CN107636774A - Conductive material and connection structural bodies - Google Patents

Conductive material and connection structural bodies Download PDF

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Publication number
CN107636774A
CN107636774A CN201680033297.9A CN201680033297A CN107636774A CN 107636774 A CN107636774 A CN 107636774A CN 201680033297 A CN201680033297 A CN 201680033297A CN 107636774 A CN107636774 A CN 107636774A
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China
Prior art keywords
mentioned
electrode
conductive material
scolding tin
particle
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CN201680033297.9A
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CN107636774B (en
Inventor
定永周治郎
永田麻衣
伊藤将大
久保田敬士
石泽英亮
夏井宏
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/02—Soldered or welded connections

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Non-Insulated Conductors (AREA)
  • Conductive Materials (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention provides a kind of conductive material, and it can optionally configure the scolding tin in electroconductive particle on electrode, and even if narrowed width between electrode width and electrode, can also suppress migration and lower maintain to connect resistance.The conductive material of the present invention contains：There are multiple electroconductive particles, Thermocurable compound, the acid anhydrides thermal curing agents of scolding tin in the outer surface part of conductive part, viscosity of the conductive material at 50 DEG C is more than 10Pas, below 200Pas.

Description

Conductive material and connection structural bodies
Technical field
The present invention relates to a kind of conductive material containing the electroconductive particle with scolding tin.It is moreover, it relates to a kind of Use the connection structural bodies for having above-mentioned conductive material.
Background technology
The anisotropic conductive material such as anisotropic conductive paste and anisotropic conductive film is well known.To above-mentioned each For anisotropy conductive material, electroconductive particle is dispersed with adhesive.
In order to obtain various connection structural bodies, above-mentioned anisotropic conductive material can be used for such as flexible printing substrate and Connection (COF (the Chip on of the connection (FOG (Film on Glass)) of glass substrate, semiconductor chip and flexible printing substrate Film)), the connection (COG (Chip on Glass)) of semiconductor chip and glass substrate and flexible printing substrate and glass Connection (FOB (Film on Board)) of epoxy substrate etc..
Above-mentioned anisotropic conductive material is being utilized to such as electricity of the electrode of flexible printing substrate and glass epoxy substrate When pole is electrically connected, the anisotropic conductive material containing electroconductive particle is configured on glass epoxy substrate.Then, lamination Flexible printing substrate, and heated and pressurizeed.Thus, solidify anisotropic conductive material, and via electroconductive particle pair It is electrically connected between electrode, so as to obtain connection structural bodies.
As an example of above-mentioned anisotropic conductive material, one kind has been recorded in following patent documents 1 respectively to different Property conductive material, its contain electroconductive particle and will not be completed under the fusing point of the electroconductive particle solidification resin component.Make For above-mentioned electroconductive particle, specifically, can enumerate：Tin (Sn), indium (In), bismuth (Bi), silver-colored (Ag), copper (Cu), zinc (Zn), lead (Pb), the alloy of the metal such as cadmium (Cd), gallium (Ga) and thallium (Tl) or these metals.
Recorded in patent document 1：By high in the fusing point than above-mentioned electroconductive particle and unfinished above-mentioned resin component Solidification at a temperature of, the resin heating stepses that are heated to anisotropic conductive resin, and solidify above-mentioned resin component Resin component curing schedule, being electrically connected electrode.In addition, recorded in patent document 1 with Fig. 8 of patent document 1 Shown temperature distribution history is installed.In patent document 1, to that will not complete at a temperature of to anisotropic conductive resin When the resin component of solidification is heated, electroconductive particle melting.
There is a kind of splicing tape disclosed in following patent documents 2, it is included：Resin bed containing heat-curing resin, weldering Glass putty and curing agent, above-mentioned solder powder and above-mentioned curing agent are present in above-mentioned resin bed.The splicing tape is membranaceous, is not paste Shape.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2004-260131 publications
Patent document 2：WO2008/023452A1
The content of the invention
The technical problems to be solved by the invention
In the anisotropic conductive paste of the conventional electroconductive particle containing solder powder or surface with soldering-tin layer, Sometimes solder powder or electroconductive particle are not efficiently configured on electrode (line).
In addition, using the anisotropic conductive material described in patent document 1 with the method described in patent document 1 to electricity When interpolar is electrically connected, it is not efficiently configured on electrode (line) sometimes with the electroconductive particle of scolding tin.In addition, patent In the embodiment of document 1, in order to make scolding tin fully move at a temperature of more than the fusing point of scolding tin, certain temperature is maintained at, The manufacture efficiency step-down of connection structural bodies.When being installed with the temperature distribution history shown in Fig. 8 of patent document 1, connection knot The manufacture efficiency step-down of structure body.
Between electrode width and electrode in the case of narrow width, even if optionally the scolding tin in electroconductive particle to be matched somebody with somebody Put on the narrow electrode of electrode width, residue solder between electrode also easily in the transverse direction, produces migration sometimes, connects resistance Rise.
In addition, the splicing tape described in patent document 2 is membranaceous, it is not pasty state.Just there is the composition that patent document 2 is recorded Splicing tape for, it is difficult to solder powder is efficiently configured on electrode (line).For example, the splicing tape described in patent document 2 In, a part for solder powder is easily configurable at the region (interval) for not forming electrode.It is configured at the weldering in the region for not forming electrode Glass putty is unfavorable for interelectrode conducting.
It is an object of the present invention to provide a kind of conductive material, and it can be by the scolding tin in electroconductive particle optionally Configuration can also suppress migration and lower maintain connection electricity on electrode, and even if narrowed width between electrode width and electrode Resistance.In addition, use the connection structural bodies for having above-mentioned conductive material it is an object of the present invention to provide a kind of.
For solving the technical scheme of technical problem
According to the broad aspect of the present invention, there is provided a kind of conductive material, it contains：Have in the outer surface part of conductive part There are multiple electroconductive particles, Thermocurable compound, the acid anhydrides thermal curing agents of scolding tin, viscosity of the conductive material at 50 DEG C For more than 10Pas, below 200Pas.
In some specific aspect of the conductive material of the present invention, the weight % of conductive material 100, the electroconductive particle Content be more than 1 weight %, below 80 weight %, the conductive material is anisotropic conductive material.
In some specific aspect of the conductive material of the present invention, viscosity of the conductive material at 50 DEG C and at 100 DEG C The ratio between viscosity be more than 10, less than 400.
At some specific aspect of the conductive material of the present invention, the electroconductive particle is scolding tin particle.
At some specific aspect of the conductive material of the present invention, the conductive material contains organic phosphorus compound.
The acid anhydrides thermal curing agents are liquid preferably at 25 DEG C.The acid anhydrides thermal curing agents are preferably cyclic acid anhydride thermosetting Agent.
At some specific aspect of the conductive material of the present invention, and to obtain within 0.5 hour first solid for heat cure at 170 DEG C During compound, and when the first obtained solidfied material is placed 100 hours in 130 DEG C and humidity 85% time and obtains the second solidfied material, The absolute value of the difference of the glass transition temperature of the glass transition temperature of first solidfied material and second solidfied material is Less than 20 DEG C.
At some specific aspect of the conductive material of the present invention, the Thermocurable compound contains with nitrogen-atoms Thermocurable compound.
At some specific aspect of the conductive material of the present invention, the Thermocurable compound contains with triazine skeleton Thermocurable compound.
At some specific aspect of the conductive material of the present invention, relative to overall the 100 of the Thermocurable compound Parts by weight, the content of the acid anhydrides thermal curing agents is more than 30 parts by weight, below 80 parts by weight.
At some specific aspect of the conductive material of the present invention, carboxyl be present in the outer surface of the electroconductive particle.
At some specific aspect of the conductive material of the present invention, the conductive material is conductive paste, and at 25 DEG C For liquid.
According to the broad aspect of the present invention, there is provided a kind of connection structural bodies, it has：Surface has at least one first First connecting object part of electrode, surface has the second connecting object part of at least one second electrode, by described first The connecting portion that connecting object part and the second connecting object part link together, the connecting portion are described conduction material The solidfied material of material, the first electrode and the second electrode realize electrical connection by the solder sections in the connecting portion.
At some specific aspect of the connection structural bodies of the present invention, along the first electrode, the connecting portion and described The stack direction of second electrode, when observing the mutually opposing part of the first electrode and the second electrode, More than 50% in the area 100% of the mutually opposing part of the first electrode and the second electrode is configured with the connection Solder sections in portion.
The effect of invention
The conductive material of the present invention contains：There is multiple electroconductive particles, the heat of scolding tin in the outer surface part of conductive part Curability compound, acid anhydrides thermal curing agents, viscosity of the conductive material at 50 DEG C be more than 10Pas, 200Pas with Under, therefore, it can optionally configure the scolding tin in electroconductive particle on electrode, and even if width between electrode width and electrode Narrow, migration can also be suppressed and lower maintain to connect resistance.
Brief description of the drawings
Fig. 1 is to schematically show the connection structural bodies obtained using the conductive material of an embodiment of the invention Profile.
Fig. 2 (a)~(c) is for illustrating that the conductive material using an embodiment of the invention manufactures connection structural bodies Method an example each operation profile.
Fig. 3 is the profile for the variation for representing connection structural bodies.
Fig. 4 is the profile for the first case for representing the electroconductive particle available for conductive material.
Fig. 5 is the profile for the second case for representing the electroconductive particle available for conductive material.
Fig. 6 is the profile of the 3rd for representing the electroconductive particle available for conductive material.
Description of symbols
1st, 1X ... connection structural bodies
2 ... first connecting object parts
2a ... first electrodes
3 ... second connecting object parts
3a ... second electrodes
4th, 4X ... connecting portions
4A, 4XA ... solder sections
4B, 4XB ... solidfied material portion
11 ... conductive materials
11A ... scolding tin particle (electroconductive particle)
11B ... Thermocurable compositions
21 ... electroconductive particles (scolding tin particle)
31 ... electroconductive particles
32 ... substrate particles
33 ... conductive parts (conductive part with scolding tin)
The conductive parts of 33A ... second
33B ... solder sections
41 ... electroconductive particles
42 ... solder sections
Embodiment
Hereinafter, the details of the present invention is illustrated.
(conductive material)
The conductive material of the present invention contains multiple electroconductive particles and adhesive.Above-mentioned electroconductive particle has conductive part. Above-mentioned electroconductive particle has scolding tin in the outer surface part of conductive part.Scolding tin is contained in conductive part, is a part for conductive part Or all.
The conductive material of the present invention contains Thermocurable compound and thermal curing agents as above-mentioned adhesive.Thermocurable Compound and thermal curing agents are Thermocurable composition.In the conductive material of the present invention, as above-mentioned thermal curing agents, contain acid anhydrides thermosetting Agent.
In the present invention, using specific electroconductive particle, and in order that Thermocurable compound cures and be applied in combination Specific acid anhydrides thermal curing agents.
Viscosity of the conductive material of the present invention at 50 DEG C is more than 10Pas, below 200Pas.
In the present invention, due to possessing above-mentioned composition, therefore, the scolding tin in electroconductive particle can optionally be matched somebody with somebody Put on electrode.In the case of being electrically connected electrode, the scolding tin in electroconductive particle easily concentrates on opposed up and down Electrode between, the scolding tin in electroconductive particle can be efficiently configured on electrode (line).
, can be with addition, a part for the scolding tin in electroconductive particle is not easy to be configured at the region (interval) for not forming electrode The amount for making to be configured at the scolding tin in the region for not forming electrode is considerably less.In the present invention, can effectively make to be not at pair The interelectrode scolding tin put is moved between opposed electrode.It is thus possible to improve interelectrode conducting reliability.Furthermore, it is possible to The interelectrode electrical connection of the adjoining on the transverse direction that can not be attached is prevented, insulating reliability can be improved.
Also, even if narrowed width between electrode width and electrode, migration can also be suppressed and lower maintain to connect resistance.
In the installation (particularly once mounting) of semiconductor element, narrowed width between electrode width and electrode.Therefore, exist On transverse direction between adjacent electrode during residue solder, migration is easily produced, the generation of migration turns into the problem of very big.In the present invention In, between electrode width and electrode in the case of narrow width, effectively suppress migration, can lower maintain to connect resistance.
By by above-mentioned conductive material at 170 DEG C heat cure 0.5 hour, can obtain the first solidfied material.By will be above-mentioned First solidfied material is placed 100 hours in 130 DEG C and humidity 85% time, can obtain the second solidfied material.Suppress solidification from further The heat deterioration of thing, from the viewpoint of further suppressing migration, the glass transition temperature (Tg1) of above-mentioned first solidfied material and upper The absolute value for stating the difference of the glass transition temperature (Tg2) of the second solidfied material is preferably less than 20 DEG C, more preferably less than 10 DEG C.
In order to which scolding tin is further efficiently configured on electrode, above-mentioned conductive material is liquid preferably at 25 DEG C, Preferably conductive paste.
In order to which scolding tin is further efficiently configured on electrode, viscosity (η 50) of the above-mentioned conductive material at 50 DEG C Preferably more than 10Pas, more preferably more than 30Pas, preferably below 200Pas, more preferably 100Pas with Under.Viscosity of the above-mentioned conductive material at 50 DEG C produces shadow to the translational speed for being conductively connected initial stage of electroconductive particle or scolding tin Ring.
In order to which scolding tin is further efficiently configured on electrode, viscosity (η 50) of the above-mentioned conductive material at 50 DEG C It is preferably more than 10, more preferably more than 30 relative to the ratio between the viscosity (η 100) of above-mentioned conductive material at 100 DEG C, is preferably Less than 400, more preferably less than 100.Viscosity of the above-mentioned conductive material at 100 DEG C connects to electroconductive particle or the conductive of scolding tin The translational speed for connecing mid-term has an impact.When ratio (η 100 of η 50/) is more than above-mentioned lower limit and below the above-mentioned upper limit, in conduction During connection, from initial stage to mid-term, electroconductive particle or scolding tin effectively move.
Above-mentioned viscosity can use STRESSTECH (manufacture of EOLOGICA company systems) etc., and 1rad, frequency are controlled in distortion It is measured under conditions of 1Hz, 20 DEG C/min of programming rate, 40~200 DEG C of measurement temperature scope.
Above-mentioned conductive material can be used in the form of conductive paste and conducting film etc..Above-mentioned conductive material be preferably it is each to Different in nature conductive material.Above-mentioned conductive paste is preferably anisotropic conductive paste.Above-mentioned conducting film is preferably anisotropic conductive Film.Above-mentioned conductive material is preferred for the electrical connection of electrode.Above-mentioned conductive material is preferably circuit connection material.
From the effect for effectively producing the present invention, the viewpoint that scolding tin is further effectively configured between upper and lower electrode goes out Hair, in the above-mentioned weight % of conductive material 100, the content of above-mentioned electroconductive particle is more than 1 weight %, below 80 weight %, on It is preferably anisotropic conductive material to state conductive material.The anisotropic conductive material is preferably anisotropic conductive paste or each Anisotropy conducting film.
Hereinafter, each composition contained in above-mentioned conductive material is illustrated.
(electroconductive particle)
Above-mentioned electroconductive particle the electrode of connecting object part being electrically connected.Above-mentioned electroconductive particle is in conductive part Outer surface part there is scolding tin.Above-mentioned electroconductive particle can be scolding tin particle.Above-mentioned scolding tin particle is formed by scolding tin.It is above-mentioned Scolding tin particle has scolding tin in the outer surface part of conductive part.Above-mentioned scolding tin particle is the core of above-mentioned scolding tin particle and led The outer surface part in electric portion is the particle of scolding tin.The core of above-mentioned scolding tin particle and the outer surface part of conductive part by Scolding tin is formed.Above-mentioned electroconductive particle can have substrate particle and the conductive part being configured on the surface of the substrate particle.Should In the case of, above-mentioned electroconductive particle has scolding tin in the outer surface part of conductive part.
It should be noted that compared with using the situation of above-mentioned scolding tin particle, in the base formed using possessing by non-scolding tin In the case of material particle and the electroconductive particle for the solder sections being configured on the surface of substrate particle, electroconductive particle is not easy to assemble Easily to move on electrode, the mutual scolding tin zygosity of electroconductive particle is low, and accordingly, there exist the electroconductive particle moved on electrode The tendency outside electrode is moved, the tendency that the inhibition step-down of interelectrode position skew be present.Therefore, above-mentioned electroconductive particle Preferably scolding tin particle.
From the connection resistance being effectively reduced in connection structural bodies, and effectively from the viewpoint of the generation of suppression hole, It is preferred that carboxyl or amino be present in the outer surface of above-mentioned electroconductive particle (outer surface of scolding tin), carboxyl preferably be present, preferably deposit In amino.The group represented preferably via Si-O keys, ehter bond, ester bond or following formula (X)s is total to the group containing carboxyl or amino Valency is bonded in the outer surface (outer surface of scolding tin) of above-mentioned electroconductive particle, more preferably via ehter bond, ester bond or following formula (X) tables The group shown makes to carry out covalent bonding containing the group of carboxyl or amino.Group containing carboxyl or amino can contain carboxyl and Both amino.It should be noted that in following formula (X)s, right part and left part represent bonding position.
[chemical formula 1]
Hydroxyl be present on the surface of scolding tin., can be with shape by making the hydroxyl and group containing carboxyl carry out covalent bonding Into stronger bonding compared with using the situation of the bondings such as other coordinate bonds (chelate coordination), therefore, obtaining can be between electrode Connection resistance reduce and can suppress the caused electroconductive particle of hole.
In above-mentioned electroconductive particle, it can not contained in the speciation of the surface of scolding tin and group containing carboxyl Coordinate bond, the bonding based on chelate coordination can also not contained.
From the viewpoint of the generation for suppressing from the connection resistance being effectively reduced in connection structural bodies and effectively hole, Above-mentioned electroconductive particle preferably by using with can with the functional group of hydroxyl reaction and the compound with carboxyl or amino (with Under, sometimes referred to as compound X), make above-mentioned to obtain with the hydroxyl reaction on scolding tin surface with the functional group of hydroxyl reaction. In above-mentioned reaction, covalent bond is formed.By the way that make can be with the hydroxyl on scolding tin surface and the above-mentioned hydroxyl reaction in above-claimed cpd X Functional group is reacted, and can be readily derived the electric conductivity grain on scolding tin surface containing carboxyl or amino group covalent bonding Son, the group containing carboxyl or amino can be obtained via the electric conductivity grain of ehter bond or ester bond covalent bonding on the surface of scolding tin Son.By making above-mentioned functional group that can be with hydroxyl reaction and the hydroxyl reaction on above-mentioned scolding tin surface, can make on the surface of scolding tin Above-claimed cpd X is chemically bonded in the form of covalent bond.
Hydroxyl, carboxyl, ester group and carbonyl etc. can be enumerated as above-mentioned with the functional group of hydroxyl reaction.It is preferred that hydroxyl or Carboxyl.Above-mentioned can be able to be hydroxyl with the functional group of hydroxyl reaction, or carboxyl.
As be able to can be enumerated with the compound of the functional group of hydroxyl reaction：Levulic acid, glutaric acid, glycolic, amber Amber acid, malic acid, oxalic acid, malonic acid, adipic acid, 5- ketone caproic acid, 3- hydracrylic acids, 4-Aminobutanoicacid, 3- mercaptopropionic acids, 3- mercaptos Base isobutyric acid, 3- methylpropanethioates, 3- phenylpropionic acids, 3- phenylisobutyrics, 4-phenylbutyrate, capric acid, dodecylic acid, 14 Alkanoic acid, pentadecanoic acid, hexadecanoic acid, palmitoleic acid, Heptadecanoic acide, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-leukotrienes, nonadecylic acid, arachidic acid, decane diacid and dodecanedioic acid etc..It is preferred that glutaric acid or glycolic.Tool Have it is above-mentioned can use independent a kind with the compound of the functional group of hydroxyl reaction, two or more can also be applied in combination.Have Above-mentioned can be preferably the compound with least one carboxyl with the compound of the functional group of hydroxyl reaction.
Above-claimed cpd X preferably has fluxing agent effect, and above-claimed cpd X is preferably to be bonded to the state on the surface of scolding tin Acted on fluxing agent.Compound with fluxing agent effect can remove the oxidation of the oxide-film and electrode surface on scolding tin surface Film.Carboxyl has fluxing agent effect.
As the compound acted on fluxing agent, can enumerate：Levulic acid, glutaric acid, glycolic, butanedioic acid, 5- ketone Caproic acid, 3- hydracrylic acids, 4-Aminobutanoicacid, 3- mercaptopropionic acids, 3- mercaptoisobutyric acids, 3- methylpropanethioates, 3- phenylpropionic acids, 3- phenylisobutyrics and 4-phenylbutyrate etc..It is preferred that glutaric acid or glycolic.The above-mentioned compound with fluxing agent effect can be with Using independent a kind, two or more can also be applied in combination.
From the connection resistance being effectively reduced in connection structural bodies, and effectively from the viewpoint of the generation of suppression hole, Above-mentioned in above-claimed cpd X can be preferably hydroxyl or carboxyl with the functional group of hydroxyl reaction.Above-mentioned in above-claimed cpd X can Functional group with hydroxyl reaction can be hydroxyl, or carboxyl.It is above-mentioned can be carboxyl with the functional group of hydroxyl reaction In the case of, above-claimed cpd X preferably has at least two carboxyl.Pass through the part of the compound that makes to have at least two carboxyl Carboxyl and the hydroxyl reaction on scolding tin surface, electroconductive particle of the radicals covalent bonds conjunction containing carboxyl on scolding tin surface can be obtained.
The manufacture method of above-mentioned electroconductive particle for example possesses following process：Using electroconductive particle, the electric conductivity is mixed Particle, have can be with the functional group of hydroxyl reaction and compound, catalyst and the solvent of carboxyl.The manufacture of above-mentioned electroconductive particle In method, by above-mentioned mixed processes, it can be readily derived and be covalently bonded with leading for the group containing carboxyl on scolding tin surface Conductive particles.
In addition, in the manufacture method of above-mentioned electroconductive particle, preferably using electroconductive particle, mix the electroconductive particle, With it is above-mentioned can be with the functional group of hydroxyl reaction and compound, above-mentioned catalyst and the above-mentioned solvent of carboxyl and being heated.It is logical Mixing and heating process are crossed, can further be readily derived and be covalently bonded with leading for the group containing carboxyl on scolding tin surface Conductive particles.
As above-mentioned solvent, can enumerate：The alcoholic solvents such as methanol, ethanol, propyl alcohol and butanol or acetone, methyl ethyl ketone, second Acetoacetic ester, toluene and dimethylbenzene etc..Above-mentioned solvent is preferably organic solvent, more preferably toluene.Above-mentioned solvent can use single Only a kind, two or more can also be applied in combination.
As above-mentioned catalyst, p-methyl benzenesulfonic acid, benzene sulfonic acid and 10- camphorsulfonic acids etc. can be enumerated.Above-mentioned catalyst is preferred For p-methyl benzenesulfonic acid.Above-mentioned catalyst can use independent a kind, and two or more can also be applied in combination.
It is preferred that heated in above-mentioned mixing.Heating-up temperature is preferably more than 90 DEG C, more preferably more than 100 DEG C, excellent Elect less than 130 DEG C, more preferably less than 110 DEG C as.
From the viewpoint of the generation for suppressing from the connection resistance being effectively reduced in connection structural bodies and effectively hole, Above-mentioned electroconductive particle is preferably through the hydroxyl for using isocyanate compound, making above-mentioned isocyanate compound and scolding tin surface The process of reaction and obtain.In above-mentioned reaction, covalent bond is formed.Pass through the hydroxyl for making scolding tin surface and above-mentioned isocyanation esterification Compound reacts, and can be readily derived electric conductivity of the nitrogen-atoms covalent bonding on scolding tin surface of the group from NCO Particle.By making the hydroxyl reaction of above-mentioned isocyanate compound and above-mentioned scolding tin surface, can make to be derived from the surface of scolding tin The group of NCO is chemically bonded in the form of covalent bond.
Furthermore it is possible to silane coupler is set easily to be reacted with the group from NCO.Due to can be easily Above-mentioned electroconductive particle is obtained, therefore, the above-mentioned group containing carboxyl is preferably by using there is the silane coupler with carboxyl Reaction and be imported into, or preferably by using after having the reaction of silane coupler, by making that there is at least one carboxyl Compound with from silane coupler radical reaction and be imported into.Above-mentioned electroconductive particle is preferably by using above-mentioned isocyanide Ester compound, and make the hydroxyl reaction of above-mentioned isocyanate compound and scolding tin surface, then make that there is at least one carboxyl Compound reaction and obtain.
From the viewpoint of the generation for suppressing from the connection resistance being effectively reduced in connection structural bodies and effectively hole, It is preferred that the above-mentioned compound with least one carboxyl is with multiple carboxyls.
As above-mentioned isocyanate compound, can enumerate：Diphenyl methane -4,4 '-diisocyanate (MDI), six methylenes Group diisocyanate (HDI), toluene di-isocyanate(TDI) (TDI) and IPDI (IPDI) etc..This can be used Isocyanate compound beyond a little.Make the compound scolding tin surface reaction after, make residual NCO and, it is residual with this Compound reaction of the NCO with reactivity and with carboxyl, it is possible thereby to via the group of formula (X) expression by carboxyl It is directed in scolding tin surface.
As above-mentioned isocyanate compound, the chemical combination with unsaturated double-bond and with NCO can be used Thing.Such as 2- acryloyloxyethyl isocyanates and 2- isocyanatoethyl methacrylates can be enumerated.Make the chemical combination The NCO of thing makes the official for having reactivity containing the unsaturated double-bond relative to residual after the reaction of the surface of scolding tin It can roll into a ball and the compound with carboxyl is reacted, the group that carboxyl represents via formula (X) is directed in scolding tin surface.
As above-mentioned silane coupler, 3- isocyanates propyl-triethoxysilicane (silicone societies of SHIN-ETSU HANTOTAI system can be enumerated " KBE-9007 " made) and 3- isocyanates propyl trimethoxy silicane (" Y-5187 " of the manufacture of MOMENTIVE companies) etc.. Above-mentioned silane coupler can use independent a kind, and two or more can also be applied in combination.
As the above-mentioned compound with least one carboxyl, can enumerate：Levulic acid, glutaric acid, glycolic, amber Acid, malic acid, oxalic acid, malonic acid, adipic acid, 5- ketone caproic acid, 3- hydracrylic acids, 4-Aminobutanoicacid, 3- mercaptopropionic acids, 3- sulfydryls Isobutyric acid, 3- methylpropanethioates, 3- phenylpropionic acids, 3- phenylisobutyrics, 4-phenylbutyrate, capric acid, dodecylic acid, the tetradecane Acid, pentadecanoic acid, hexadecanoic acid, palmitoleic acid, Heptadecanoic acide, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9, 12,15)-leukotrienes, nonadecylic acid, arachidic acid, decanedioic acid and dodecanedioic acid etc..It is preferred that glutaric acid, adipic acid or glycolic. The above-mentioned compound with least one carboxyl can use independent a kind, and two or more can also be applied in combination.
Using above-mentioned isocyanate compound, make the hydroxyl reaction of above-mentioned isocyanate compound and scolding tin surface, then, Make a part of carboxyl and the hydroxyl reaction on scolding tin surface of compound with multiple carboxyls, it is possible thereby to make the base containing carboxyl Group's residual.
In the manufacture method of above-mentioned electroconductive particle, make using electroconductive particle, and using isocyanate compound The hydroxyl reaction of isocyanate compound and scolding tin surface is stated, then, makes to have the compound of at least one carboxyl to be reacted, obtains On the surface of scolding tin the electroconductive particle of the group containing carboxyl is bonded with via the group that above-mentioned formula (X) represents.Above-mentioned In the manufacture method of electroconductive particle, by above-mentioned process, it can be readily derived to have imported on the surface of scolding tin and contain carboxylic The electroconductive particle of the group of base.
As the specific manufacture method of above-mentioned electroconductive particle, following method can be enumerated.Disperse electroconductive particle In organic solvent, silane coupler of the addition with NCO.Thereafter, using electroconductive particle scolding tin surface hydroxyl With the catalysts of NCO, silane coupler is set to carry out covalent bonding on the surface of scolding tin.Then, by making bonding It is hydrolyzed in the alkoxy of the silicon atom of silane coupler and generates hydroxyl.Make the carboxylic with the compound of at least one carboxyl Base and the hydroxyl reaction of generation.
In addition, the specific manufacture method as above-mentioned electroconductive particle, can enumerate following method.Make electroconductive particle It is scattered in organic solvent, compound of the addition with NCO and unsaturated double-bond.Thereafter, using the weldering of electroconductive particle The hydroxyl of tin surfaces and the catalysts of NCO form covalent bond.Thereafter, relative to the unsaturated double-bond imported, React unsaturated double-bond and the compound with carboxyl.
As the hydroxyl on scolding tin surface and the catalysts of NCO of electroconductive particle, can enumerate：Tin class is urged Agent (dibutyltin dilaurate etc.), amines catalyst (triethylenediamine etc.), carboxylic acid ester catalyst (lead naphthenate, acetic acid Potassium etc.) and trialkyl phosphine catalyst (triethyl phosphine etc.) etc..
From the connection resistance being effectively reduced in connection structural bodies, and effectively from the viewpoint of the generation of suppression hole, The above-mentioned compound with least one carboxyl is preferably the compound that following formula (1) represents.The compound that following formula (1) represents Acted on fluxing agent.In addition, the compound that following formula (1) represents has fluxing agent in the state of the surface of scolding tin is directed in Effect.
[chemical formula 2]
In above-mentioned formula (1), X represents that the organic group of the divalent of carbon number 1~5 can be represented with the functional group of hydroxyl reaction, R Group.The organic group can contain carbon atom, hydrogen atom and oxygen atom.The organic group can be the divalent of carbon number 1~5 Alkyl.The main chain of above-mentioned organic group is preferably the alkyl of divalent.For organic group, it can be bonded on the alkyl of divalent Carboxyl or hydroxyl.Such as citric acid is included in the compound that above-mentioned formula (1) represents.
The above-mentioned compound with least one carboxyl is preferably the compound that following formula (1A) or following formula (1B) represent. The above-mentioned compound with least one carboxyl is preferably the compound that following formula (1A) represents, more preferably following formula (1B) table The compound shown.
[chemical formula 3]
In above-mentioned formula (1A), R represents the organic group of the divalent of carbon number 1~5.R and above-mentioned formula in above-mentioned formula (1A) (1) R in is identical.
[chemical formula 4]
In above-mentioned formula (1B), R represents the organic group of the divalent of carbon number 1~5.R and above-mentioned formula in above-mentioned formula (1B) (1) R in is identical.
It is preferred that the surface bond in scolding tin has the group that following formula (2A) or following formula (2B) represent.It is preferred that in the table of scolding tin Face is bonded with the group of following formula (2A) expression, is more preferably bonded with the group of following formula (2B) expression.It should be noted that In following formula (2A) and following formula (2B), left part represents bonding position.
[chemical formula 5]
In above-mentioned formula (2A), R represents the organic group of the divalent of carbon number 1~5.R and above-mentioned formula in above-mentioned formula (2A) (1) R in is identical.
[chemical formula 6]
In above-mentioned formula (2B), R represents the organic group of the divalent of carbon number 1~5.R and above-mentioned formula in above-mentioned formula (2B) (1) R in is same.
From the viewpoint of scolding tin wettability of the surface is improved, the molecular weight of the above-mentioned compound with least one carboxyl Preferably less than 10000, more preferably less than 1000, more preferably less than 500.
It is not polymer in the above-mentioned compound with least one carboxyl for above-mentioned molecular weight, and on State the compound with least one carboxyl structural formula it is confirmable in the case of, it is intended that can be calculated by the structural formula point Son amount.In addition, in the case that the above-mentioned compound with least one carboxyl is polymer, it is intended that weight average molecular weight.
From the aspect of it can effectively improve the compendency of electroconductive particle when being conductively connected, above-mentioned electroconductive particle It is preferred that conductive particle main body and the anionic polymer being configured on the surface of above-mentioned electroconductive particle main body.It is above-mentioned Electroconductive particle using electroconductive particle main body by the use of anionic polymer or as the compound of anionic polymer preferably by entering Row is surface-treated and obtained.Above-mentioned electroconductive particle is preferably anionic polymer or the compound shape as anionic polymer Into surface treatment.Above-mentioned anionic polymer and the above-mentioned compound as anionic polymer can use independent respectively 1 kind, two or more can also be applied in combination.Above-mentioned anionic polymer is the polymer with acidic groups.
As the method for being surface-treated electroconductive particle main body with anionic polymer, it is for example right use can be enumerated (methyl) acrylic acid is copolymerized and forms (methyl) acrylate copolymer；Synthesized by dicarboxylic acids and glycol and had in two ends There are the polyester polymers of carboxyl；Obtained by the intermolecular dehydration condensation of dicarboxylic acids and there is the polymerization of carboxyl in two ends Thing；Synthesized by dicarboxylic acids and diamines and there are the polyester polymers of carboxyl in two ends；And the modified poly ethylene with carboxyl Alcohol (Japan synthesize the manufacture of chemical society " Gohsenol T ") etc. as anionic polymer, make anionic polymer carboxyl and The method of the hydroxyl reaction on the surface of electroconductive particle main body.
As the anionicsite of above-mentioned anionic polymer, above-mentioned carboxyl can be enumerated, in addition, toluene sulphur can be enumerated Acyl group (p-H3CC6H4S (=O)2-), sulfonate ion (- SO3 -) and phosphate anion (- PO4 -) etc..
In addition, other methods as surface treatment, can enumerate following methods：Using with electroconductive particle body table The functional group of the hydroxyl reaction in face, and have and this can be made by the compound for the functional group that addition condensation reaction is polymerize The method that compound carries out polymerization on the surface of electroconductive particle main body.As the surface with electroconductive particle main body The functional group of hydroxyl reaction, carboxyl and NCO etc. can be enumerated, as by addition, condensation reaction and the official that is polymerize It can roll into a ball, hydroxyl, carboxyl, amino and (methyl) acryloyl group can be enumerated.
The weight average molecular weight of above-mentioned anionic polymer is preferably more than 2000, and more preferably more than 3000, be preferably Less than 10000, more preferably less than 8000., can be with when above-mentioned weight average molecular weight is more than above-mentioned lower limit and below the above-mentioned upper limit An adequate amount of electric charge and fluxibility are imported on the surface of electroconductive particle.Thus, it can effectively improve and lead when being conductively connected The compendency of conductive particles, and can effectively remove in the connection of connecting object part the oxide-film of electrode surface.
When above-mentioned weight average molecular weight is more than above-mentioned lower limit and below the above-mentioned upper limit, easily in the table of electroconductive particle main body Anionic polymer is configured on face, the compendency of electroconductive particle can be effectively improved when being conductively connected, can be in electrode It is upper further effectively to configure electroconductive particle.
Above-mentioned weight average molecular weight represents the weight average molecular weight of the polystyrene basis using gel permeation chromatography (GPC) measure.
The weight average molecular weight of anionic polymer can be obtained as follows：Scolding tin in electroconductive particle is melted, profit Watery hydrochloric acid with the decomposition for not causing anionic polymer etc. removes electroconductive particle, then, determines the anionic polymerisation of residual The weight average molecular weight of thing.
On the import volume on the surface of the electroconductive particle of anionic polymer, electroconductive particle 1g acid number is preferably More than 1mgKOH, more preferably more than 2mgKOH, preferably below 10mgKOH, more preferably below 6mgKOH.
Above-mentioned acid number can be measured as follows.Electroconductive particle 1g is added in acetone 36g, makes it using ultrasonic wave It is scattered 1 minute.Thereafter, using phenolphthalein as indicator, titrated with 0.1mol/L potassium hydroxide-ethanol solution.
Below, on one side referring to the drawings, while the concrete example of explanation electroconductive particle.
Fig. 4 is the profile for the first case for representing the electroconductive particle available for conductive material.
Electroconductive particle 21 shown in Fig. 4 is scolding tin particle.The entirety of electroconductive particle 21 is formed by scolding tin.Electric conductivity grain Son 21 does not have substrate particle in core, is not core shell particle.The core of electroconductive particle 21 and the outer surface of conductive part Part is formed by scolding tin.
Fig. 5 is the profile for the second case for representing the electroconductive particle available for conductive material.
The conduction that electroconductive particle 31 shown in Fig. 5 possesses substrate particle 32 and is configured on the surface of substrate particle 32 Portion 33.Conductive part 33 is coated to the surface of substrate particle 32.Electroconductive particle 31 is to substrate particle by conductive part 33 The coating particles that 32 surface is coated.
Conductive part 33 has the second conductive part 33A and solder sections 33B (the first conductive part).Electroconductive particle 31 is in base material grain Possesses the second conductive part 33A between 32 and solder sections 33B of son.Therefore, electroconductive particle 31 possesses：Substrate particle 32, it is configured at The second conductive part 33A on the surface of the substrate particle 32 and solder sections 33B being configured on the second conductive part 33A outer surface.
Fig. 6 is the profile of the 3rd for representing the electroconductive particle available for conductive material.
As described above, the conductive part 33 in electroconductive particle 31 has 2 Rotating fields.Electroconductive particle 41 shown in Fig. 6 is made For the conductive part of individual layer, there are solder sections 42.Electroconductive particle 41 possesses：Substrate particle 32 and it is configured at substrate particle 32 Solder sections 42 on surface.
As above-mentioned substrate particle, resin particle, the inorganic particulate in addition to metallic, organic inorganic hybridization can be enumerated Particle and metallic etc..Above-mentioned substrate particle is preferably substrate particle in addition to metal, preferably resin particle, except metal Inorganic particulate or organic inorganic hybridization particle outside particle.Above-mentioned substrate particle can be copper particle.Above-mentioned substrate particle can With with core and the shell being configured on the surface of the core, or core shell particle.Above-mentioned core can be organic core, and above-mentioned shell can Think inorganic shell.
As the resin for forming above-mentioned resin particle, preferably using various organic matters.As for forming above-mentioned tree The resin of fat granule, can be enumerated for example：Polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, poly- isobutyl The vistanexes such as alkene, polybutadiene；The acrylic resin such as polymethyl methacrylate and PMA；Poly- carbonic acid Ester, polyamide, phenol formaldehyde resin, melamine resin, benzoguanamin formaldehyde resin, urea-formaldehyde resin, phenolic aldehyde tree It is fat, melmac, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, poly- Ethylene glycol terephthalate, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone, polyether sulfone, Divinyl benzene polymers and divinylbenzene analog copolymer etc..As above-mentioned divinylbenzene analog copolymer etc., can enumerate Divinyl benzene styrene copolymer and divinylbenzene-(methyl) acrylate copolymer etc..Due to can be by above-mentioned resin The hardness of particle is readily controlled in suitable scope, therefore, for formed above-mentioned resin particle resin be preferably make a kind or The polymer that polymerizable monomer of more than two kinds with ethylenically unsaturated group aggregates into.
In the case of being polymerize in the polymerizable monomer for making there is ethylenically unsaturated group and obtaining above-mentioned resin particle, There is the polymerizable monomer of ethylenically unsaturated group as this, the monomer of non-crosslinked property and the monomer of bridging property can be enumerated.
As the monomer of above-mentioned non-crosslinked property, can enumerate for example：The styrene monomers such as styrene, α-methylstyrene； The carboxylic 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 base ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid are different Norbornene ester etc. (methyl) acrylic acid alkyl ester compound；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) glycerol acrylate, gather (methyl) acrylate compounds containing oxygen atom such as oxygen ethene (methyl) acrylate, (methyl) glycidyl acrylate； The monomers containing nitrile such as (methyl) acrylonitrile；The vinyl ethers chemical combination such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether Thing；The acetate compounds such as vinyl acetate, vinyl butyrate, vinyl laurate, stearic acid vinyl ester；Ethene, propylene, The unsaturated hydrocarbons such as isoprene, butadiene；(methyl) acrylic acid trifluoromethyl ester, the fluorine ethyl ester of (methyl) acrylic acid five, vinyl chloride, fluorine Halogen monomer such as ethene, chlorostyrene etc..
As the monomer of above-mentioned bridging property, can enumerate for example：Tetramethylol methane four (methyl) acrylate, tetra methylol Methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid Ester, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) propylene acid glycerols Ester, two (methyl) glycerol acrylates, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propane diols two (methyl) acrylic acid Multifunctional (methyl) such as ester, (poly-) tetramethylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate Acrylate compounds；(different) triallyl cyanurate, triallyltrimelitate, divinylbenzene, diallyl phthalate Propyl ester, diallyl acrylamide, diallyl ether and γ-(methyl) propenyloxy group propyl trimethoxy silicane, trimethoxy Monomers of silane-containing such as base silicyl styrene, vinyltrimethoxy silane etc..
It is polymerize the above-mentioned polymerizable monomer with ethylenically unsaturated group by using known method, can be obtained To above-mentioned resin particle.As this method, can enumerate for example：Suspension polymerisation is carried out in the presence of radical polymerization initiator Method；And use noncrosslinking kind of particle, the method that monomer swell is made together with radical polymerization initiator and is polymerize Deng.
In the case where above-mentioned substrate particle is inorganic particulate or organic inorganic hybridization particle in addition to metal, as with In the inorganic matter for forming substrate particle, silica, aluminium dioxide, barium titanate, zirconium oxide and carbon black etc. can be enumerated.It is above-mentioned inorganic Thing is preferably nonmetallic.As the above-mentioned particle formed by silica, it is not particularly limited, can enumerates for example by that will have The silicon compound of the water-disintegrable alkoxysilyl of more than 2 is hydrolyzed and forms cross-linking polymer particle, then, according to Need particle obtained from being burnt till.As above-mentioned organic inorganic hybridization particle, the alkoxy first for example by being crosslinked can be enumerated Organic inorganic hybridization particle that silane based polyalcohol and acrylic resin are formed etc..
In the case where above-mentioned substrate particle is metallic, as the metal for forming the metallic, can enumerate Silver, copper, nickel, silicon, gold and titanium etc..In the case where above-mentioned substrate particle is metallic, the metallic is preferably copper particle. But above-mentioned substrate particle is not preferably metallic.
The particle diameter of above-mentioned substrate particle is preferably more than 0.1 μm, more preferably more than 1 μm, more preferably 1.5 μm with On, particularly preferably more than 2 μm, preferably less than 100 μm, more preferably less than 50 μm, it is still more preferably less than 40 μm, More preferably less than 20 μm, be still more preferably less than 10 μm, particularly preferably less than 5 μm, most preferably 3 μm with Under.When the particle diameter of above-mentioned substrate particle is more than above-mentioned lower limit, the contact area of electroconductive particle and electrode becomes big, therefore, can Further to improve interelectrode conducting reliability, can further reduce via the interelectrode of electroconductive particle connection Connect resistance.When the particle diameter of above-mentioned substrate particle is below the above-mentioned upper limit, electroconductive particle is easily fully compressed, Ke Yigeng Interelectrode connection resistance is further reduced, and can more reduce interelectrode interval.
For the particle diameter of above-mentioned substrate particle, in substrate particle in the case of just spherical, diameter to be represented, in base material grain In the case that son is not just spherical, maximum gauge is represented.
The particle diameter of above-mentioned substrate particle is particularly preferably more than 2 μm, less than 5 μm.The particle diameter of above-mentioned substrate particle be 2 μm with When above, in less than 5 μm of scope, interelectrode interval can be more reduced, and even if thickening the thickness of conductive layer, can also obtain To small electroconductive particle.
On the surface of above-mentioned substrate particle formed conductive part method and on the surface of above-mentioned substrate particle or on The method for stating formation solder sections on the surface of the second conductive part is not particularly limited.As the above-mentioned conductive part of formation and above-mentioned scolding tin The method in portion, it can enumerate for example：Using the method for electroless plating, using electric plating method, using physics conflict method, Using the method for mechanico-chemical reaction, using the method for physical vapor deposition or physical absorption and by metal dust or contain metal The paste coating of powder and adhesive is in the method on substrate particle surface etc..Preferably by electroless plating, plating or physics The method of conflict.As the method for the above-mentioned evaporation using physics, the side such as vacuum evaporation, ion plating and ion sputtering can be enumerated Method.In addition, above-mentioned using in the method for physics conflict, (Co., Ltd.'s moral longevity works usable such as Theta composer It is manufactured) etc..
Fusing point of the fusing point of above-mentioned substrate particle preferably than above-mentioned conductive part and above-mentioned solder sections is high.Above-mentioned substrate particle Fusing point is preferably greater than 160 DEG C, more preferably above 300 DEG C, further preferably more than 400 DEG C, particularly preferably more than 450 DEG C.Need Illustrate, the fusing point of above-mentioned substrate particle can be less than 400 DEG C.The fusing point of above-mentioned substrate particle can be less than 160 DEG C. The softening point of above-mentioned substrate particle is preferably more than 260 DEG C.The softening point of above-mentioned substrate particle can be less than 260 DEG C.
Above-mentioned electroconductive particle can have the solder sections of individual layer.Above-mentioned electroconductive particle can have the conductive part of multilayer (solder sections, the second conductive part).That is, can be with the conductive part of more than 2 layers of lamination in above-mentioned electroconductive particle.Above-mentioned conductive part In the case of for more than 2 layers, above-mentioned electroconductive particle preferably has scolding tin in the outer surface part of conductive part.
Above-mentioned scolding tin is preferably the metal (low-melting-point metal) that fusing point is less than 450 DEG C.Above-mentioned solder sections are preferably fusing point For less than 450 DEG C of metal levels (low-melting-point metal layer).Above-mentioned low-melting-point metal layer is the layer containing low-melting-point metal.It is above-mentioned to lead Scolding tin in conductive particles is preferably the metallic (low-melting-point metal particle) that fusing point is less than 450 DEG C.Above-mentioned low melting point gold Category particle is the particle containing low-melting-point metal.The low-melting-point metal represents the metal that fusing point is less than 450 DEG C.Low-melting-point metal Fusing point be preferably less than 300 DEG C, more preferably less than 160 DEG C.In addition, the scolding tin in above-mentioned electroconductive particle preferably comprises Tin.The contained weight of metal 100 in scolding tin in above-mentioned solder sections in the contained weight % of metal 100 and in above-mentioned electroconductive particle Measure in %, the content of tin is preferably more than 30 weight %, more preferably more than 40 weight %, more preferably 70 weight % with On, particularly preferably more than 90 weight %.In scolding tin in above-mentioned electroconductive particle the content of contained tin for above-mentioned lower limit with When upper, the conducting reliability of electroconductive particle and electrode further raises.
It should be noted that the content of above-mentioned tin can use high-frequency inductive coupling plasma body emission spectrophotometer (" ICP-AES " of Horiba Ltd's manufacture) or fluorescent x-ray analyzer (Shimadzu Scisakusho Ltd's system " EDX-800HS " made) etc. be measured.
The electroconductive particle of above-mentioned scolding tin is had by using the outer surface part in conductive part, scolding tin occur melting and with Electrode engagement, scolding tin make to turn between electrode.For example, due to scolding tin and electrode, easily the face of progress contacts rather than a contact, therefore, Connect resistance step-down.In addition, the electroconductive particle of scolding tin, scolding tin and electrode are had by using the outer surface part in conductive part Bond strength rise, as a result, be further not likely to produce the stripping of scolding tin and electrode, conducting reliability effectively raises.
The low-melting-point metal for forming above-mentioned solder sections and above-mentioned scolding tin particle is not particularly limited.The low-melting-point metal is preferred Alloy for tin or containing tin.The alloy can be enumerated：Tin-silver alloy, tin-copper alloy, tin-silver-copper alloy, tin-bismuth alloy electroplating, Tin-zinc alloy, Sn-In alloy etc..From the aspect of the wetability to electrode is excellent, above-mentioned low-melting-point metal be preferably tin, tin- Silver alloy, tin-silver-copper alloy, tin-bismuth alloy electroplating, Sn-In alloy.More preferably tin-bismuth alloy electroplating, Sn-In alloy.
The material for forming above-mentioned scolding tin (solder sections) is preferably based on JISZ3001：Weld term, liquidus curve be 450 DEG C with Under filling metal.As the composition of above-mentioned scolding tin, the metal such as containing zinc, gold, silver, lead, copper, tin, bismuth, indium can be enumerated Composition.Preferably low melting point and unleaded tin-indium system (117 DEG C of eutectics) or Sn-Bi system (139 DEG C of eutectics).That is, above-mentioned scolding tin It is preferred that lead is not contained, the scolding tin preferably containing tin and indium or the scolding tin containing tin and bismuth.
In order to further improve the bond strength of above-mentioned scolding tin and electrode, the scolding tin in above-mentioned electroconductive particle can contain There are the metals such as nickel, copper, antimony, aluminium, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, chromium, molybdenum, palladium.In addition, from further carrying From the viewpoint of the bond strength of high scolding tin and electrode, the scolding tin in above-mentioned electroconductive particle preferably comprise nickel, copper, antimony, aluminium or Zinc.From the viewpoint of from the bond strength of the further scolding tin improved in solder sections or electroconductive particle and electrode, for carrying In the weight % of scolding tin 100 of the content of these metals of high bond strength in above-mentioned electroconductive particle, preferably 0.0001 weight More than % is measured, preferably below 1 weight %.
Fusing point of the fusing point of above-mentioned second conductive part preferably than above-mentioned solder sections is high.The fusing point of above-mentioned second conductive part is preferred More than 160 DEG C, more preferably above 300 DEG C, further preferably more than 400 DEG C, still more preferably more than 450 DEG C, particularly preferably More than 500 DEG C, most preferably more than 600 DEG C.Because the fusing point of above-mentioned solder sections is low, therefore, melted when being conductively connected.On The second conductive part is stated preferably not melt when being conductively connected.Above-mentioned electroconductive particle preferably makes scolding tin melt and use, excellent Choosing makes above-mentioned solder sections melt and use, and preferably melts above-mentioned solder sections and above-mentioned second conductive part is melted and is used. By making the fusing point of above-mentioned second conductive part higher than the fusing point of above-mentioned solder sections, above-mentioned solder sections can be only made when being conductively connected Melting is without melting above-mentioned second conductive part.
The absolute value of the difference of the fusing point of the fusing point of above-mentioned solder sections and above-mentioned second conductive part more than 0 DEG C, preferably 5 DEG C with On, more preferably more than 10 DEG C, more preferably more than 30 DEG C, particularly preferably more than 50 DEG C, most preferably 100 DEG C with On.
Above-mentioned second conductive part preferably comprises metal.The metal for forming above-mentioned second conductive part is not particularly limited.As The metal, it can enumerate for example：Gold, silver, copper, platinum, palladium, zinc, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium and it Alloy etc..In addition, as above-mentioned metal, tin-doped indium oxide (ITO) can be used.Above-mentioned metal can use independent 1 Kind, two or more can also be applied in combination.
Above-mentioned second conductive part is preferably nickel dam, palladium layers, layers of copper or layer gold, more preferably nickel dam or layer gold, further excellent Elect layers of copper as.Electroconductive particle preferably has nickel dam, palladium layers, layers of copper or layer gold, further excellent more preferably with nickel dam or layer gold Choosing has layers of copper.By the way that the electroconductive particle with these preferable conductive parts is used for into interelectrode connection, interelectrode company The further step-down of connecting resistance.Furthermore it is possible to further it is readily formed solder sections on the surface of these preferable conductive parts.
The thickness of above-mentioned solder sections is preferably more than 0.005 μm, more preferably more than 0.01 μm, preferably less than 10 μm, More preferably less than 1 μm, more preferably less than 0.3 μm.The thickness of solder sections be above-mentioned lower limit more than and the above-mentioned upper limit with When lower, sufficient electric conductivity is can obtain, and electroconductive particle will not become really up to the mark, in interelectrode connection, electroconductive particle fills Divide ground deformation.
The average grain diameter of above-mentioned electroconductive particle is preferably more than 0.5 μm, more preferably more than 1 μm, more preferably 3 More than μm, preferably less than 100 μm, more preferably less than 50 μm, more preferably less than 40 μm, particularly preferably 30 μm with Under.When above-mentioned electroconductive particle is more than above-mentioned lower limit and below the above-mentioned upper limit, the scolding tin in electroconductive particle can be made more to enter One step is efficiently configured on electrode, the scolding tin in electroconductive particle is more configured between electrode, turns on reliability Further rise.
" average grain diameter " of above-mentioned electroconductive particle represents number average bead diameter.The average grain diameter of electroconductive particle for example by using Electron microscope or the arbitrary electroconductive particle of observation by light microscope 50 simultaneously calculate average value and obtained.
The shape of above-mentioned electroconductive particle is not particularly limited.The shape of above-mentioned electroconductive particle can be spherical, also may be used Think the shape beyond flat equal sphere.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned electroconductive particle is preferably more than 1 weight %, more preferably For more than 2 weight %, more preferably more than 10 weight %, particularly preferably more than 20 weight %, most preferably 30 weights More than % is measured, preferably below 80 weight %, more preferably below 60 weight %, more preferably below 50 weight %.On When stating the content of electroconductive particle as more than above-mentioned lower limit and below the above-mentioned upper limit, the scolding tin in electroconductive particle can more be entered One step is efficiently configured on electrode, the scolding tin in electroconductive particle is easily more configured between electrode, conducting reliability is more Further rise.From the viewpoint of further raising conducting reliability, the content of preferably above-mentioned electroconductive particle is more.
(Thermocurable compound)
Above-mentioned Thermocurable compound is compound that can be by heating to solidify.As above-mentioned Thermocurable compound, It can enumerate：Oxetane compound, epoxide, episulfide compound, (methyl) acyclic compound, phenolate are closed Thing, amino-compound, unsaturated polyester compound, urethanes, polysiloxane compound and polyimide compound etc.. It is further good from the curability and viscosity for making conductive material, from the viewpoint of further improving connection reliability, preferably Epoxide or episulfide compound.Above-mentioned Thermocurable compound can use independent a kind, can also be applied in combination 2 More than kind.
From the further corrosion for suppressing electrode, and further low land is maintained from the viewpoint of connecting resistance, above-mentioned heat Curability compound preferably comprises the Thermocurable compound with nitrogen-atoms, preferably comprises the Thermocurable with triazine skeleton Compound.
It is highly effective especially by being applied in combination for the Thermocurable compound with nitrogen-atoms and acid anhydrides thermal curing agents Ground suppresses the generation of migration.
As the above-mentioned Thermocurable compound with nitrogen-atoms, triazine triglycidyl group ether etc. can be enumerated, can be enumerated Nissan Chemical Industries society TEPIC series (TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC- PAS, TEPIC-VL, TEPIC-UC) etc..
As above-mentioned epoxide, aromatic epoxy compound can be enumerated.Preferably resorcinol type ring oxygen compound, The crystallinity epoxides such as naphthalene type ring oxygen compound, biphenyl type epoxy compound and diphenyl ketone type epoxide.It is preferred that Be solid under normal temperature (23 DEG C) and melting temperature be below the fusing point of scolding tin epoxide.Melting temperature is preferably 100 Below DEG C, more preferably less than 80 DEG C, preferably more than 40 DEG C.By using above-mentioned preferable epoxide, to even The stage that object Part is bonded is connect, viscosity is high, when assigning acceleration due to the impact such as transport, can suppress first The position of connecting object part and the second connecting object part is offset, and is additionally, since heat during solidification, can be made conductive material Viscosity is substantially reduced, and the aggegation of scolding tin can be made effectively to carry out.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned Thermocurable compound and the above-mentioned heat with nitrogen-atoms Curability compound is preferably more than 20 weight %, more preferably more than 40 weight %, more preferably more than 50 weight %, Preferably below 99 weight %, more preferably below 98 weight %, more preferably below 90 weight %, particularly preferably 80 Below weight %.The content of above-mentioned Thermocurable compound and the above-mentioned Thermocurable compound with nitrogen-atoms is above-mentioned lower limit When above and below the above-mentioned upper limit, the scolding tin in electroconductive particle can be further efficiently configured on electrode, more entered One step suppresses interelectrode position skew, further improves interelectrode conducting reliability.Impact resistance is improved from further From the viewpoint of property, the content of preferably above-mentioned Thermocurable compound is more.More enter from the curability and viscosity for making conductive material One step is good, and further from the viewpoint of raising connection reliability, in the above-mentioned weight % of conductive material 100, above-mentioned epoxy The content of compound is preferably more than 10 weight %, more preferably more than 15 weight %, preferably below 50 weight %, more preferably For below 30 weight %.
(thermal curing agents)
Above-mentioned thermal curing agents make above-mentioned Thermocurable compound carry out heat cure.As above-mentioned thermal curing agents, have：Imidazoles is consolidated Agent, phenol cured agent, polythiol hardener, amine hardener, acid anhydrides thermal curing agents, hot cationic initiator (hot cationic curing Agent) and hot radical producing agent etc..In the present invention, above-mentioned thermal curing agents are used as using acid anhydrides thermal curing agents.From by electric conductivity Scolding tin in particle is efficiently configured to the viewpoint on electrode, and effectively suppress migration generation from the viewpoint of, leading In the case that the outer surface part in electric portion uses the electroconductive particle with scolding tin, there is huge meaning using acid anhydrides thermal curing agents Justice.Above-mentioned acid anhydrides thermal curing agents can use independent a kind, and two or more can also be applied in combination.
As above-mentioned acid anhydrides thermal curing agents, can enumerate：Trialkyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, Phthalic anhydride derivative, maleic anhydride, methyl butene base tetrabydrophthalic anhydride and three acrylic tetrahydrochysene O-phthalics The acid anhydrides thermal curing agents of 3 functions such as the acid anhydrides thermal curing agents of the function of acid anhydrides etc. 2, trimellitic anhydride, pyromellitic dianhydride, hexichol first Acid anhydrides thermal curing agents more than ketone tetracarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride etc. or 4 functions such as poly- azelaic acid acid anhydride etc..
From the viewpoint of further effectively scolding tin is configured on electrode, above-mentioned acid anhydrides thermal curing agents are preferably at 25 DEG C It is liquid down.Acid anhydrides thermal curing agents for liquid at 25 DEG C help to reduce the viscosity of the conductive material under low temperature, are not easy to hamper Hinder the movement of the scolding tin under low temperature.
From the viewpoint of the heat deterioration for effectively suppressing solidfied material, above-mentioned acid anhydrides thermal curing agents are preferably cyclic acid anhydride heat Curing agent.As cyclic acid anhydride thermal curing agents, can enumerate：Trialkyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride and Triallyl tetrabydrophthalic anhydride etc..
Relative to overall 100 parts by weight of above-mentioned Thermocurable compound, the content of above-mentioned acid anhydrides thermal curing agents is preferably More than 30 parts by weight, more preferably more than 40 parts by weight, preferably below 80 parts by weight, more preferably below 60 parts by weight.Acid When the content of acid anhydride thermal curing agents is more than above-mentioned lower limit, conductive material easily is cured sufficiently, makes scolding tin further effective Ground is configured on electrode, further suppresses the generation of migration.When the content of acid anhydrides thermal curing agents is below the above-mentioned upper limit, solid The remaining acid anhydrides thermal curing agents that solidification is had neither part nor lot in after change are not easy to remain, and the heat resistance of solidfied material further raises.
(organic phosphorus compound and curing accelerator)
From the viewpoint of connection reliability is improved, above-mentioned conductive material preferably comprises curing accelerator.Above-mentioned solidification promotees Can be used by entering agent by independent a kind, and two or more can also be applied in combination.
As above-mentioned curing accelerator, it is not particularly limited, specifically, can enumerates：Imidazoles, 2-methylimidazole and 2- benzene The imidazoles curing accelerator such as base imidazoles；The organophosphor such as methyl San Ding Ji Phosphonium Dimethyl phosphates and Si Zheng Ding Ji Phosphonium tetrafluoro boric acid esters Curing accelerator.
From the viewpoint of scolding tin is further efficiently configured on electrode, above-mentioned conductive material preferably comprises organic Phosphorus compound.From the viewpoint of scolding tin is further efficiently configured on electrode, above-mentioned organic phosphorus compound is preferably Organophosphor curing accelerator.Made by being combined to organic phosphorus compound or organophosphor curing accelerator and acid anhydrides thermal curing agents With the oxide-film for being formed at scolding tin and electrode surface further can effectively being removed, and it is possible to which scolding tin is further It is efficiently configured on electrode.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned curing accelerator is preferably more than 0.5 weight %, more excellent Elect as more than 1 weight %, preferably below 15 weight %, more preferably below 10 weight %, more preferably 5 weight % with Under.When the content of above-mentioned curing accelerator is more than above-mentioned lower limit, the configuration precision of scolding tin further raises.Above-mentioned solidification promotees When entering the content of agent for below the above-mentioned upper limit, migration is further not likely to produce.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned organic phosphorus compound and above-mentioned organophosphor curing accelerator Content be preferably more than 0.5 weight %, more preferably more than 1 weight %, preferably below 15 weight %, more preferably 10 weights Below % is measured, more preferably below 5 weight %.The content of above-mentioned organic phosphorus compound and above-mentioned organophosphor curing accelerator Content to be more than above-mentioned lower limit when, the configuration precision of scolding tin further raises.The content of above-mentioned organic phosphorus compound and on When stating the content of organophosphor curing accelerator as below the above-mentioned upper limit, the configuration precision of scolding tin further raises, and more enters One step is not likely to produce migration.
(fluxing agent)
Above-mentioned conductive material preferably comprises fluxing agent., can be by scolding tin further effectively by the use of fluxing agent It is configured on electrode.The fluxing agent is not particularly limited.As fluxing agent, it can use and be generally used for the fluxing of scolding tin engagement etc. Agent.Above-mentioned conductive material can not contain fluxing agent.
As above-mentioned fluxing agent, can enumerate for example：Zinc chloride, the mixture of zinc chloride and inorganic halides, zinc chloride and Mixture, fuse salt, phosphoric acid, the derivative of phosphoric acid, organohalogen compounds, hydrazine, organic acid and rosin of inorganic acid etc..It is above-mentioned fluxing Agent can use independent a kind, and two or more can also be applied in combination.
As above-mentioned fuse salt, ammonium chloride etc. can be enumerated.As above-mentioned organic acid, lactic acid, citric acid, tristearin can be enumerated Acid, glutamic acid and glutaric acid etc..As above-mentioned rosin, activation rosin and disactivation rosin etc. can be enumerated.Above-mentioned fluxing agent is preferred For organic acid or rosin with more than 2 carboxyls.Above-mentioned fluxing agent can be the organic acid with more than 2 carboxyls, also may be used Think rosin.By using the organic acid with more than 2 carboxyls, rosin, interelectrode conducting reliability further raises.
Above-mentioned rosin is the rosin using rosin acid as principal component.Fluxing agent is preferably rosin, more preferably rosin acid. By using the preferable fluxing agent, interelectrode conducting reliability further raises.
The active temperature (fusing point) of above-mentioned fluxing agent is preferably more than 50 DEG C, more preferably more than 70 DEG C, further preferably Preferably less than 200 DEG C, more preferably less than 190 DEG C, it is still more preferably less than 160 DEG C for more than 80 DEG C, it is further excellent Elect less than 150 DEG C as, be still more preferably less than 140 DEG C.The active temperature of above-mentioned fluxing agent be above-mentioned lower limit more than and on When stating below the upper limit, fluxing agent effect is further effectively played, scolding tin is further efficiently configured on electrode.It is above-mentioned The active temperature (fusing point) of fluxing agent is preferably more than 80 DEG C, less than 190 DEG C.The active temperature (fusing point) of above-mentioned fluxing agent is special Preferably more than 80 DEG C, less than 140 DEG C.
Active temperature (fusing point) as fluxing agent is more than 80 DEG C, less than 190 DEG C of above-mentioned fluxing agent, can be enumerated：Amber Amber acid (186 DEG C of fusing point), glutaric acid (96 DEG C of fusing point), adipic acid (152 DEG C of fusing point), pimelic acid (104 DEG C of fusing point), suberic acid Dicarboxylic acids such as (142 DEG C of fusing points), benzoic acid (122 DEG C of fusing point), malic acid (130 DEG C of fusing point) etc..
In addition, the boiling point of above-mentioned fluxing agent is preferably less than 200 DEG C.
From the viewpoint of scolding tin is further efficiently configured on electrode, the fusing point of above-mentioned fluxing agent is preferably than upper It is high to state the fusing point of the scolding tin in electroconductive particle, it is more preferably high more than 5 DEG C, it is further preferably high more than 10 DEG C.
From the viewpoint of scolding tin is further efficiently configured on electrode, the fusing point of preferably above-mentioned fluxing agent is than upper It is high to state the reaction start temperature of thermal curing agents, it is more preferably high more than 5 DEG C, it is further preferably high more than 10 DEG C.
Above-mentioned fluxing agent can be scattered in conductive material, can also be attached on the surface of electroconductive particle.
By making the fusing point of fluxing agent higher than the fusing point of scolding tin, can make scolding tin effectively aggegation in electrode part.This is Due to：In the case of heat being assigned in engagement, the electrode and the connecting object of electrode perimeter that will be formed on connecting object part When the part of part is compared, the thermal conductivity of the connecting object element portion of the thermal conductivity ratio electrode perimeter of electrode part is high, Thus, the quick heating of electrode part.The stage of the fusing point of scolding tin in more than electroconductive particle, the weldering in electroconductive particle Tin melts, but the oxide film thereon for being formed at surface is not up to the fusing point (active temperature) of fluxing agent, it is thus impossible to remove. In this condition, the temperature of electrode part reaches the fusing point (active temperature) of fluxing agent first, therefore, preferential to reach on electrode The oxide film thereon on the surface of the scolding tin in electroconductive particle is removed, or using the fluxing agent activated to electroconductive particle In the electric charge on surface of scolding tin neutralized, thus, scolding tin can moisten diffusion on the surface of electrode.Thus, it is possible to make Scolding tin effectively aggegation on electrode.
Above-mentioned fluxing agent preferably releases the fluxing agent of cation by heating.Cation is released using by heating Fluxing agent, scolding tin can be further efficiently configured on electrode.
As the above-mentioned fluxing agent that cation is released because of heating, hot cationic initiator can be enumerated.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned fluxing agent is preferably more than 0.5 weight % preferably 30 Below weight %, more preferably below 25 weight %.When the content of fluxing agent is more than above-mentioned lower limit and below the above-mentioned upper limit, oxygen Change envelope to be further not easy to be formed at the surface of scolding tin and electrode, weldering is formed at and it is possible to further effectively remove The oxide film thereon on the surface of tin and electrode.
(other compositions)
Above-mentioned conductive material can contain such as filler, extender, softening agent, plasticizer, polymerization catalyzed as needed Agent, curing catalysts, colouring agent, antioxidant, heat stabilizer, light stabilizer, ultra-violet absorber, lubricant, antistatic agent And the various additives such as fire retardant.
(manufacture method of connection structural bodies and connection structural bodies)
The connection structural bodies of the present invention includes：Surface has the first connecting object part, the table of at least one first electrode Face has the second connecting object part of at least one second electrode, connects above-mentioned first connecting object part and above-mentioned second The connecting portion that object Part links together.In the connection structural bodies of the present invention, the material of above-mentioned connecting portion is led to be above-mentioned Electric material, above-mentioned connecting portion are the solidfied material of above-mentioned conductive material.In the connection structural bodies of the present invention, above-mentioned first electrode With above-mentioned second electrode electrical connection is realized by the solder sections in above-mentioned connecting portion.
The manufacture method of above-mentioned connection structural bodies possesses：Using above-mentioned conductive material, have at least one on surface The process that above-mentioned conductive material is configured on the surface of first connecting object part of one electrode；Above-mentioned conductive material with it is above-mentioned Configuration surface has the second connecting object part of at least one second electrode on the opposite surface of first connecting object component side, Make above-mentioned first electrode and the opposed process of above-mentioned second electrode；By the way that above-mentioned conductive material is heated into above-mentioned electroconductive particle In scolding tin fusing point more than, formed by above-mentioned conductive material by above-mentioned first connecting object part and above-mentioned second connecting object The connecting portion that part connects, and above-mentioned first electrode and above-mentioned second electrode are carried out by the solder sections in above-mentioned connecting portion The process of electrical connection.It is preferred that by above-mentioned conductive material be heated to above-mentioned Thermocurable composition, Thermocurable compound solidification temperature It is more than degree.
In the connection structural bodies of the present invention and the manufacture method of above-mentioned connection structural bodies, due to using specific conduction material Material, therefore, the scolding tin in multiple electroconductive particles is easily concentrated between first electrode and second electrode, can be effective by scolding tin Ground is configured on electrode (line).In addition, a part for scolding tin is not easy to be configured at the region (interval) for not forming electrode, can make to match somebody with somebody The amount for being placed in the scolding tin in the region for not forming electrode is seldom.It is thus possible to improve the conducting between first electrode and second electrode Reliability.Furthermore, it is possible to prevent the electrical connection between the adjacent electrode on the transverse direction that can not be attached, can improve insulation can By property.
In addition, in order to which the scolding tin in multiple electroconductive particles is efficiently configured on electrode and makes to be configured at not formed The amount of the scolding tin in the region of electrode is seldom, as above-mentioned conductive material, preferably using conductive paste without using conducting film.
The thickness of interelectrode solder sections is preferably more than 10 μm, more preferably more than 20 μm, preferably less than 100 μm, More preferably less than 80 μm.(scolding tin in the area 100% exposed of electrode connects scolding tin wetting areas on the surface of electrode Area) be preferably more than 50%, more preferably more than 60%, more preferably more than 70%, preferably less than 100%.
In the manufacture method of the connection structural bodies of the present invention, the process and shape of above-mentioned second connecting object part are being configured Into in the process of above-mentioned connecting portion, the above-mentioned conductive material of preferred pair apply the weight of above-mentioned second connecting object part and without Pressurization, configuring the process of above-mentioned second connecting object part and formed in the process of above-mentioned connecting portion, the above-mentioned conduction of preferred pair Material does not apply the moulding pressure of the power of the weight more than above-mentioned second connecting object part.In these cases, in multiple welderings In tin portion, the uniformity of soldering tin amount can be further improved.And it is possible to the thickness of solder sections is set further effectively to become Thickness, the scolding tin in multiple electroconductive particles are easily more concentrated between electrode, can be by the scolding tin in multiple electroconductive particles Further it is efficiently configured on electrode (line).In addition, a part for the scolding tin in multiple electroconductive particles is not easy to be configured at The region (interval) of electrode is not formed, can further be reduced and is configured in the electroconductive particle in the region for not forming electrode The amount of scolding tin.Therefore, interelectrode conducting reliability can further be improved.Furthermore, it is possible to further prevent from entering The electrical connection between adjacent electrode on the transverse direction of row connection, can further improve insulating reliability.
And, it has been found that：Configuring the process of above-mentioned second connecting object part and formed in the process of above-mentioned connecting portion, If applying the weight of above-mentioned second connecting object part to above-mentioned conductive material without pressurization, formed connecting portion it Before be configured at the scolding tin in the region (interval) for not forming electrode and further easily concentrate between first electrode and second electrode, Scolding tin in multiple electroconductive particles can be further efficiently configured on electrode (line).In the present invention, combination is adopted With：Apply above-mentioned second connecting object portion without using the technical scheme of conducting film and to above-mentioned conductive paste using conductive paste The weight of part and without the technical scheme of pressurization, obtained with further high level in the effect of the present invention have it is very big Meaning.
It should be noted that in WO2008/023452A1, recording from along electrode surface promotion solder powder has it From the viewpoint of effect ground is mobile, is pressurizeed in bonding with specified pressure, record and be further reliably formed scolding tin In terms of the viewpoint in region, moulding pressure is for example set to more than 0MPa, preferably more than 1MPa, even if also recording intentional to splicing tape The pressure of application is 0MPa, due to the deadweight of part being configured on splicing tape, can also apply the pressure that specify to splicing tape. In WO2008/023452A1, it is 0MPa to describe to the pressure of the intentional application of splicing tape, but to being applied with more than 0MPa Pressure situation and be set to 0MPa situation between the difference of effect there is no any record.In addition, in WO2008/ In 023452A1, to the importance using pasty state rather than membranaceous conductive paste, also without any understanding.
In addition, if the non-conductive film using conductive paste, then easily adjust connection according to the coating weight of conductive paste Portion and the thickness of solder sections.On the other hand, there are the following problems in the conductive film：In order to change the thickness of connecting portion or be adjusted It is whole, it is necessary to prepare the conducting film of different-thickness, or prepare the conducting film of specific thickness.In addition, conducting film is compared with conductive paste, The melt viscosity of conducting film can not fully be reduced under the melting temperature of scolding tin by having, and tend to interfere with inclining for the aggegation of scolding tin To.
Hereinafter, on one side referring to the drawings, while the specific embodiment of the explanation present invention.
Fig. 1 is to schematically show the connection structural bodies obtained using the conductive material of an embodiment of the invention Profile.
Connection structural bodies 1 shown in Fig. 1 possesses：First connecting object part 2, the second connecting object part 3, by first connect Connect the connecting portion 4 that the connecting object part 3 of object Part 2 and second connects.Connecting portion 4 is formed by above-mentioned conductive material. In present embodiment, conductive material contains scolding tin particle as electroconductive particle.
Connecting portion 4 has：Multiple scolding tin particle buildups and the solder sections 4A that is bonded with each other and Thermocurable composition is carried out Solidfied material portion 4B obtained from heat cure.
First connecting object part 2 has multiple first electrode 2a in surface (upper surface).Second connecting object part 3 exists Surface (lower surface) has multiple second electrode 3a.First electrode 2a and second electrode 3a realize electrical connection by solder sections 4A. Therefore, the first connecting object part 2 and the second connecting object part 3 realize electrical connection by solder sections 4A.It should be noted that In connecting portion 4, in different region (the solidfied material portions of the solder sections 4A from being gathered between first electrode 2a and second electrode 3a 4B parts) in, in the absence of scolding tin.In the region (solidfied material portion 4B part) different from solder sections 4A, it is not present and solder sections The scolding tin that 4A departs from.It should be noted that if a small amount of, then it is being gathered between first electrode 2a and second electrode 3a Regions (solidfied material portion 4B parts) different solder sections 4A, may have scolding tin.
As shown in figure 1, in connection structural bodies 1, multiple scolding tin particle buildups first electrode 2a and second electrode 3a it Between, after multiple scolding tin pellet meltings, the fused mass of scolding tin particle moistens diffusion on the surface of electrode and solidified afterwards, shape Into solder sections 4A.Therefore, solder sections 4A and first electrode 2a and solder sections 4A and second electrode 3a connection area become big. That is, by using scolding tin particle, the feelings of the electroconductive particle with being divided into the metals such as nickel, gold or copper using the outer surface portion of conductive part Condition is compared, and solder sections 4A and first electrode 2a and solder sections 4A and second electrode 3a contact area become big.Therefore, connect Conducting reliability and connection reliability rise in structure 1.
It should be noted that conductive material can not contain fluxing agent.In the case of using fluxing agent, it is however generally that, Fluxing agent is gradually inactivated due to heating.
It should be noted that in the connection structural bodies 1 shown in Fig. 1, solder sections 4A is entirely located in first electrode 2a, second Opposed region between electrode 3a.For the connection structural bodies 1X of the variation shown in Fig. 3, shown in only connecting portion 4X and Fig. 1 Connection structural bodies 1 it is different.Connecting portion 4X has solder sections 4XA and solidfied material portion 4XB.As connection structural bodies 1X, largely Solder sections 4XA is located at the opposed region of first electrode 2a, second electrode 3a, and a part of of solder sections 4XA can be from first electrode 2a, second electrode 3a opposed region is spilled over to sidepiece.Side is spilled over to from first electrode 2a, second electrode 3a opposed region The solder sections 4XA in portion is a solder sections 4XA part, is not the scolding tin for departing from solder sections 4XA.It should be noted that this implementation In mode, it is possible to reduce depart from the amount of the scolding tin of solder sections, but the scolding tin for departing from solder sections may reside in solidfied material portion.
If reducing the usage amount of scolding tin particle, connection structural bodies 1 is readily obtained.If increase the use of scolding tin particle Amount, then be readily obtained connection structural bodies 1X.
From it is further improve conducting reliability from the viewpoint of, in above-mentioned first electrode, above-mentioned connecting portion and above-mentioned the When the stack directions of two electrodes observes the mutually opposing part of above-mentioned first electrode and above-mentioned second electrode, preferably above-mentioned the In the area 100% of the mutually opposing part of one electrode and above-mentioned second electrode more than 50% (preferably more than 60%, it is more excellent More than 70%, further preferred more than 80% is selected, particularly preferred more than 90%) is configured with the solder sections in above-mentioned connecting portion.
Below, an example of the method for connection structural bodies 1 is manufactured to the conductive material using one embodiment of the present invention Son illustrates.
First, the first connecting object part 2 that there is first electrode 2a in surface (upper surface) is prepared.Then, such as Fig. 2 (a) shown in, configured on the surface of the first connecting object part 2 and contain Thermocurable composition 11B's and multiple scolding tin particle 11A Conductive material 11 (the first process).The conductive material 11 used contains Thermocurable compound and thermal curing agents as Thermocurable Composition 11B.
Conductive material 11 is configured on the surface of the first electrode 2a provided with the first connecting object part 2.Configure conduction material After material 11, scolding tin particle 11A is configured on first electrode 2a (line) and not formed on first electrode 2a region (interval) The two regions.
As the collocation method of conductive material 11, it is not particularly limited, can enumerates：Utilize the coating of point gum machine progress, silk Spraying of wire mark brush and utilization ink discharge device etc..
In addition, prepare the second connecting object part 3 that there is second electrode 3a in surface (lower surface).Then, such as Fig. 2 (b) shown in, in the conductive material 11 on the surface of the first connecting object part 2, it is connected pair with the first of conductive material 11 As the side opposite side of part 2 surface on configure the second connecting object part 3 (the second process).On the surface of conductive material 11 On, it is initially configured the second connecting object part 3 from second electrode 3a sides.Now, make first electrode 2a and second electrode 3a opposed.
Then, conductive material 11 is heated to more than scolding tin particle 11A fusing point (the 3rd process).It is preferred that by conductive material 11 are heated to more than Thermocurable composition 11B (adhesive) solidification temperature.When carrying out the heating, it is present in and does not form electrode The scolding tin particle 11A in region concentrate between first electrode 2a and second electrode 3a aggregation (self alignment effect).Led in use Electrolemma and without using conductive paste in the case of, scolding tin particle 11A be effectively gathered in first electrode 2a and second electrode 3a it Between.In addition, scolding tin particle 11A is melted and is bonded with each other.In addition, heat cure occurs for Thermocurable composition 11B.The result, such as Fig. 2 (c) shown in, the connection that the first connecting object part 2 and the second connecting object part 3 are connected is formed by conductive material 11 Portion 4.Connecting portion 4 is formed by conductive material 11, engagement occurs to form solder sections 4A by multiple scolding tin particle 11A, passes through heat Curability composition 11B carries out heat cure and forms solidfied material portion 4B.
In present embodiment, in above-mentioned second process and above-mentioned 3rd process, preferably without pressurization.In the situation Under, to the weight of the second connecting object part 3 of application of conductive material 11.Therefore, when connecting portion 4 is formed, scolding tin particle 11A has It is gathered between first electrode 2a and second electrode 3a to effect.It should be noted that in above-mentioned second process and above-mentioned 3rd work In at least one process in sequence, if pressurizeed, hinder scolding tin particle will first electrode 2a and second electrode 3a it Between assemble effect tendency rise.
In addition, in present embodiment, due to without pressurization, therefore, being coated with the first connecting object of conductive material On part during overlapping second connecting object part, even in the electrode and the second connecting object part of the first connecting object part In the case of making the first connecting object part and the second connecting object part overlapping in the state of the alignment generation deviation of electrode, The deviation can be corrected, makes the electrode of the first connecting object part and electrode connection (the autoregistration effect of the second connecting object part Should).Because there occurs self-coagulation between the electrode of the first connecting object part and the electrode of the second connecting object part Melting scolding tin in, scolding tin between the electrode of the electrode of the first connecting object part and the second connecting object part with it is conductive It is stable on the energy for the area minimum that other compositions of material are in contact, therefore, form the connection knot for becoming minimum area Structure is that the power for the attachment structure being aligned plays a role.Now, preferred conductive material is without solidification and in the temperature, in the time The viscosity of composition beyond the electroconductive particle of conductive material is substantially low.
As described above, it can obtain the connection structural bodies 1 shown in Fig. 1.It should be noted that above-mentioned second process and above-mentioned Three processes can be carried out continuously.In addition, after above-mentioned second process is carried out, the first obtained connecting object part can be made 2nd, the laminated body of the connecting object part 3 of conductive material 11 and second is moved to heating part, carries out above-mentioned 3rd process.In order to carry out Above-mentioned heating, above-mentioned laminated body can be configured on heater block, above-mentioned laminated body can also be configured in heated space.
Above-mentioned heating-up temperature in above-mentioned 3rd process is preferably more than 140 DEG C, more preferably more than 160 DEG C, is preferably Less than 450 DEG C, more preferably less than 250 DEG C, more preferably less than 200 DEG C.
As the heating means in above-mentioned 3rd process, can enumerate using reflow ovens or using baking oven that connection structural bodies is whole Body is heated to the method more than fusing point of scolding tin and more than the solidification temperature of Thermocurable compound or only to connection structural bodies The method that connecting portion is partly heated.
Above-mentioned first connecting object part, the second connecting object part are not particularly limited.As the above-mentioned first connection pair As part, the second connecting object part, specifically, can enumerate：Semiconductor chip, semiconductor packages, LED chip, LED envelopes The electronic unit such as dress, capacitor and diode and resin film, printed base plate, flexible printing substrate, flexble flat's cable, just Scratch with reference to electronic component of the circuit substrates such as substrate, glass epoxy substrate and glass substrate etc. etc..Above-mentioned first, second connection pair As part is preferably electronic component.
At least one of above-mentioned first connecting object part and above-mentioned second connecting object part are preferably resin film, scratched Property printed base plate, flexible flat cable or rigid-flexible combination substrate.Above-mentioned second connecting object part is preferably resin film, flexible print Brush substrate, flexible flat cable or rigid-flexible combination substrate.Resin film, flexible printing substrate, flexible flat cable and rigid-flexible combination Substrate has flexibility height, than the property of relatively lightweight.In the case of conducting film being used in the connection of this connecting object part, Scolding tin be present and be not easy to be gathered in tendency on electrode.On the other hand, by using conductive paste, even if using resin film, flexibility Printed base plate, flexible flat cable or rigid-flexible combination substrate, can also be by making scolding tin effectively concentrate on electrode and abundant Improve interelectrode conducting reliability in ground.Using resin film, flexible printing substrate, flexible flat cable or rigid-flexible combination substrate In the case of, compared with using the situation of other connecting object parts such as semiconductor chip, further effectively it is based on The raising effect of caused interelectrode conducting reliability without pressurization.
Periphery or face battle array etc. be present in the form of above-mentioned connecting object part.As the feature of each part, in peripheral substrate, Electrode exists only in the peripheral part of substrate.In the battle array substrate of face, electrode is present in face.
As the electrode for being arranged at above-mentioned connecting object part, can enumerate：Gold electrode, nickel electrode, tin electrode, aluminium electrode, The metal electrodes such as copper electrode, molybdenum electrode, silver electrode, SUS electrodes and tungsten electrode.It is flexible printing in above-mentioned connecting object part In the case of substrate, above-mentioned electrode is preferably gold electrode, nickel electrode, tin electrode, silver electrode or copper electrode.In above-mentioned connecting object In the case that part is glass substrate, above-mentioned electrode is preferably aluminium electrode, copper electrode, molybdenum electrode, silver electrode or tungsten electrode.Need Illustrate, can be the electrode individually formed by aluminium, or in metal oxygen in the case where above-mentioned electrode is aluminium electrode The surface stack of compound layer has the electrode of aluminium lamination.As the material of above-mentioned metal oxide layer, the metal doped with trivalent can be enumerated The indium oxide of element and the zinc oxide of metallic element doped with trivalent etc..As the metallic element of above-mentioned trivalent, Sn, Al can be enumerated And Ga etc..
Hereinafter, embodiment and comparative example are enumerated, specifically describes the present invention.The present invention is not limited to following implementation Example.
Thermocurable compound 1：" YL980 ", the bisphenol A type epoxy resin of society of Mitsubishi Chemical manufacture
Thermocurable compound 2：" HP-7200HH ", the dicyclopentadiene-type epoxy resin of DIC societies manufacture
Thermocurable compound 3：" TEPIC-HP ", the Triazine epoxy resin of Nissan Chemical Industries society manufacture
Thermal curing agents 1：Cyclic acid anhydride thermal curing agents, at 25 DEG C for liquid, society of Mitsubishi Chemical manufacture " YH306 "
Thermal curing agents 2：Acid anhydrides thermal curing agents, tetrapropenyl succinic anhydride beyond cyclic acid anhydride thermal curing agents, at 25 DEG C It is down liquid, " DDSA " that new Japan Chemical society manufactures
Thermal curing agents 3：Acid anhydrides thermal curing agents, " trimellitic anhydride (the ピ リ manufactured at 25 DEG C for solid and Guang Chun medicines society メリット)”
Thermal curing agents 4：Amine hardener, society of Mitsubishi Chemical system " DICY "
Fluxing agent 1：Glutaric acid
Curing accelerator 1：：" Fujicure7000 " of T＆KTOKA societies manufacture
Curing accelerator 2：" PX-4MP " organophosphor curing accelerator of Japan Chemical Industry society manufacture
Curing accelerator 3：" PX-4FB " organophosphor curing accelerator of Japan Chemical Industry society manufacture
Curing accelerator 4：" PX-4B " organophosphor curing accelerator of Japan Chemical Industry society manufacture
Scolding tin particle 1：
The preparation method of scolding tin particle 1：
It is using the p-methyl benzenesulfonic acid as catalyst, SnBi scolding tin particle is (" ST-5 " of the manufacture of society of Mitsui Metal Co., Ltd., average 5 μm of particle diameter (median particle diameter)) and glutaric acid (compound, " glutaric acid " of Wako Pure Chemical Industries, Ltd.'s manufacture with 2 carboxyls) While be dehydrated at 90 DEG C in toluene solvant, while stirring 8 hours, thus obtain being covalently bonded with the surface of scolding tin containing The scolding tin particle 1 of the group of carboxyl.
For obtained scolding tin particle 1, it is CV values 20%, forms the molecular weight Mw=2000 of the polymer on surface.
(embodiment 1~12 and comparative example 1~3)
(1) making of anisotropic conductive paste
Composition shown in following tables 1,2 is coordinated with the use level shown in following tables 1,2, obtains anisotropic conductive Paste.
(2) making of connection structural bodies (L/S=50 μm/50 μm)
It is 50 μm/50 μm, the electrode length 3mm copper electrode pattern (μ of thickness 12 of copper electrode to prepare upper surface to have L/S M) glass epoxy substrate (FR-4 substrates, thickness 0.6mm) (the first connecting object part).In addition, preparing lower surface has L/S Flexible printing substrate for 50 μm/50 μm, electrode length 3mm copper electrode pattern (12 μm of the thickness of copper electrode) is (sub- by polyamides The second connecting object part, the thickness 0.1mm of amine formation).
The overlapping area of glass epoxy substrate and flexible printing substrate is set to 1.5cm × 3mm, and the number of electrodes of connection is set to 75 It is right.
On the upper surface of above-mentioned glass epoxy substrate, the anisotropic conductive paste after coating just making so that Thickness on the electrode of glass epoxy substrate is 100 μm, forms anisotropic conductive paste layer.Then, in anisotropic conductive The above-mentioned flexible printing substrate of lamination above the upper surface of paste layer, and make electrode opposite each other.Now, without pressurization.To each Anisotropy electroconductive paste oxidant layer is applied with the weight for stating flexible printing substrate.
Thereafter, heated so that the temperature of anisotropic conductive paste layer turns into 139 DEG C of (welderings since heating after 5 seconds The fusing point of tin).Also, heated so that since heating after 15 seconds, the temperature of anisotropic conductive paste layer is 160 DEG C, Make anisotropic conductive paste curing, obtain connection structural bodies.
(evaluation)
(1) viscosity
Using STRESSTECH (manufacture of EOLOGICA companies), distortion control 1rad, frequency 1Hz, 20 DEG C of programming rate/ Minute, determine under conditions of 40~200 DEG C of measurement temperature scope viscosity (η 25) at 25 DEG C of anisotropic conductive paste and Viscosity (η 100) at 100 DEG C.
(2) heat deterioration characteristic
By anisotropic conductive paste in 170 DEG C of heat cures 0.5 hour, the first solidfied material is obtained.Obtain first is consolidated Compound is placed 100 hours in 130 DEG C and humidity 85% time, obtains the second solidfied material.Use viscoplasticity device, evaluation above-mentioned first The glass transition temperature (Tg1) of solidfied material and the glass transition temperature (Tg2) of above-mentioned second solidfied material.Obtain Tg1 and Tg2 Difference absolute value.
(3) the configuration precision 1 of the scolding tin on electrode
In obtained connection structural bodies, in the electricity of stack direction observation first of first electrode, connecting portion and second electrode When pole and the mutually opposing part of second electrode, the area of the mutually opposing part of first electrode and second electrode is evaluated The ratio X of the area of the solder sections being configured with connecting portion in 100%.Judge the scolding tin on electrode according to following benchmark Configure precision 1.
[determinating reference of the configuration precision 1 of the scolding tin on electrode]
○○○：Ratio X is more than 80%
○○：Ratio X is more than 70% and less than 80%
○：Ratio X is more than 60% and less than 7 0%
△：Ratio X is more than 50% and less than 60%
×：Ratio X is less than 50%
(4) the configuration precision 2 of the scolding tin on electrode
In obtained connection structural bodies, in the side vertical with the stack direction of first electrode, connecting portion and second electrode During to the mutually opposing part of observation first electrode and second electrode, evaluate in the solder sections 100% in connecting portion, be configured at The ratio Y of solder sections in the connecting portion of the mutually opposing part of first electrode and second electrode.Sentence according to following benchmark The configuration precision 2 of scolding tin on fixed electrode.
[determinating reference of the configuration precision 2 of the scolding tin on electrode]
○○：Ratio Y is more than 99%
○：Ratio Y is more than 90% and less than 99%
△：Ratio Y is more than 70% and less than 90%
×：Ratio Y is less than 70%
(5) migrate
By obtained connection structural bodies after 110 DEG C, humidity 85% time are placed 100 hours, 4 terminal methods are utilized respectively to upper Under interelectrode insulaion resistance be measured.Calculate the average value of insulaion resistance.It should be noted that by voltage=electric current × The relation of resistance, by measure voltage during certain electric current flowing can be made to obtain insulaion resistance.According to following benchmark Judge migration.
[determinating reference of migration]
○○：After placement, the average value of insulaion resistance is 10 × 1014More than Ω
○：After placement, the average value of insulaion resistance is 10 × 1012More than Ω, and less than 10 × 1014Ω
△：After placement, the average value of insulaion resistance is 10 × 1010More than Ω, and less than 10 × 1012Ω
×：After placement, the average value of insulaion resistance is less than 10 × 1010, it is considered to be conducting
Show the result in following tables 1,2.
It should be noted that the assessment item on above-mentioned (3), the ratio X of the configuration precision 1 of embodiment 10,11 is than real The ratio X for applying the configuration precision 1 of example 9 is high.On the assessment item of above-mentioned (3), the ratio X ratios of the configuration precision 1 of embodiment 12 The ratio X of the configuration precision 1 of embodiment 1~5 is high.On the assessment item of above-mentioned (5), after placement exhausted of embodiment 9~11 The average value of edge resistance is higher than the average value of the insulaion resistance of embodiment 12.
In addition to flexible printing substrate, even in the situation using resin film, flexible flat cable and rigid-flexible combination substrate Under, it can be seen that same tendency.

Claims (15)

1. a kind of conductive material, it contains：
The outer surface part of conductive part have scolding tin multiple electroconductive particles,
Thermocurable compound,
Acid anhydrides thermal curing agents,
Viscosity of the conductive material at 50 DEG C is more than 10Pas, below 200Pas.
2. conductive material as claimed in claim 1, wherein,
In the weight % of conductive material 100, the content of the electroconductive particle is more than 1 weight %, below 80 weight %,
The conductive material is anisotropic conductive material.
3. conductive material as claimed in claim 1 or 2, the ratio between its viscosity at 50 DEG C and the viscosity at 100 DEG C are 10 Above, less than 400.
4. such as conductive material according to any one of claims 1 to 3, wherein,
The electroconductive particle is scolding tin particle.
5. such as conductive material according to any one of claims 1 to 4, it contains organic phosphorus compound.
6. such as conductive material according to any one of claims 1 to 5, wherein,
The acid anhydrides thermal curing agents are liquid at 25 DEG C.
7. such as conductive material according to any one of claims 1 to 6, wherein,
The acid anhydrides thermal curing agents are cyclic acid anhydride thermal curing agents.
8. such as conductive material according to any one of claims 1 to 7, wherein,
The heat cure 0.5 hour at 170 DEG C and when obtaining the first solidfied material, it is and the first obtained solidfied material is at 130 DEG C and wet When spending 85% time placement 100 hours and obtaining the second solidfied material,
The difference of the glass transition temperature of the glass transition temperature of first solidfied material and second solidfied material it is absolute It is worth for less than 20 DEG C.
9. such as conductive material according to any one of claims 1 to 8, wherein,
The Thermocurable compound contains the Thermocurable compound with nitrogen-atoms.
10. conductive material as claimed in claim 9, wherein,
The Thermocurable compound contains the Thermocurable compound with triazine skeleton.
11. such as conductive material according to any one of claims 1 to 10, wherein,
Relative to overall 100 parts by weight of the Thermocurable compound, the content of the acid anhydrides thermal curing agents is 30 parts by weight Above, below 80 parts by weight.
12. the conductive material as any one of claim 1~11, wherein,
Carboxyl be present in the outer surface of the electroconductive particle.
13. the conductive material as any one of claim 1~12, it is conductive paste, and is liquid at 25 DEG C.
14. a kind of connection structural bodies, it has：
Surface has the first connecting object part of at least one first electrode,
Surface has the second connecting object part of at least one second electrode,
The connecting portion that the first connecting object part and the second connecting object part are linked together,
The connecting portion is the solidfied material of the conductive material any one of claim 1~13,
The first electrode and the second electrode realize electrical connection by the solder sections in the connecting portion.
15. connection structural bodies as claimed in claim 14, wherein,
Along the stack direction of the first electrode, the connecting portion and the second electrode, to the first electrode and described When the mutually opposing part of two electrodes is observed, in the mutually opposing part of the first electrode and the second electrode More than 50% in area 100% is configured with the solder sections in the connecting portion.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102484326A (en) * 2009-08-26 2012-05-30 积水化学工业株式会社 Anisotropic conductive material, connection structure, and connection structure producing method
JP2012142271A (en) * 2010-12-14 2012-07-26 Sekisui Chem Co Ltd Anisotropic conductive material and connection structure
JP2013149610A (en) * 2011-12-20 2013-08-01 Sekisui Chem Co Ltd Electronic component connection material and connection structure
CN103443869A (en) * 2012-02-21 2013-12-11 积水化学工业株式会社 Conductive particles, method for producing conductive particles, conductive material and connection structure
JP2015026606A (en) * 2013-06-20 2015-02-05 積水化学工業株式会社 Conductive material and connection structure
TW201514241A (en) * 2013-09-05 2015-04-16 Sekisui Chemical Co Ltd Curable composition and connection structure
JP2015098588A (en) * 2013-10-17 2015-05-28 デクセリアルズ株式会社 Anisotropic conductive adhesive and connection structure

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3769688B2 (en) 2003-02-05 2006-04-26 独立行政法人科学技術振興機構 Terminal connection method and semiconductor device mounting method
JPWO2008023452A1 (en) 2006-08-25 2010-01-07 住友ベークライト株式会社 Adhesive tape, joined body and semiconductor package

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102484326A (en) * 2009-08-26 2012-05-30 积水化学工业株式会社 Anisotropic conductive material, connection structure, and connection structure producing method
JP2012142271A (en) * 2010-12-14 2012-07-26 Sekisui Chem Co Ltd Anisotropic conductive material and connection structure
JP2013149610A (en) * 2011-12-20 2013-08-01 Sekisui Chem Co Ltd Electronic component connection material and connection structure
CN103443869A (en) * 2012-02-21 2013-12-11 积水化学工业株式会社 Conductive particles, method for producing conductive particles, conductive material and connection structure
JP2015026606A (en) * 2013-06-20 2015-02-05 積水化学工業株式会社 Conductive material and connection structure
TW201514241A (en) * 2013-09-05 2015-04-16 Sekisui Chemical Co Ltd Curable composition and connection structure
JP2015098588A (en) * 2013-10-17 2015-05-28 デクセリアルズ株式会社 Anisotropic conductive adhesive and connection structure

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