 6000N/mm2,
Load value when compressing 30% and the ratio between load value when compression 10% are 3 or less.
In some particular aspects of the substrate particle of the present invention, the core is to have movement, and the shell is inorganic shell.
It it is 100nm or more and 5 μm or less in the thickness of some particular aspects of the substrate particle of the present invention, the shell.
Modulus of elasticity in comperssion when by substrate particle compression 30% is preferably 3000N/mm2Below.By the base material Load value when particle compression 40% and the ratio between the load value when substrate particle is compressed 10% are preferably 6 or less.It is described The breaking strain of substrate particle is preferably 10% or more and 30% or less.
According to the wide in range aspect of the present invention, a kind of electroconductive particle is provided, with above-mentioned substrate particle and is set to institute State the conductive layer on the surface of substrate particle.
In some particular aspects of the electroconductive particle of the present invention, which, which is also equipped with, is set to the conduction Insulating properties substance on layer outer surface.
In some particular aspects of the electroconductive particle of the present invention, the electroconductive particle is in the outer surface of the conductive layer With protrusion.
According to the wide in range aspect of the present invention, a kind of conductive material is provided, containing electroconductive particle and adhesive resin, The conductive layer that the electroconductive particle has above-mentioned substrate particle and is configured on the substrate particle surface.
According to the wide in range aspect of the present invention, a kind of connection structural bodies is provided comprising：
Surface have first electrode the first connecting object component,
Surface have second electrode the second connecting object component,
The interconnecting piece that the first connecting object component and the second connecting object component are connected,
The interconnecting piece is formed by electroconductive particle, or by the conduction containing the electroconductive particle and adhesive resin Material is formed,
The electroconductive particle has substrate particle according to any one of claims 1 to 6 and is set to the base material Conductive layer on particle surface,
The first electrode and the second electrode are electrically connected by the electroconductive particle.
The effect of invention
The substrate particle of the present invention is the core shell particle for the shell for having core and being configured on the wicking surface, in addition, in this hair The compression recovery of bright substrate particle is less than 50%, and modulus of elasticity in comperssion when compressing 10% is 3000N/mm2It is above and low In 6000N/mm2, load value when compression 30% is with the ratio between load value when compression 10% for 3 hereinafter, therefore, using table The electroconductive particle of conductive layer is formd on face when being electrically connected between electrode, can reduce connection resistance, and can be with Inhibit electrode in caused by cracking bad connection or the bad connection caused by rebound.
Description of the drawings
Fig. 1 is the sectional view for the electroconductive particle for indicating first embodiment of the invention；
Fig. 2 is the sectional view for the electroconductive particle for indicating second embodiment of the invention；
Fig. 3 is the sectional view for the electroconductive particle for indicating third embodiment of the invention；
Fig. 4 is the connection structural bodies for schematically showing the electroconductive particle for having used first embodiment of the invention Front cross-sectional view.
Description of symbols
1 ... electroconductive particle
2 ... conductive layers
11 ... substrate particles
12 ... cores
13 ... shells
21 ... electroconductive particles
22 ... conductive layers
The first conductive layers of 22A ...
The second conductive layers of 22B ...
31 ... electroconductive particles
31a ... protrusions
32 ... conductive layers
32a ... protrusions
33 ... core materials
34 ... insulating properties substances
51 ... connection structural bodies
52 ... first connecting object components
52a ... first electrodes
53 ... second connecting object components
53a ... second electrodes
54 ... interconnecting pieces
Specific implementation mode
Hereinafter, illustrating the detailed content of the present invention.
(substrate particle)
The substrate particle of the present invention obtains the electric conductivity grain with the conductive layer for forming conductive layer on the surface Son.That is, the substrate particle of the present invention is electroconductive particle substrate particle.
The compression recovery of the substrate particle of the present invention is less than 50%.Pressure when the substrate particle compression 10% of the present invention Contracting elasticity modulus (10%K values) is 3000N/mm2Less than 6000N/mm2.By the substrate particle compression 30% of the present invention When load value (30% load value) (30% load value/10% carries with the ratio between the load value (10% load value) when compression 10% Charge values) it is 3 or less.
The compression recovery of the substrate particle of the present invention is relatively low, and above-mentioned substrate particle have at compression initial stage it is appropriate hard Degree.In addition, for the substrate particle of the present invention, in the stage compressed to a certain degree, hardness generates variation, and shows Now more soft property.Therefore, with the load little with the load value difference under the initial deformation moment (10% compressive deformation moment) Charge values generate the deformation of mid-term (30% compressive deformation moment).As a result, being formed with conduction on the surface using substrate particle The electroconductive particle of layer is between electrode when being electrically connected, can by the hardness that displays in the early stage to adhesive resin into Row fully exclude, and fully perforation conductive layer or electrode surface oxidation film, and can by the flexibility of mid-term come pair The contact area of electrode and electroconductive particle is fully increased.In addition, the flexibility based on mid-term, it can also be to conduction The damage of electrode and substrate caused by property particle is inhibited, and can also be inhibited to cracking in the electrodes.Also, The compression recovery of the substrate particle of the present invention is low, therefore, after being attached between electrode, compressed electric conductivity grain The bounce that son will be restored to original form is small, the phenomenon that being not susceptible to referred to as spring back.Therefore, by using the base of the present invention Material particle, can in electrode caused by cracking bad connection or caused by rebound bad connection into Row inhibits.
The compression recovery of above-mentioned substrate particle is less than 50%.Above-mentioned compression recovery is preferably 40% hereinafter, more excellent It is selected as 30% or less.If above-mentioned compression recovery is above-mentioned lower limit or more, when being attached between electrode, compressed Electroconductive particle to be restored to original form bounce it is small, be easy to happen be referred to as rebound the phenomenon that, cause interelectrode It connects unstable.
Above-mentioned compression recovery can be measured.
Substrate particle is spread on sample table.Using micro-compression tester to 1 substrate particle of distribution along base material grain The center position of son applies load (reversion load value) until 30% compressive deformation occurs for substrate particle.Then, it is straight to carry out release of pressure To origin with load value (0.40mN).Load-compression displacement of above-mentioned period can be measured, and compression is found out according to following formula Recovery rate.In addition, load speed is set as 0.33mN/ seconds.Such as the manufacture of Fischer Co., Ltd. can be used " Fischerscope H-100 " etc. is used as above-mentioned micro-compression tester.
Compression recovery=[L2/L1] × 100%
L1：The compression displacement of load value is inverted origin load value when applying load up to reaching
L2：Up to reaching the release of pressure displacement of origin load value reversion load value when discharging
Above-mentioned 10%K values are 3000N/mm2Less than 6000N/mm2.Above-mentioned 10%K values are preferably 3500N/mm2 More than, more preferably 4000N/mm2More than, further preferably 4500N/mm2More than, particularly preferably 5000N/mm2More than, Preferably 5500N/mm2Below.If above-mentioned 10%K values are above-mentioned lower limit or more, adhesive resin is effectively arranged It removes, and effectively penetrates through the oxidation film of conductive layer or electrode surface, therefore, interelectrode connection resistance is effectively reduced. If above-mentioned 10%K values be the above-mentioned upper limit hereinafter, if be more not easy to crack on the electrode.If above-mentioned 10%K values are 4500N/mm2More than, then it connects resistance and is effectively reduced.Further, if it is preferred that 5000N/mm2More than, then it is not easy very much Generate the gap in electrode.
The ratio between above-mentioned 30% load value and above-mentioned 10% load value (30% load value/10% load value) are 3.0 or less. Above-mentioned ratio (30% load value/10% load value) is more preferably 2.8 or less.If (30% load value/10% carries above-mentioned ratio Charge values) it is the above-mentioned upper limit hereinafter, then the contact area of electrode and electroconductive particle fully becomes larger, to which interelectrode connection is electric Resistance is effectively reduced, and interelectrode connection reliability is further got higher.(30% load value/10% carries above-mentioned ratio Charge values) it is preferably 1.5 or more.
Above-mentioned substrate particle has been carried out to the modulus of elasticity in comperssion (30%K values) when 30% compressive deformation is preferably 3000N/mm2Hereinafter, more preferably 2500N/mm2Below.If above-mentioned 30%K values be the above-mentioned upper limit hereinafter, if electroconductive particle Further become larger with the contact area of electrode, and is less susceptible to crack on the electrode.Above-mentioned 30%K values are preferably 500N/ mm2More than.If above-mentioned 10%K values are 3000N/mm2Hereinafter, being then more not easy to crack on the electrode.If above-mentioned 10%K values For 2300N/mm2Hereinafter, being then not easy very much to crack on the electrode.
Load value (40% load value) when above-mentioned substrate particle compression 40% and the load value (10% when compression 10% Load value) the ratio between (40% load value/10% load value) be preferably 6 hereinafter, more preferably 5 or less.If above-mentioned ratio (40% The load value of load value/10%) it is the above-mentioned upper limit hereinafter, the scope of design for then improving connection reliability further becomes wide.Above-mentioned ratio Value (40% load value/10% load value) is preferably 2 or more.If above-mentioned ratio (40% load value/10% load value) is above-mentioned The upper limit is effectively lower hereinafter, then connecting resistance.
The above-mentioned load value of above-mentioned substrate particle and above-mentioned modulus of elasticity in comperssion (10%K values and 30%K values) can be as follows It measures.
Using micro-compression tester, at 25 DEG C, the condition of compression speed 0.3mN/ seconds and maximum test load 20mN Under, substrate particle is compressed using the smooth pressure head end face of cylinder (100 μm of diameter, diamond fabrication).It measures at this time Load value (N) and compression displacement (mm).Above-mentioned modulus of elasticity in comperssion can be asked according to the measured value of acquisition and by following formula Go out.Such as " FischerscopeH-100 " etc. of the manufacture of Fischer Co., Ltd. can be used to be tested as above-mentioned slight compression Machine.
10%K values or 30%K values (N/mm2)=(3/21/2)·F·S-3/2·R-1/2
F：Substrate particle has carried out the load value (N) when 10% or 30% compressive deformation
S：Substrate particle has carried out the compression displacement (mm) when 10% or 30% compressive deformation
R：The radius (mm) of substrate particle
Above-mentioned modulus of elasticity in comperssion is universal and is quantitatively indicated to the hardness of substrate particle.By using above-mentioned pressure Contracting elasticity modulus can quantify and uniquely indicate the hardness of substrate particle.
The breaking strain of above-mentioned substrate particle is 10% or more and 30% or less.The compression behavior of particle is evaluated When, observe the point being widely varied in some constantly acting load value bottom offset amount.The load value of the point of the variation is cripping load Value, displacement are rupture displacement.The ratio between grain size by the rupture displacement and before compressing (grain size before rupture displacement/compression) × 100 It is defined as breaking strain (%).For example, the particle that grain size before compression is 5 μm observes rupture at the time of 1 μm of displacement When behavior, it is 20% to calculate breaking strain.In the case of core shell particle, the rupture of shell is usually observed at the initial stage of displacement Behavior.If above-mentioned breaking strain is above-mentioned lower limit or more, the removing property of adhesive resin, the oxidation film of conductive layer and electrode Connectivity further get higher, and connect resistance and be further lower.If above-mentioned breaking strain be the above-mentioned upper limit hereinafter, if show Go out mid-term flexibility, the contact area of electroconductive particle and electrode further becomes larger, and connection resistance is further lower.
Above-mentioned breaking strain can be evaluated according to the measurement of above-mentioned modulus of elasticity in comperssion, and can pass through reading The displacement of the discontinuity point of compression displacement curve is measured.
Preferably 0.5 μm or more of the grain size of above-mentioned core, more preferable 1 μm or more, and preferably 500 μm hereinafter, more preferable 100 μm Hereinafter, further preferred 50 μm hereinafter, particularly preferred 20 hereinafter, most preferably 10 μm or less.Under if the grain size of above-mentioned core is above-mentioned Limit is above and the above-mentioned upper limit hereinafter, then 10%K values, 30%K values, above-mentioned ratio (30% load value/10% load value) and above-mentioned Ratio (40% load value/10% load value) is easy the preferred value of display, and can be by substrate particle for electroconductive particle Purposes.For example, if above-mentioned core grain size be above-mentioned lower limit more than and the above-mentioned upper limit hereinafter, if state electroconductive particle in use In the case of being attached between electrode, the contact area of electroconductive particle and electrode fully becomes larger, and is not easy to lead in formation The electroconductive particle agglomerated is formed when electric layer.In addition, will not become via the interelectrode interval that electroconductive particle connects It is too much, and conductive layer is not easy the sur-face peeling from substrate particle.
Refer to diameter in the case where above-mentioned core is proper sphere shape about the grain size of above-mentioned core, above-mentioned core be proper sphere shape with Refer to diameter when being assumed to be equivalent to the proper sphere of its volume in the case of outer shape.In addition, the grain size of core refers to passing through Arbitrary particle size determination device measures core and the average grain diameter that obtains.It can be used for example and become using laser light scattering, resistance value The particle size distribution machine of the principles such as the image analysis after change, shooting.
Above-mentioned substrate particle is core shell particle, the shell for having core and being configured on the wicking surface.The compression of core shell particle Recovery rate, 10%K values, 30%K values, above-mentioned ratio (30% load value/10% load value) and above-mentioned ratio (40% load value/ 10% load value) meet above-mentioned value, thus, it is possible to interelectrode connection resistance is reduced, and it is reliable to improve interelectrode connection Property.
Above-mentioned core preferably has movement.Above-mentioned shell is preferably inorganic shell.It is preferred that above-mentioned core is to have the movement and above-mentioned shell to be Inorganic shell.Above-mentioned substrate particle preferably has the core shell particle of movement and the inorganic shell being configured on organic wicking surface, and The preferably organic inorganic hybridization particle of core-shell-type.If above-mentioned core is inorganic shell to have movement or above-mentioned shell, recovery is compressed Rate, 10%K values, 30%K values, above-mentioned ratio (30% load value/10% load value) and above-mentioned ratio (40% load value/10% Load value) readily satisfy above-mentioned value.
Above-mentioned core preferably has movement, and preferably organic filler.It is above-mentioned to have movement and above-mentioned organic filler and inorganic core And inorganic particulate is compared, flexible relative, therefore, the result of shell is formed on the softer surface for having movement：It readily satisfies Compression recovery, above-mentioned ratio (30% load value/10% load value) and above-mentioned ratio (40% load value/10% load value).
Above-mentioned there is the material of movement, it is preferable to use various organic matters as being used to form.It is above-mentioned organic as being used to form The material of core, such as can be used：It is polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, poly- different The vistanexes such as butylene, polybutadiene；The acrylic resins such as polymethyl methacrylate, polymethyl acrylate；Gather to benzene two Formic acid alkylidene diol ester, polysulfones, makrolon, polyamide, phenol formaldehyde resin, melamine resin, benzoguanamine Formaldehyde resin, urea formaldehyde resin and make one or more kinds of various polymerizable monomers with ethylenically unsaturated group The polymer etc. of polymerization and acquisition.By making one or more kinds of various polymerizable monomers with ethylenically unsaturated group Polymerize, be easy design and synthesis suitable for conductive material with arbitrary compression when physical property substrate particle.
Make there is the monomer of ethylenically unsaturated group to be polymerize obtained movement in the case of, as above-mentioned tool There is the monomer of ethylenically unsaturated group, the monomer of the monomer and bridging property of non-crosslinked 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, (methyl) cyclohexyl acrylate, (methyl) acrylic acid are different Norbornene ester etc. (methyl) alkyl-acrylates；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) glycerol acrylate, (first Base) (methyl) esters of acrylic acid containing oxygen atom such as acrylic acid polycyclic 2-ethoxyethyl acetate, (methyl) glycidyl acrylate；(first Base) monomer containing nitrile such as acrylonitrile；The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether；Second The acid vinyl ester such as vinyl acetate, vinyl butyrate, vinyl laurate, stearic acid vinyl ester；Ethylene, propylene, isoamyl two The unsaturated hydrocarbons such as alkene, butadiene；(methyl) acrylic acid trifluoromethyl ester, five fluorine ethyl ester of (methyl) acrylic acid, vinyl chloride, vinyl fluoride, Halogen containing monomers such as chlorostyrene etc..
As the monomer of above-mentioned bridging property, such as can enumerate：Tetramethylol methane four (methyl) acrylate, four hydroxyl first Methylmethane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) propylene Acid esters, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine three (methyl) propylene Acid esters, glycerine two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propylene glycol two (methyl) propylene Acid esters, (poly-) tetramethylene glycol (methyl) acrylate, 1,4- butanediols glycol two (methyl) acrylate etc. are multifunctional (methyl) esters of acrylic acid；(different) triallyl cyanurate, trihemellitic acid triallyl, divinylbenzene, phthalic acid two Allyl ester, diallyl acrylamide, diallyl ether, γ-(methyl) acryloyloxypropyltrimethoxysilane, front three The monomer etc. of the silane-containings such as oxygroup silicyl styrene, vinyltrimethoxysilane.
The above-mentioned polymerizable monomer with ethylenically unsaturated group is set to polymerize by well known method, thus, it is possible to obtain It is above-mentioned to have movement.As this method, for example,：Suspension polymerisation is carried out in the presence of radical polymerization initiator Method and it is used together noncrosslinking kind of particle and radical polymerization initiator makes monomer expansion and the method etc. that polymerize.
Especially with regard to the core for being most suitable for the present invention, following core may be used：Elasticity of compression when by core compression 10% Modulus (10%K values) is preferably 1500N/mm2Above and 4000N/mm2Hereinafter, more preferably 2000N/mm2Above and 3500N/ mm2Below.The compression recovery of above-mentioned core is preferably shorter than 50%, and more preferable 40% hereinafter, further preferred 30% or less.If Above-mentioned core meets above-mentioned 10%K values, or meets above-mentioned modulus of elasticity in comperssion, then is easy to coat above-mentioned core with inorganic shell and obtain The 10%K values of the substrate particle arrived, it is above-mentioned than (10% load value/30% load value) and compression recovery control suitable Range.
The method that the physical property of above-mentioned core is designed as above range is not limited, such as is made with olefinic unsaturated group The monomer polymerization of group and in the case of obtaining above-mentioned core, following methods can be enumerated：Use the bridging property list of 70 weight % or more Body and using the non-crosslinked property monomer with alicyclic skeleton of 10 weight % or more as the compound for being used to form core.Make For this non-crosslinked property monomer with alicyclic skeleton, for example,：(methyl) cyclohexyl acrylate and (methyl) Isobornyl acrylate etc..In addition, making vinyltrimethoxysilane or (methyl) acryloxy trimethoxy silane in this way Silane coupling agent particle compound is obtained to which particlized occur by sol-gal process polycondensation, make with olefinic unsaturation The monomer absorption of group is polymerize to obtain particle after the particle compound, and such particle can also design the physical property of core For best value.The material for constituting above-mentioned core does not comprise only machine compound, can also include the compound with silicon atom. The ratio between the content of carbon atom in above-mentioned core and the content of silicon atom (content of content/silicon atom of carbon atom) are preferably 1.2 More than.The core that above-mentioned ratio (content of content/silicon atom of carbon atom) is 1.2 or more has been equivalent to movement.
From the viewpoint of hull shape at when and using substrate particle when inhibit core deformation, the decomposition temperature of above-mentioned core is excellent It is selected as more than 200 DEG C, more preferably above 250 DEG C, further preferably more than 300 DEG C.The decomposition temperature of above-mentioned core can also be more than 400 DEG C, can also be more than 500 DEG C, can also be more than 600 DEG C, can also be more than 800 DEG C.
Above-mentioned substrate particle is core shell particle.Above-mentioned shell is configured on the surface of above-mentioned core.Above-mentioned shell preferably coats above-mentioned The surface of core.Above-mentioned shell is preferably inorganic shell.
Above-mentioned inorganic shell preferably comprises the silicon atom of 50 weight % or more, at this point, above-mentioned inorganic shell is made containing silicon atom For the inorganic shell of principal component.Above-mentioned inorganic shell can also contain carbon atom, but containing carbon atom, if silicon is former Son is principal component, then referred to as inorganic shell.
Above-mentioned inorganic shell is preferably shelly-shaped by the way that metal alkoxides are made using sol-gal process on the surface of above-mentioned core The husk is burnt into after object and is formed.When using sol-gal process, it is easy to configure on the surface of above-mentioned core shelly-shaped Object.In the case where carrying out above-mentioned firing, for above-mentioned substrate particle, above-mentioned core will left behind after being burnt into Rather than it is removed by volatilization etc..Above-mentioned substrate particle has above-mentioned core after firing.If in addition, assuming on after firing It states core to be removed by volatilization etc., then above-mentioned 10%K values can become at a fairly low.
As the specific method of above-mentioned sol-gal process, can enumerate：The inorganic monomers such as tetraethoxysilane are made to coexist in In dispersion liquid containing the catalyst such as core, water or alcohol equal solvent, surfactant and ammonia spirit, and carry out interface colloidal sol The method of reaction；And the inorganic monomers such as tetraethoxysilane by being coexisted with water or alcohol equal solvent and ammonia spirit come into After row solgel reaction, make the different cohesion of solgel reaction object in the method etc. of core.It is above-mentioned in above-mentioned sol-gal process Metal alkoxides are preferably hydrolyzed and polycondensation.
, it is preferable to use surfactant in above-mentioned sol-gal process.It is preferred that in the presence of surfactant, pass through Husk is made in above-mentioned metal alkoxides by sol-gal process.Above-mentioned surfactant is not particularly limited.It is good in order to be formed Husk, above-mentioned surfactant can suitably be selected and be used.As above-mentioned surfactant, can enumerate： Cationic surfactant, anionic surfactant and nonionic surfactant etc..Wherein, from can be formed Good inorganic shell is set out, preferably cationic surfactant.
As above-mentioned cationic surfactant, quaternary ammonium salt can be enumerated Ji quaternary alkylphosphonium salt etc..As above-mentioned cationic The concrete example of surfactant can enumerate cetyl ammonium bromide etc..
In order to form above-mentioned inorganic shell on the surface of above-mentioned core, preferably above-mentioned husk is burnt into.It can basis Firing condition is adjusted the degree of cross linking in inorganic shell.In addition, by being burnt into, compared with the case where not being burnt into, The 10%K values and 30%K values of above-mentioned substrate particle show further preferred value.Especially by the raising degree of cross linking, 10%K Value is fully got higher.
It is preferred that above-mentioned inorganic shell is shelly-shaped by the way that metal alkoxides are made using sol-gal process on the surface of above-mentioned core After object, the husk is burnt at 100 DEG C or more (firing temperatures) and is formed.Above-mentioned firing temperature is more preferably 150 DEG C More than, further preferably 200 DEG C or more.If above-mentioned firing temperature is above-mentioned lower limit or more, the degree of cross linking in inorganic shell into One-step optimization, and (40% carries for 10%K values, 30%K values, above-mentioned ratio (30% load value/10% load value) and above-mentioned ratio The load value of charge values/10%) the further preferred value of display, and can further preferably be made according to the purposes of electroconductive particle Use substrate particle.
It is preferred that above-mentioned inorganic shell is shelly-shaped by the way that metal alkoxides are made using sol-gal process on the surface of above-mentioned core After object, by the husk, (firing temperature) is burnt into and is formed below the above-mentioned decomposition temperature for having movement.Above-mentioned firing temperature The temperature that preferably 10 DEG C lower than the decomposition temperature of above-mentioned core or more of degree is 50 DEG C more preferably lower than the decomposition temperature of above-mentioned core Above temperature.In addition, above-mentioned firing temperature be preferably 500 DEG C hereinafter, more preferably 300 DEG C hereinafter, further preferably 200 DEG C or less.If above-mentioned firing temperature be the above-mentioned upper limit hereinafter, if the heat deterioration and deformation of above-mentioned core can be inhibited, And 10%K values, 30%K values, above-mentioned ratio (30% load value/10% load value) and above-mentioned ratio (40% load can be obtained It is worth/10% load value) substrate particle of the good value of display.
As above-mentioned metal alkoxides, can enumerate：Alkoxy silane, alkoxytitanium, zirconium alkoxide and aluminum alkoxide Deng.From the viewpoint of forming good inorganic shell, above-mentioned metal alkoxides are preferably alkoxy silane, alkoxytitanium, alcoxyl Base zirconium or aluminum alkoxide, more preferably alkoxy silane, alkoxytitanium or zirconium alkoxide, further preferably alkoxy silane. From the viewpoint of forming good inorganic shell, the metallic atom in above-mentioned metal alkoxides be preferably silicon atom, titanium atom, Zirconium atom or aluminium atom, more preferably silicon atom, titanium atom or zirconium atom, further preferably silicon atom.Above-mentioned alcoxyl fund One kind can be used only by belonging to, and can also be applied in combination two or more.
From the viewpoint of forming good inorganic shell, above-mentioned metal alkoxides are preferably the alcoxyl that following formula (1) indicates Base Metal.
M(R1)n(OR2)4-n···(1)
In above-mentioned formula (1), M be silicon atom, titanium atom or zirconium atom, R1 indicate phenyl, carbon atom number 1~30 alkyl, The organic group of the organic group of carbon atom number 1~30 with polymeric double bond or the carbon atom number 1~30 with epoxy group Group, R2 indicate that the alkyl of carbon atom number 1~6, n indicate 0~2 integer.When n is 2, multiple R1 can also be identical, can not also Together.Multiple R2 can also be identical, can also be different.
From the viewpoint of forming good inorganic shell, above-mentioned metal alkoxides are preferably the alkane that following formula (1A) indicates Oxysilane.
Si(R1)n(OR2)4-n···(1A)
In above-mentioned formula (1A), R1 indicates phenyl, the alkyl of carbon atom number 1~30, with polymeric double bond and carbon atom number 1~30 organic group or organic group with epoxy group and carbon atom number 1~30, R2 indicate the alkane of carbon atom number 1~6 Base, n indicate 0~2 integer.When n is 2, multiple R1 can also be identical, can also be different.Multiple R2 can also be identical, also may be used With difference.In order to effectively improve the content of the silicon atom contained in shell, the preferred expressions 0 or 1 of n in above-mentioned formula (1A), more preferably Indicate 0.If the content of the silicon atom contained by shell is higher, the effect obtained by the present invention is further excellent.
In the case where above-mentioned R1 is the alkyl of carbon atom number 1~30, as the concrete example of R1, can enumerate：Methyl, Ethyl, propyl, isopropyl, isobutyl group, n-hexyl, cyclohexyl, n-octyl and positive decyl etc..The carbon atom number of the alkyl is preferred For 10 hereinafter, more preferably 6 or less.In addition, alkyl includes naphthenic base.
As above-mentioned polymeric double bond, carbon-to-carbon double bond can be enumerated.It is that the carbon with polymeric double bond is former in above-mentioned R1 In the case of the organic group of subnumber 1~30, as the concrete example of R1, it can enumerate：Vinyl, allyl, isopropenyl and 3- (methyl) acryloxyalkyl etc..As above-mentioned (methyl) acryloxyalkyl, can enumerate：(methyl) acryloyl Oxygroup methyl, (methyl) acryloyl-oxyethyl and (methyl) acryloxypropyl etc..It is above-mentioned that there is polymeric double bond and carbon The carbon atom number of the organic group of atomicity 1~30 is preferably 2 or more, and preferably 30 hereinafter, more preferably 10 or less.On It refers to methacryloxy or acryloxy to state " (methyl) acryloxy ".
In the case where above-mentioned R1 is the organic group with epoxy group and carbon atom number 1~30, as the specific of R1 Example, can enumerate：1,2- epoxy groups ethyl, 1,2- epoxypropyls, 2,3- epoxypropyls, 3,4- epoxy groups butyl, 3- rings Oxygen propoxypropyl and 2- (3,4- expoxycyclohexyls) ethyl etc..The above-mentioned carbon atom number 1~30 with epoxy group has The carbon atom number of machine group is preferably 8 hereinafter, more preferably 6 or less.In addition, above-mentioned have epoxy group and carbon atom number 1~30 Organic group be not only containing carbon atom and hydrogen atom also contain from epoxy group oxygen atom group.
As the concrete example of above-mentioned R2, can enumerate：Methyl, ethyl, n-propyl, isopropyl, normal-butyl and isobutyl group Deng.In order to effectively improve the content of the silicon atom contained in shell, above-mentioned R2 preferably indicates methyl or ethyl.
As the concrete example of above-mentioned alkoxy silane, can enumerate：Tetramethoxy-silicane, tetraethoxysilane, methyl three Methoxy silane, methyltriethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, isopropyl trimethoxy Silane, trimethoxysilane, cyclohexyl trimethoxy silane, n-hexyl trimethoxy silane, n-octyl triethoxy Silane, positive decyl trimethoxy silane, phenyltrimethoxysila,e, dimethyldimethoxysil,ne and diisopropyl dimethoxy Base silane etc..The alkoxy silane other than these can also be used.
In order to effectively improve the content of institute's silicon atoms in shell, it is preferable to use tetramethoxy-silicane or tetraethoxysilane Material as above-mentioned shell.In 100 weight % of the material of above-mentioned shell, the total of tetramethoxy-silicane and tetraethoxysilane Content is preferably 50 weight % or more (or total amount).In 100 weight % of above-mentioned shell, it is originated from the bone of tetramethoxy-silicane The total content of frame and skeleton from tetraethoxysilane is preferably 50 weight % or more (or total amount).
As the concrete example of above-mentioned alkoxytitanium, can enumerate：Titanium tetramethoxide, purity titanium tetraethoxide, tetraisopropoxy titanium And four titanium butoxide etc..The alkoxytitanium other than these can also be used.
As the concrete example of above-mentioned zirconium alkoxide, can enumerate：Tetramethoxy zirconium, tetraethoxy zirconium, zirconium tetraisopropoxide And tetrabutyl zirconate etc..The zirconium alkoxide other than these can also be used.
It is preferred that above-mentioned metal alkoxides include on metallic atom Direct Bonding have 4 oxygen atoms structure alkane Oxygroup metal.It is preferred that above-mentioned metal alkoxides include the metal alkoxides that following formula (1a) indicates.
M(OR2)4···(1a)
In above-mentioned formula (la), M is silicon atom, titanium atom or zirconium atom, and R2 indicates the alkyl of carbon atom number 1~6.It is multiple R2 can also be identical, can also be different.
It is preferred that above-mentioned metal alkoxides include the alcoxyl for the structure for having 4 oxygen atoms with Direct Bonding on the silicon atoms Base silane.In the alkoxy silane, usual 4 oxygen atoms are bonded to silicon atom by singly-bound.It is preferred that above-mentioned alcoxyl fund Belong to the alkoxy silane indicated comprising following formula (1Aa).
Si(OR2)4···(1Aa)
In above-mentioned formula (1Aa), R2 indicates the alkyl of carbon atom number 1~6.Multiple R2 can also be identical, can also be different.
From the viewpoint of effectively improving 10%K values and effectively reducing 30%K values, the above-mentioned inorganic shell that is used to form In 100 moles of % of metal alkoxides, it is above-mentioned have on metallic atom Direct Bonding have 4 oxygen atoms structure alkoxy Metal, the metal alkoxides of above-mentioned formula (1a) expression, the above-mentioned structure for having 4 oxygen atoms with Direct Bonding on the silicon atoms Alkoxy silane or the respective content of alkoxy silane that indicates of above-mentioned formula (1Aa) be preferably 20 moles of % or more, it is more excellent 40 moles of % or more, further preferably 50 moles of % or more are selected as, are still more preferably 55 moles of % or more, it is especially excellent 60 moles of % or more are selected as, and are 100 moles of % or less.The total amount of the above-mentioned metal alkoxides for being used to form inorganic shell can be with To be above-mentioned there is the Direct Bonding on metallic atom to have the metal alkoxides of structure of 4 oxygen atoms, above-mentioned formula (1a) to indicate Metal alkoxides, it is above-mentioned have on the silicon atoms Direct Bonding have 4 oxygen atoms structure alkoxy silane or above-mentioned formula The alkoxy silane that (1Aa) is indicated.
From the viewpoint of effectively improving 10%K values and being effectively reduced 30%K values, it is originated from contained by above-mentioned inorganic shell Above-mentioned metal alkoxides metallic atom total number 100% in, Direct Bonding have the metallic atom of 4 oxygen atoms Several ratio, Direct Bonding have 4-O-Si bases and with the silicon atom of 4 oxygen atom Direct Bondings in 4 above-mentioned-O-Si bases The ratio of number be respectively preferably 20% or more, more preferably 40% or more, further preferably 50% or more, more into one It is preferably 55 moles of % or more to walk, and particularly preferably 60% or more.
In addition, from making 10%K values suitably get higher and by above-mentioned ratio (30% load value/10% load value) and above-mentioned ratio Value (40% load value/10% load value) control is metallic atom contained in above-mentioned inorganic shell from the perspective of proper range Total number 100% in, it is preferably 20% or more that Direct Bonding, which has the ratio of the number of the metallic atom of 4 oxygen atoms, more excellent It is selected as 40% or more, further preferably 50% or more, is still more preferably 55 moles of % or more, particularly preferably 60% More than.From so that 10%K values is suitably got higher and by above-mentioned ratio (30%K values/10%K values) control be proper range viewpoint go out Hair, above-mentioned metal alkoxides are alkoxy silane, and in the total number 100% of silicon atom contained in above-mentioned inorganic shell, directly Be bonded with 4-O-Si bases and with the ratio of the number of the silicon atom of 4 oxygen atom Direct Bondings in 4 above-mentioned-O-Si bases Preferably 20% or more, more preferably 40% or more, further preferably 50% or more are still more preferably 55% or more, Particularly preferably 60% or more.
In addition, Direct Bonding have 4-O-Si bases and with the silicon of 4 oxygen atom Direct Bondings in 4 above-mentioned-O-Si bases Atom is, for example, the silicon atom in the structure that following formula (11) indicates.Specifically, being in the structure that following formula (11X) indicates The silicon atom that indicates of arrow A.
[chemical formula 2]
In addition, the oxygen atom in above-mentioned formula (11) usually forms siloxanes key with adjacent silicon atom.
[chemical formula 3]
As to Direct Bonding have 4-O-Si bases and with 4 oxygen atom Direct Bondings in 4 above-mentioned-O-Si bases The method that the ratio (ratio (%) of the number of Q4) of the number of silicon atom is measured, for example, following method：Make With NMR spectra resolver, by Q4 (Direct Bonding have 4-O-Si bases and with 4 oxygen atoms in 4 above-mentioned-O-Si bases it is straight Connect the silicon atom of bonding) peak area and Q1~Q3 (Direct Bonding have 1~3-O-Si base and with 1~3 above-mentioned-O-Si The silicon atom of 1~3 oxygen atom Direct Bonding in base) peak area be compared.In this way, can find out above-mentioned In the total number 100% of silicon atom contained in inorganic shell, Direct Bonding have 4-O-Si bases and with 4 above-mentioned-O-Si The ratio (the number ratio of Q4) of the number of the silicon atom of 4 oxygen atom Direct Bondings in base.
The thickness of above-mentioned shell is preferably 100nm or more, more preferably 200nm or more, and preferably 5 μm hereinafter, more preferably It is 3 μm or less.If above-mentioned shell thickness be above-mentioned lower limit or more and the above-mentioned upper limit hereinafter, if 10%K values and 30%K values show Further preferred value, and substrate particle can be suitably used on the way in the use of electroconductive particle.The thickness of above-mentioned shell is one The average thickness of substrate particle.The thickness of above-mentioned shell can be controlled by controlling sol-gal process.
In the present invention, the thickness of shell can be found out according to the average value of the difference of the grain size of substrate particle and core particles diameter. The grain size of above-mentioned substrate particle refers to diameter in the case where above-mentioned substrate particle is proper sphere shape, is true in above-mentioned substrate particle In the case of shape other than spherical, refer to be assumed to volume therewith comparable proper sphere when diameter.In the measurement of grain size In, such as can utilize and the size distribution of the principles such as the image analysis after laser light scattering, resistance change, shooting has been used to survey Determine machine.
The length-width ratio of above-mentioned substrate particle is preferably 2 hereinafter, more preferably 1.5 hereinafter, further preferably 1.2 or less. Above-mentioned length-width ratio indicates major diameter/minor axis.
(electroconductive particle)
The conductive layer that above-mentioned electroconductive particle has above-mentioned substrate particle and is configured on the substrate particle surface.
In Fig. 1, the electroconductive particle of first embodiment of the invention is indicated using sectional view.
The conductive layer 2 that electroconductive particle 1 shown in FIG. 1 has substrate particle 11 and is configured on 11 surface of substrate particle. Conductive layer 2 coats the surface of substrate particle 11.Electroconductive particle 1 be by conductive layer 2 to 11 surface of substrate particle into Particle obtained from row cladding.
The shell 13 that substrate particle 11 has core 12 and is configured on 12 surface of core.Shell 13 wraps the surface of core 12 It covers.Conductive layer 2 is configured on the surface of shell 13.Conductive layer 2 coats the surface of shell 13.
In Fig. 2, the electroconductive particle of second embodiment of the invention is indicated using sectional view.
The conductive layer that electroconductive particle 21 shown in Fig. 2 has substrate particle 11 and is configured on 11 surface of substrate particle 22.Conductive layer 22 has the first conductive layer 22A as internal layer and the second conductive layer 22B as outer layer.In substrate particle 11 Surface on be configured with the first conductive layer 22A.The first conductive layer 22A is configured on the surface of shell 13.In the first conductive layer The second conductive layer 22B is configured on the surface of 22A.
In Fig. 3, the electroconductive particle of third embodiment of the invention is illustrated using section.
Electroconductive particle 31 shown in Fig. 3 has：Substrate particle 11, conductive layer 32, multiple core materials 33 and multiple insulation Property substance 34.
Conductive layer 32 is configured on the surface of substrate particle 11.Conductive layer 32 is configured on the surface of shell 13.
Electroconductive particle 31 has multiple protrusion 31a on the surface of electric conductivity.Conductive layer 32 has more on the outer surface A protrusion 32a.As described above, above-mentioned electroconductive particle can have protrusion on the surface of electric conductivity, it can also be in conductive layer Outer surface on have protrusion.Multiple core materials 33 configure on the surface of substrate particle 11.It is configured on the surface of shell 13 Multiple core materials 33.Multiple core materials 33 are embedded into conductive layer 32.Core material 33 is configured at the inside of protrusion 31a, 32a.It leads Electric layer 32 coats multiple core materials 33.Since the outer surface of 33 conductive layer 32 of multiple core materials is swelled, so as to form protrusion 31a、 32a。
Electroconductive particle 31 has the insulating properties substance 34 being configured on 32 outer surface of conductive layer.32 outer surface of conductive layer At least part region coated by insulating properties substance 34.Insulating properties substance 34 is formed by the material with insulating properties, is insulation Property particle.As described above, above-mentioned electroconductive particle can also have the insulating properties substance being configured on the outer surface of conductive layer.
The metal for being used to form above-mentioned conductive layer is not particularly limited.As the metal, for example,：Gold, silver, Palladium, copper, platinum, zinc, iron, tin, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon and their alloy etc..In addition, As above-mentioned metal, can enumerate：Tin-doped indium oxide (ITO) and scolding tin etc..Wherein, since electrode can be further decreased Between connection resistance, it is therefore preferable that the alloy, nickel, palladium, copper containing tin or gold, preferably nickel or palladium.
Above-mentioned conductive layer can be formed such as electroconductive particle 1,31 by one layer.Conductive layer can as electroconductive particle 21 by Multilayer is formed.That is, conductive layer can be with 2 layers or more of laminated construction.It is outermost in the case where conductive layer is formed by multilayer Layer preferably layer gold, nickel layer, palladium layers, layers of copper or the alloy-layer containing tin and silver, more preferable layer gold.It is that these are preferred in outermost layer Conductive layer in the case of, interelectrode connection resistance is further lower.In addition, in the case where outermost layer is layer gold, corrosion resistant Corrosion is further got higher.
The method that conductive layer is formed on the surface of above-mentioned substrate particle is not particularly limited.As formation conductive layer Method, for example,：Using the method for non-electrolytic plating, using electric plating method, using physical vapor deposition method and Metal powder or the cream comprising metal powder and adhesive are coated on to the method etc. on the surface of substrate particle.Wherein, due to leading The formation of electric layer is easy, it is therefore preferable that utilizing the method for non-electrolytic plating.It, can be with as the above-mentioned method using physical vapor deposition It enumerates：The methods of vacuum evaporation, ion plating and ion sputtering.
The grain size of above-mentioned electroconductive particle is preferably 0.5 μm or more, more preferably 1 μm or more, and preferably 520 μm with Under, more preferably 500 μm hereinafter, still more preferably for 100 μm hereinafter, further preferably 50 μm hereinafter, particularly preferably 20 μm or less.If electroconductive particle grain size be above-mentioned lower limit more than and the above-mentioned upper limit hereinafter, if use electroconductive particle pair In the case of being attached between electrode, the contact area of electroconductive particle and electrode fully becomes larger, and is led when forming conductive layer Conductive particles are not susceptible to agglomerate.In addition, will not become too much via the interelectrode interval that electroconductive particle connects, and lead Electric layer is not easy the sur-face peeling from substrate particle.In addition, if the grain size of electroconductive particle is above-mentioned lower limit or more and the above-mentioned upper limit Hereinafter, electroconductive particle can be then suitable for the purposes of conductive material.
The grain size of above-mentioned electroconductive particle refers to diameter in the case where electroconductive particle is proper sphere shape, in electric conductivity grain Son be proper sphere shape other than shape in the case of, refer to be assumed to volume therewith comparable proper sphere when diameter.
The thickness of above-mentioned conductive layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, and preferably 10 μm with Under, more preferably 1 μm hereinafter, further preferably 0.3 μm or less.The thickness of above-mentioned conductive layer is in the feelings that conductive layer is multilayer Refer to the thickness of conductive layer entirety under condition.If conductive layer thickness be above-mentioned lower limit more than and the above-mentioned upper limit hereinafter, if obtain Sufficient electric conductivity, and electroconductive particle will not become really up to the mark, when being attached between electrode, electroconductive particle can fully become Shape.
In the case where above-mentioned conductive layer is formed by multilayer, the thickness of outermost conductive layer be preferably 0.001 μm with On, more preferably 0.01 μm or more, and preferably 0.5 μm hereinafter, more preferably 0.1 μm or less.If above-mentioned outermost conduction The thickness of layer is above-mentioned lower limit or more and the above-mentioned upper limit hereinafter, the cladding then carried out by outermost conductive layer becomes uniform, resistance to Corrosivity is fully got higher, and interelectrode connection resistance is further lower.In addition, in the case where above-mentioned outermost layer is layer gold, The thickness of layer gold is thinner, and cost is lower.
The thickness of above-mentioned conductive layer can observe electroconductive particle by using such as transmission electron microscope (TEM) Section and measure.
Above-mentioned electroconductive particle can have protrusion on the surface of electric conductivity.Above-mentioned electroconductive particle can also be upper Stating has protrusion on the outer surface of conductive layer.The protrusion is preferably several.In most cases, the surface of conductive layer and by It is formed with oxide film thereon on the surface of the electrode of electroconductive particle connection.The case where using the electroconductive particle with protrusion Under, electroconductive particle is configured between electrode and is crimped, and effectively excludes above-mentioned oxide film thereon using protrusion as a result,.Cause This, can be such that the conductive layer of electrode and electroconductive particle further reliably contacts, and can reduce interelectrode connection electricity Resistance.In addition, being scattered in bonding in the case where having insulating properties substance on the surface of electroconductive particle, or by electroconductive particle In agent resin and as in the case of conductive material, using the protrusion of electroconductive particle, electric conductivity grain can be effectively excluded Insulating properties substance or adhesive resin between son and electrode.It is thus possible to improve interelectrode conducting reliability.
As the method for forming protrusion on the surface of above-mentioned electroconductive particle, can enumerate：Core material is set to be attached to base Behind the surface of material particle, pass through the method that non-electrolytic plating forms conductive layer；And conductive layer shape is made by non-electrolytic plating At after on the surface of substrate particle, core material is made to adhere to, further passes through the conformal method etc. at conductive layer of electroless plating. Protrusion is formed alternatively, it is also possible to not use above-mentioned core material.
Above-mentioned electroconductive particle can have the insulating properties substance being configured on the outer surface of above-mentioned conductive layer.In the feelings Under condition, if electroconductive particle is used for interelectrode connection, adjacent interelectrode short circuit can be prevented.Specifically, When multiple electroconductive particle contacts, there are insulating properties substances between multiple electrodes, accordingly it is possible to prevent laterally upper adjacent electricity The short circuit of interpolar, and the not short circuit between upper/lower electrode.In addition, when being attached between electrode, two electrodes pair are utilized Electroconductive particle pressurizes, thus, it is possible to the easily insulating properties object between the conductive layer and electrode of exclusion electroconductive particle Matter.In electroconductive particle in the case where having protrusion on the surface of above-mentioned conductive layer, it further can easily exclude to lead Insulating properties substance between the conductive layer and electrode of conductive particles.Above-mentioned insulating properties substance be preferably insulative resin layer or absolutely Edge particle, more preferable insulating properties particle.The above-mentioned preferred insulative resin particle of insulating properties particle.
(conductive material)
Above-mentioned conductive material contains above-mentioned electroconductive particle and adhesive resin.It is preferred that above-mentioned electroconductive particle is dispersion It is used as conductive material in adhesive resin.Above-mentioned conductive material is preferably anisotropic conductive material.Above-mentioned conductive material It is applicable to the electrical connection of electrode.Above-mentioned conductive material is preferably circuit connection material.
Above-mentioned adhesive resin is not particularly limited.Well known insulative resin can be used as above-mentioned adhesive tree Fat.As above-mentioned adhesive resin, for example,：Vinylite, thermoplastic resin, curable resin, thermoplasticity are embedding Section copolymer and elastomer etc..One kind can be used only in above-mentioned adhesive resin, can also be applied in combination two or more.
As above-mentioned vinylite, for example,：Vinyl acetate resin, acrylic resin and styrene Resin etc..As above-mentioned thermoplastic resin, for example,：Vistanex, ethylene-vinyl acetate copolymer and poly- Amide resin etc..As above-mentioned curable resin, for example,：Epoxy resin, polyurethane resin, polyimide resin And unsaturated polyester resin etc..In addition, above-mentioned curable resin may be normal temperature cured type resin, thermohardening type resin, light Gel-type resin or moisture-curable resin.Above-mentioned curable resin can be applied in combination with curing agent.As above-mentioned thermoplasticity Block copolymer, for example,：Styrene-Butadiene-Styrene Block Copolymer, styrene-isoprene-benzene second The hydride and styrene-isoprene-phenylethene of alkene block copolymer, Styrene-Butadiene-Styrene Block Copolymer The hydride etc. of block copolymer.As above-mentioned elastomer, for example,：Styrene butadiene copolymers close rubber and third Alkene nitrile-styrene closes rubber etc..
Above-mentioned conductive material is other than containing above-mentioned electroconductive particle and above-mentioned adhesive resin, such as can also contain There are filler, incremental agent, softening agent, plasticizer, polymerization catalyst, curing catalysts, colorant, antioxidant, thermostabilization The various additives such as agent, light stabilizer, ultra-violet absorber, lubricant, antistatic agent and fire retardant.
In the present invention, in the case of the flexibility height of the above-mentioned adhesive resin after solidification, it can further suppress back Bullet can further play the effect of the present invention.
The method that above-mentioned electroconductive particle is scattered in above-mentioned adhesive resin is set to use known dispersion side Method, and be not particularly limited.As making above-mentioned electroconductive particle be scattered in the method in above-mentioned adhesive resin, such as can be with It enumerates：After above-mentioned electroconductive particle is added in above-mentioned adhesive resin, it is kneaded and is made using planetary-type mixer etc. Dispersion method；After so that above-mentioned electroconductive particle is homogeneously dispersed in water or organic solvent using homogenizer etc., it is added to In above-mentioned adhesive resin, it is kneaded using planetary-type mixer etc. and is allowed to the method disperseed；And utilize water or organic After solvent etc. dilutes above-mentioned adhesive resin, above-mentioned electroconductive particle is added, is kneaded and is made using planetary-type mixer etc. Dispersion method etc..
Conductive paste and conductive film etc. can be made to use in above-mentioned conductive material.It is conduction in the conductive material of the present invention It, can be by the pellicular cascade without electroconductive particle on the conductive film containing electroconductive particle in the case of film.Above-mentioned conduction Cream is preferably anisotropic conductive cream.Above-mentioned conductive film is preferably anisotropic conductive film.
In 100 weight % of above-mentioned conductive material, the content of above-mentioned adhesive resin is preferably 10 weight % or more, more excellent 30 weight % or more, further preferably 50 weight % or more, particularly preferably 70 weight % or more are selected as, and preferably 99.99 weight % are hereinafter, more preferably 99.9 weight % or less.If the content of above-mentioned adhesive resin is above-mentioned lower limit or more And the above-mentioned upper limit is hereinafter, the connecting object that then can effectively configure electroconductive particle between electrode, and be connected by conductive material The connection reliability of component is further enhanced.
In 100 weight % of above-mentioned conductive material, the content of above-mentioned electroconductive particle is preferably 0.01 weight % or more, more Preferably 0.1 weight % or more, and preferably 40 weight % are hereinafter, more preferably 20 weight % are hereinafter, further preferably 10 Weight % or less.If above-mentioned electroconductive particle content be above-mentioned lower limit more than and the above-mentioned upper limit hereinafter, if interelectrode conducting Reliability is further enhanced.
(connection structural bodies)
It is right using above-mentioned electroconductive particle or using the conductive material containing above-mentioned electroconductive particle and adhesive resin Connecting object component is attached, thus, it is possible to obtain connection structural bodies.
Above-mentioned connection structural bodies preferably has the first connecting object component, the second connecting object component and connects first The interconnecting piece that object Part and the second connecting object component connect is connect, and the interconnecting piece is formed by above-mentioned electroconductive particle, Or it is formed by the conductive material containing above-mentioned electroconductive particle and adhesive resin.The case where electroconductive particle is used alone Under, interconnecting piece sheet is as electroconductive particle.That is, the first connecting object component, the second connecting object component are connected by electroconductive particle It connects.Above-mentioned conductive material for obtaining above-mentioned connection structural bodies is preferably anisotropic conductive material.
Above-mentioned first connecting object component preferably has first electrode on the surface.Above-mentioned second connecting object component is excellent Choosing has second electrode on the surface.It is preferred that above-mentioned first electrode and above-mentioned second electrode are carried out by above-mentioned electroconductive particle Electrical connection.
Fig. 4 is the front cross-sectional view for schematically showing the connection structural bodies for having used electroconductive particle 1 shown in FIG. 1.
Connection structural bodies 51 shown in Fig. 4 has the first connecting object component 52, the second connecting object component 53 and by The interconnecting piece 54 that one connecting object component 52 and the second connecting object component 53 connect.Interconnecting piece 54 is conductive by containing The conductive material of particle 1 and adhesive resin is formed.In Fig. 4, for the ease of illustration, electroconductive particle 1 is simply illustrated. Other than electroconductive particle 1, other electroconductive particles such as electroconductive particle 21,31 can also be used.
First connecting object component 52 has multiple first electrode 52a on surface (upper surface).Second connecting object portion Part 53 has multiple second electrode 53a on surface (lower surface).First electrode 52a and second electrode 53a passes through 1 or more A electroconductive particle 1 realizes electrical connection.Therefore, the first connecting object component 52, the second connecting object component 53 pass through conduction Property particle 1 realizes electrical connection.
The manufacturing method of above-mentioned connection structural bodies is not particularly limited.One of manufacturing method as connection structural bodies Example can be enumerated：Above-mentioned conductive material is configured between the first connecting object component and the second connecting object component and is obtained After laminated body, method etc. which is heated and pressurizeed.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.For making the electrode of flexible printing substrate, being configured at resin The above-mentioned moulding pressure that the electrode of electrode and touch panel on film connects is 9.8 × 104~1.0 × 106Pa or so.
As above-mentioned connecting object component, specifically, can enumerate：The electricity such as semiconductor chip, capacitor and diode The electronic components such as the circuit boards such as sub- part and printed base plate, flexible printing substrate, epoxy glass substrate and glass substrate Deng.Above-mentioned conductive material is preferably used for the conductive material of connection electronic component.Above-mentioned conductive paste is preferably paste conduction material Material, and be coated on connecting object component with pasta state.
Above-mentioned electroconductive particle and above-mentioned conductive material can be adapted for touch panel.Therefore, above-mentioned connecting object component It is preferred that flexible printing substrate or the connecting object component configured with electrode on resin film surface.Above-mentioned connecting object component Preferably flexible printing substrate, and the connecting object component of electrode is preferably configured on the surface of resin film.It is above-mentioned to scratch Property printed base plate usually on the surface have electrode.
Especially in the present invention, in order to inhibit damage of the electroconductive particle to the connecting objects component such as substrate, and by base The initial hardness of material particle is designed as proper range.Therefore, in the present invention, to thickness than relatively thin glass substrate (thickness 0.2mm or so) and in the case that flexible printing substrate is connected, the present invention will play larger effect.
Above-mentioned first connecting object component, the preferred glass substrate of combination of the second connecting object component and flexible printing base The combination of plate.In this case, above-mentioned first connecting object component can be glass substrate, above-mentioned second connecting object component It may be glass substrate.The thickness of above-mentioned glass substrate is 0.05mm less than 0.5mm.
As the electrode for being set to above-mentioned connecting object component, can enumerate：Gold electrode, nickel electrode, tin electrode, aluminium electricity The metal electrodes such as pole, copper electrode, molybdenum electrode and tungsten electrode, Ti electrode.Particularly, in the present invention, for Ti electrode the case where It is lower to play larger effect.It is preferred that at least one of above-mentioned first electrode, second electrode are Ti electrode, preferably above-mentioned the One electrode, second electrode are both for Ti electrode.It preferably comprises in the material on the surface of above-mentioned first electrode, second electrode extremely One of few to contain titanium, the both for preferably comprising the surface of above-mentioned first electrode, second electrode contains titanium.
The present invention is concretely demonstrated hereinafter, enumerating Examples and Comparative Examples.The present invention is not limited to realities below Apply example.
(embodiment 1)
(1) making of substrate particle
(making of core)
P-divinyl benzene (96 weight % of purity) 600 parts by weight and 400 parts by weight of isobornyl acrylate are mixed It closes, obtains mixed liquor.20 parts by weight of benzoyl peroxide are added into the mixed liquor of acquisition, are stirred until equably molten Solution obtains monomer mixed solution.The polyvinyl alcohol of molecular weight about 1700 is dissolved in the 2 weight % aqueous solutions formed in pure water Reaction kettle is added in 4000 parts by weight.The monomer mixed solution of acquisition is added thereto, stir within 4 hours to adjust grain size so that The drop of monomer becomes specified grain size.Then, reaction 9 hours is carried out under 85 DEG C of nitrogen atmosphere, carries out monomer droplet Polymerisation, and obtain particle.After being cleaned the particle of acquisition for several times with hot water, progressive operation is carried out, a variety of grain sizes are recycled Different polymer particles (having movement).
Prepare the polymer beads that grain size is 3.00 μm in the polymer particle for utilizing progressive operation to recycle in embodiment 1 Sub (having movement).
(making of core shell particle)
By 30 parts by weight of polymer particle (having movement) of acquisition, as the cetyl ammonium bromide 12 of surfactant Parts by weight and 24 parts by weight of ammonia spirit of 25 weight %, which are added in 540 parts by weight of methanol and 60 parts by weight of pure water, to be mixed, And obtain the dispersion liquid of polymer particle.120 parts by weight of tetraethoxysilane are added into the dispersion liquid, carry out utilizing colloidal sol The condensation reaction of gel reaction.So that the condensation product of tetraethoxysilane is precipitated on the surface of polymer particle, form shell, and obtains Obtain particle.The particle of acquisition is cleaned for several times using ethyl alcohol, is dried, obtains core shell particle (substrate particle) as a result,.It obtains The grain size of the core shell particle obtained is 4.02 μm.According to the grain size of the grain size of core and core shell particle, the thickness for calculating shell is 0.51 μ m。
(2) making of electroconductive particle
Washing is carried out to the substrate particle of acquisition, and dry.Then, by electroless plating method acquisition base material grain Nickel layer is formed on the surface of son, makes electroconductive particle.In addition, the thickness of nickel layer is 0.1 μm.
(embodiment 2)
Prepare the polymer beads that grain size is 2.50 μm in the polymer particle for utilizing progressive operation to recycle in embodiment 1 Sub (having movement).Using the polymer particle of acquisition, and when making core shell particle 540 parts by weight of methanol are changed to different 540 parts by weight of propyl alcohol, and the additive amount of tetraethoxysilane is changed to 140 parts by weight, in addition to this, similarly to Example 1 Ground operates, and obtains core shell particle and electroconductive particle.
(embodiment 3)
Prepare the polymer beads that grain size is 2.25 μm in the polymer particle for utilizing progressive operation to recycle in embodiment 1 Sub (having movement).Using the polymer particle of acquisition, and when making core shell particle 540 parts by weight of methanol are changed to different 540 parts by weight of propyl alcohol, and the additive amount of tetraethoxysilane is changed to 310 parts by weight, in addition to this, similarly to Example 1 Ground operates, and obtains core shell particle and electroconductive particle.
(embodiment 4)
In electric furnace, in the state of being filled with nitrogen, the substrate particle obtained in embodiment 1 is heated at 200 DEG C Processing 30 minutes.Then, electroconductive particle is made using operating similarly with example 1.
(embodiment 5)
(1) palladium adheres to process
Prepare the substrate particle obtained in embodiment 1.The substrate particle of acquisition is etched and is washed.It connects It, substrate particle is added in the palladium catalyst liquid 100mL comprising 8 weight % of palladium catalyst and is stirred.Then, It is filtered, cleans.It is attached to obtain by substrate particle addition in the 0.5 weight % dimethylamine borane solution that pH value is 6 The substrate particle of palladium.
(2) core material adheres to process
The substrate particle for being attached with palladium is stirred 3 minutes in ion exchange water 300mL, it is made to disperse and be disperseed Liquid.Then, metallic Ni particles slurry (average grain diameter 100nm) 1g was made an addition to by 3 minutes in above-mentioned dispersion liquid, is obtained attached The substrate particle of core material.
(3) process for electroless nickel plating process
It operates similarly with example 1, forms nickel layer on the surface of substrate particle, make electroconductive particle.In addition, The thickness of nickel layer is 0.1 μm.
(embodiment 6)
(1) making of insulating properties particle
Dividing for the 1000mL of four mouthfuls of detachable lids, paddle, triple valve, cooling tube and temperature probe is being installed From weighing ion exchange water in formula flask so that the solid component content of monomer composition is 5 weight %, the combination of monomers Object contains methyl methacrylate 100mmol, N, N, N- trimethyl-N-2- methylacryoyloxyethyl ammonium chloride 1mmol and Then bis- (2- amidine propanes) the dihydrochloride 1mmol of 2,2'- azos are stirred with 200rpm, in a nitrogen atmosphere, 70 Polymerization 24 hours is carried out at DEG C.After reaction, it is freeze-dried, there is ammonium and average grain on the surface to obtain The insulating properties particle of diameter 220nm and CV value 10%.
So that insulating properties particle is scattered in ion exchange water under ultrasonic irradiation, obtains 10 weights of insulating properties particle Measure % aqueous dispersions.
So that the electroconductive particle 10g obtained in embodiment 1 is scattered in ion exchange water 500mL, adds insulating properties grain The aqueous dispersions 4g of son, is stirred at room temperature 6 hours.After being filtered using 3 μm of granular membrane, first is further utilized Alcohol is cleaned, and is dried and is obtained the electroconductive particle for being attached with insulating properties particle.
It is observed using scanning electron microscope (SEM), as a result, 1 layer is only formd on the surface of electroconductive particle The clad formed by insulating properties particle.By image analysis, insulating properties particle cladding area is calculated (that is, insulating properties particle The projected area of grain size) with apart from electroconductive particle center be 2.5 μm place area ratio, obtain clad ratio be 30%.
(embodiment 7)
Prepare the polymer beads that grain size is 2.50 μm in the polymer particle for utilizing progressive operation to recycle in embodiment 1 Sub (having movement).Using the polymer particle of acquisition, and when making core shell particle, 540 parts by weight of methanol are changed to second 540 parts by weight of nitrile, and the additive amount of tetraethoxysilane is changed to 140 parts by weight, in addition to this, similarly to Example 1 Ground operates, and obtains core shell particle and electroconductive particle.
(embodiment 8)
It is (organic for 2.75 μm of polymer particle to prepare to be classified grain size in the polymer particle of recycling in embodiment 1 Core).Using the polymer particle of acquisition, and when making core shell particle, 540 parts by weight of methanol are changed to isopropanol 540 The additive amount of tetraethoxysilane is changed to 50 parts by weight, in addition to this, operates similarly with example 1, obtain by parts by weight Obtain core shell particle and electroconductive particle.
(embodiment 9)
It is (organic for 2.75 μm of polymer particle to prepare to be classified grain size in the polymer particle of recycling in embodiment 1 Core).Using the polymer particle of acquisition, and when making core shell particle, 540 parts by weight of methanol are changed to 540 weight of acetonitrile Part is measured, the additive amount of tetraethoxysilane is changed to 50 parts by weight, in addition to this, is operated similarly with example 1, is obtained Core shell particle and electroconductive particle.
(embodiment 10)
In electric furnace, in the state of being filled with nitrogen, the substrate particle obtained in embodiment 1 is heated at 200 DEG C Processing 30 minutes.Then, electroconductive particle is made using operation similarly to Example 1.
(embodiment 11)
It is (organic for 3.5 μm of polymer particle to prepare to be classified grain size in the polymer particle of recycling in embodiment 1 Core).Using the polymer particle of acquisition, and when making core shell particle, 540 parts by weight of methanol are changed to 540 weight of acetonitrile Part is measured, the additive amount of tetraethoxysilane is changed to 50 parts by weight, in addition to this, is operated similarly with example 1, is obtained Core shell particle and electroconductive particle.
(comparative example 1)
Prepare the polymer beads that grain size is 3.00 μm in the polymer particle for utilizing progressive operation to recycle in embodiment 1 Son.It using the polymer particle of acquisition as substrate particle, operates similarly with example 1, obtains electroconductive particle.
(comparative example 2)
When making core, by divinylbenzene (96 weight % of purity) 400 weight of 600 parts by weight and isobornyl acrylate Amount part be changed to 50 parts by weight of 950 parts by weight of 1,4-butanediol diacrylate and ethylene glycol dimethacrylate, except this with Outside, it operates similarly with example 1, obtains particle.After being cleaned for several times to the particle of acquisition using hot water, progressive operation is carried out, Recycle the different polymer particle of a variety of grain sizes.
Prepare the polymer beads for being 3.02 μm using grain size in the polymer particle of progressive operation recycling in comparative example 2 Son.It using the polymer particle of acquisition as substrate particle, operates similarly with example 1, obtains electroconductive particle.
(comparative example 3)
When making core, by divinylbenzene (96 weight % of purity) 400 weight of 600 parts by weight and isobornyl acrylate Amount part is changed to divinylbenzene (96 weight % of purity) 1000 parts by weight, and the additive amount of benzoyl peroxide is changed to 40 parts by weight operate similarly with example 1 in addition to this, obtain particle.Using hot water to the particle washing of acquisition for several times Afterwards, progressive operation is carried out, the different polymer particle of a variety of grain sizes is recycled.
Prepare the polymer beads for being 3.01 μm using grain size in the polymer particle of progressive operation recycling in comparative example 3 Son.It using the polymer particle of acquisition as substrate particle, operates similarly with example 1, obtains electroconductive particle.
(comparative example 4)
It is (organic for 3.00 μm of polymer particle to prepare to be classified grain size in the polymer particle of recycling in embodiment 1 Core).When making core shell particle using the polymer particle obtained, the additive amount of tetraethoxysilane is changed to 10 weight Part, it in addition to this, operates similarly with example 1, obtains core shell particle and electroconductive particle.
(evaluation)
(1) thickness of the grain size of substrate particle, the grain size of core and shell
For the substrate particle of acquisition, using particle size distribution device, (Beckman Coulter Co., Ltd. manufactures " Multisizer3 "), measure about 10000 grain sizes, average grain diameter and standard deviation etc. are measured.For making base The core used when material particle measures grain size also by identical method.It is asked according to the difference of the grain size of substrate particle and the grain size of core Go out the thickness of shell.
(2) modulus of elasticity in comperssion (10%K values and 30%K values) and 10% load value and 30% load of substrate particle Value and 40% load value
Under conditions of 23 DEG C, by the above method, using micro-compression tester, (Fischer Co., Ltd. manufactures " Fischer scope H-100 "), to the above-mentioned modulus of elasticity in comperssion (10%K values and 30%K values) of the substrate particle of acquisition And 10% load value and 30% load value and 40% load value be measured.
(3) compression recovery of substrate particle
By above-mentioned method, micro-compression tester (" the Fischer scope of Fischer Co., Ltd. manufacture are used H-100 "), the above-mentioned compression recovery of the substrate particle of acquisition is measured.
(4) breaking strain of substrate particle
Under conditions of 23 DEG C, micro-compression tester (" the Fischer scope of Fischer Co., Ltd. manufacture are used H-100 "), breaking strain is measured by the above method.
(5) resistance is connected
The making of connection structural bodies：
By bisphenol A type epoxy resin (" Epikote 1009 " of Mitsubishi chemical Co., Ltd's manufacture) 10 parts by weight, propylene 40 parts by weight of sour rubber (weight average molecular weight about 800,000), 200 parts by weight of methyl ethyl ketone, the microcapsule-type curing agent (rising sun " HX3941HP " manufactured at E-MATERIALS Co., Ltd.) 50 parts by weight and silane coupling agent (Dow Corning " SH6040 " of silicone Co., Ltd. manufacture) 2 parts by weight are mixed, and are added electroconductive particle and so that its content is 3 Weight % makes it disperse and obtain resin combination.
The resin combination of acquisition is coated on PET (the poly- terephthaldehydes that single side has carried out 50 μm of the thickness of demoulding processing Sour second diester) film, drying in 5 minutes is carried out using 70 DEG C of hot winds, makes anisotropic conductive film.The anisotropy of acquisition The thickness of conductive film is 12 μm.
The anisotropic conductive film of acquisition is cut into the size of 5mm × 5mm.The anisotropy cut is led Electrolemma is attached at ITO electrode (height 0.1 μm, L/S=20 μm/20 μ around line being provided on one side with resistance measurement M) substantial middle of the ITO electrode side of pet substrate (width 3cm, length 3cm).Then, the 2 of identical gold electrode will be provided with Layer flexible printing substrate (width 2cm, length 1cm) fits together after carrying out position alignment and so that electrode overlaps each other.It will The laminated body that the pet substrate and 2 layers of flexible printing substrate are formed carries out heat under the conditions of the crimping of 10N, 180 DEG C and 20 seconds It crimps and obtains connection structural bodies.In addition, using copper electrode is formed on polyimide film, and copper electrode surface is coated with Au 2 layers of flexible printing substrate.
Connect the measurement of resistance：
By 4 terminal methods, the opposed interelectrode connection resistance in the connection structural bodies of acquisition is measured.Profit With following benchmark judgement connection resistance.
[evaluation criteria of connection resistance]
○○：Connection resistance is 3.0 Ω or less
○：Connection resistance is more than 3.0 Ω and is 4.0 Ω or less
△：Connection resistance is more than 4.0 Ω and is 5.0 Ω or less
×：It is more than 5.0 Ω to connect resistance
(6) whether there are cracks in electrode
To the electrode of 100 connection structural bodies obtained in the evaluation that above-mentioned (5) connect resistance whether crack into Row observation.
[whether there are cracks in electrode]
○○：100 electrodes do not crack
○：In 100 electrodes, the number cracked is two or less
△：In 100 electrodes, the number cracked is 3~5
×：In 100 electrodes, the number cracked is 6~10
××：In 100 electrodes, the number cracked is 11 or more
(7) there is tight in electrode
Use the electrode of 100 connection structural bodies obtained in the evaluation that above-mentioned (5) connect resistance of metallurgical microscopes pair It is observed, the electrode section contacted to electrically conductive microparticle has tight generation to observe.
[having tight in electrode]
○○：In 100 electrodes, the electrode in gap is not generated
○：In 100 electrodes, the number for generating gap is 2 or less
△：In 100 electrodes, the number for generating gap is 3~5
×：In 100 electrodes, the number for generating gap is 6 or more
As a result it is illustrated in following table 1.In addition, the length-width ratio of the substrate particle obtained in Examples 1 to 4,7~11 It is 1.2 or less.In addition, the evaluation result of the connection resistance in embodiment 3~5,10 is " 00 ", but in embodiment 5 The value for connecting resistance is lower than the value of the connection resistance in embodiment 3,4,10.Probably due to receiving the influence of protrusion.

Claims (10)

1. a kind of substrate particle is used to form conductive layer on the surface and obtain the electroconductive particle with the conductive layer, Wherein,
Following compression recoveries when the compressive deformation 30% of the substrate particle are less than 50%,
The substrate particle is core shell particle, and with core and the shell that is set on the surface of the core,
Following moduluss of elasticity in comperssion when compressing 10% are 3000N/mm2Less than 6000N/mm2,
The ratio between load value when compressing 30% and load value when compression 10% for 3 hereinafter,
The core is to have movement,
The shell is inorganic shell,
The assay method of above-mentioned compression recovery when compressive deformation 30%：
Apply load until substrate particle is sent out along the center position of substrate particle using 1 substrate particle of micro-compression tester pair Then raw 30% compressive deformation carries out release of pressure until origin load value, measures load-compression displacement of above-mentioned period, and root Compression recovery is found out according to following formula, load speed is set as 0.33mN/ seconds,
Compression recovery=[L2/L1] × 100%
L1：Compression displacement from origin load value when applying load up to reaching reversion load value
L2：Release of pressure displacement from reversion load value when discharging up to reaching origin load value,
The assay method of above-mentioned modulus of elasticity in comperssion when compressing 10%：
Using micro-compression tester, in the smooth pressure head end face of 100 μm of cylinder of diameter, in 25 DEG C, compression speed 0.3mN/ Substrate particle is compressed under conditions of second and maximum test load 20mN, measures load value at this time and compression displacement, root According to acquisition measured value and above-mentioned modulus of elasticity in comperssion is found out by following formula,
10%K values or 30%K values=(3/21/2)·F·S-3/2·R-1/2
F：Substrate particle has carried out load value when 10% or 30% compressive deformation
S：Substrate particle has carried out compression displacement when 10% or 30% compressive deformation
R：The radius of substrate particle.
2. substrate particle as described in claim 1, wherein
The thickness of the shell be 100nm or more, 5 μm or less.
3. substrate particle as described in claim 1, wherein
Modulus of elasticity in comperssion when compressing 30% is 3000N/mm2Below.
4. substrate particle as described in claim 1, wherein
Load value when compressing 40% and the ratio between load value when compression 10% are 6 or less.
5. substrate particle as described in claim 1, breaking strain is 10% or more and 30% or less.
6. a kind of electroconductive particle, has：
Substrate particle according to any one of claims 1 to 5 and
The conductive layer being set on the substrate particle surface.
7. electroconductive particle as claimed in claim 6 also has the insulating properties object being set on the conductive layer outer surface Matter.
8. electroconductive particle as claimed in claims 6 or 7, wherein
There is protrusion in the outer surface of the conductive layer.
9. a kind of conductive material,
It contains electroconductive particle and adhesive resin,
The electroconductive particle has substrate particle according to any one of claims 1 to 5 and is set to the substrate particle Conductive layer on surface.
10. a kind of connection structural bodies comprising：
Surface have first electrode the first connecting object component,
Surface have second electrode the second connecting object component,
The interconnecting piece that the first connecting object component and the second connecting object component are connected,
The interconnecting piece is formed by electroconductive particle, or by the conductive material shape containing the electroconductive particle and adhesive resin At,
The electroconductive particle has substrate particle according to any one of claims 1 to 5 and is set to the substrate particle Conductive layer on surface,
The first electrode and the second electrode are electrically connected by the electroconductive particle.
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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102095290B1 (en) * 2012-12-28 2020-03-31 세키스이가가쿠 고교가부시키가이샤 Organic-inorganic hybrid particle, conductive particle, conductive material and connection structure
JP6188392B2 (en) * 2013-04-12 2017-08-30 積水化学工業株式会社 Conductive particles, conductive materials, and connection structures
JP6460673B2 (en) * 2013-08-02 2019-01-30 積水化学工業株式会社 Base particle, conductive particle, conductive material, and connection structure
JP6337630B2 (en) * 2014-06-12 2018-06-06 日立化成株式会社 Circuit connection material and circuit connection structure
US11027374B2 (en) 2015-11-20 2021-06-08 Sekisui Chemical Co., Ltd. Particles, connecting material and connection structure
EP3378915A4 (en) 2015-11-20 2019-07-03 Sekisui Chemical Co., Ltd. Connecting material and connection structure
EP3378916A4 (en) 2015-11-20 2019-07-03 Sekisui Chemical Co., Ltd. Particles, connecting material and connection structure
KR102248989B1 (en) * 2016-09-30 2021-05-06 세키스이가세이힝코교가부시키가이샤 Conductive resin particles and their uses
CN108987962B (en) * 2017-06-05 2021-12-03 日立金属株式会社 Crimp terminal, electric wire with terminal, and method for manufacturing electric wire with terminal
CN107393633A (en) * 2017-06-26 2017-11-24 张家港康得新光电材料有限公司 Conductive metal balls and 3D display device
KR102095115B1 (en) * 2018-07-27 2020-03-30 한국전력공사 Self-healing silicon insulator and manufacturing method for thereof
DE102019107633A1 (en) * 2019-03-25 2020-10-29 Sphera Technology Gmbh Multi-component system and method for producing a multi-component system
JPWO2021025114A1 (en) * 2019-08-08 2021-02-11

Citations (2)

* 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
CN101153080A (en) * 2006-09-29 2008-04-02 日清纺织株式会社 Conductive particles and method of preparing the same

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3280139B2 (en) 1993-11-19 2002-04-30 日立化成工業株式会社 Display panel
JP4163316B2 (en) 1999-01-14 2008-10-08 株式会社日本触媒 Organic-inorganic composite particles, method for producing the same, and use thereof
JP2001011503A (en) * 1999-06-25 2001-01-16 Catalysts & Chem Ind Co Ltd New conductive fine particle and its use
JP2006156068A (en) 2004-11-29 2006-06-15 Sanyo Chem Ind Ltd Conductive particulate
KR100861010B1 (en) * 2006-12-22 2008-09-30 제일모직주식회사 Insulated Conductive Particles for Anisotropic Conduction and Anisotropic Conductive Film Using Same
JP4669905B2 (en) * 2008-03-27 2011-04-13 積水化学工業株式会社 Conductive particles, anisotropic conductive materials, and connection structures
JP5430093B2 (en) * 2008-07-24 2014-02-26 デクセリアルズ株式会社 Conductive particles, anisotropic conductive film, joined body, and connection method
US20110127068A1 (en) * 2008-07-31 2011-06-02 Takuya Wada Polymer particle, conductive particle, anisotropic conductive material and connection structure
JP2011060502A (en) * 2009-09-08 2011-03-24 Sekisui Chem Co Ltd Conductive particle with insulating particles, anisotropic conductive material, and connection structure
JP5476210B2 (en) * 2010-05-19 2014-04-23 積水化学工業株式会社 Conductive particles, anisotropic conductive materials, and connection structures
JP5856379B2 (en) * 2011-03-03 2016-02-09 株式会社日本触媒 Conductive fine particles and anisotropic conductive material using the same
JP2012209097A (en) * 2011-03-29 2012-10-25 Sekisui Chem Co Ltd Anisotropic conductive material and connection structure

Patent Citations (2)

* 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
CN101153080A (en) * 2006-09-29 2008-04-02 日清纺织株式会社 Conductive particles and method of preparing the same

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