CN106716550B - The manufacturing method of conductive paste, connection structural bodies and connection structural bodies - Google Patents

The manufacturing method of conductive paste, connection structural bodies and connection structural bodies Download PDF

Info

Publication number
CN106716550B
CN106716550B CN201580052378.9A CN201580052378A CN106716550B CN 106716550 B CN106716550 B CN 106716550B CN 201580052378 A CN201580052378 A CN 201580052378A CN 106716550 B CN106716550 B CN 106716550B
Authority
CN
China
Prior art keywords
electrode
scolding tin
mentioned
conductive paste
connecting object
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201580052378.9A
Other languages
Chinese (zh)
Other versions
CN106716550A (en
Inventor
石泽英亮
上野山伸也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Publication of CN106716550A publication Critical patent/CN106716550A/en
Application granted granted Critical
Publication of CN106716550B publication Critical patent/CN106716550B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/14—Structural association of two or more printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3485—Applying solder paste, slurry or powder
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/36—Assembling printed circuits with other printed circuits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods
    • H01L2224/115—Manufacturing methods by chemical or physical modification of a pre-existing or pre-deposited material
    • H01L2224/1152—Self-assembly, e.g. self-agglomeration of the bump material in a fluid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Combinations Of Printed Boards (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

The present invention provides a kind of conductive paste, scolding tin particle can be efficiently configured on electrode, can prevent interelectrode position deviation, and interelectrode conducting reliability can be improved.Conductive paste of the invention contains Thermocurable compound and thermal curing agents and multiple scolding tin particles as Thermocurable ingredient, and the ratio of viscosity of the conductive paste in the viscosity at -80 DEG C of fusing point of the scolding tin particle relative to conductive paste at -30 DEG C of fusing point of the scolding tin particle is 1.5 or more, 4 or less.

Description

The manufacturing method of conductive paste, connection structural bodies and connection structural bodies
Technical field
The present invention relates to the conductive pastes containing scolding tin particle.The invention further relates to the connections for having used above-mentioned conductive paste The manufacturing method of structural body and connection structural bodies.
Background technique
The anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are well known.Above-mentioned each In anisotropy conductive material, electroconductive particle is dispersed in adhesive resin.
In order to obtain various connection structural bodies, above-mentioned anisotropic conductive material have been used for such as flexible printing substrate with The connection (FOG (Film on Glass)) of glass substrate, semiconductor chip and flexible printing substrate connection (COF (Chip on 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..
In the electricity using above-mentioned anisotropic conductive material to such as 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.Solidify anisotropic conductive material as a result, by electroconductive particle to electricity Interpolar is electrically connected, to obtain connection structural bodies.
As an example of above-mentioned anisotropic conductive material, the following patent document 1 discloses a kind of jointing tape, It includes the resin layer containing heat-curing resin, solder powder and curing agent, and above-mentioned solder powder and above-mentioned curing agent are present in In above-mentioned resin layer.The splicing tape is membranaceous rather than paste.
A kind of adhering method for having used above-mentioned jointing tape is also disclosed in patent document 1.Specifically, opening from below Begin successively lamination first substrate, splicing tape, the second substrate, splicing tape and third substrate, to obtain laminated body.At this point, making to set Be placed in first substrate surface first electrode and set on the second substrate surface second electrode opposite one another.In addition, making to be set to the The second electrode of two substrate surfaces and set on third substrate surface third electrode opposite one another.Moreover, with specified temperature pair Laminated body is heated and is bonded.Connection structural bodies is obtained as a result,.
A kind of electroconductive particle is disclosed in following patent documents 2 is scattered in anisotropy made of in insulating properties adhesive Conductive material.Lowest melt viscosity [the η of the anisotropic conductive material0] it is 1.0 × 102~1.0 × 106mPa·sec.This is each In anisotropy conductive material, meet 1 < [η1]/[η0]≤3([η0] be anisotropic conductive material lowest melt viscosity, [η1] It is the temperature T than showing lowest melt viscosity0Low 30 DEG C of temperature T1Under melt viscosity).
In addition, being disclosed in following patent documents 3 a kind of free containing curability compound, thermal free radical initiator, light The anisotropic conductive material of base initiator and electroconductive particle.
Existing technical literature
Patent document
Patent document 1:WO2008/023452A1
Patent document 2: Japanese Unexamined Patent Publication 2009-32657 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2012-186161 bulletin
Summary of the invention
The technical problems to be solved by the invention
The jointing tape recorded in patent document 1 is membranaceous rather than paste.Accordingly, it is difficult to which solder powder is efficiently configured In on electrode (line).For example, a part of solder powder is easily configurable at not formed in jointing tape documented by patent document 1 The region (interval) of electrode.The solder powder for being configured at not formed electrode zone does not contribute to interelectrode conducting.
In addition, even the anisotropic conductive paste containing solder powder, sometimes can not efficiently configure solder powder In on electrode (line).
In addition, position occurs between the upper/lower electrode that should be connected sometimes in existing anisotropic conductive paste Deviation.
In addition, not remembering specifically in patent document 2 to electroconductive particle used in anisotropic conductive material material It carries.In addition, even with anisotropic conductive material material documented by patent document 2,3, it sometimes can not be by electric conductivity grain Son is efficiently configured on electrode (line), or position deviation occurs between the upper/lower electrode that should be connected.
The object of the present invention is to provide a kind of conductive pastes, scolding tin particle efficient can be configured on electrode, can To prevent interelectrode position deviation, interelectrode conducting reliability can be improved.The present invention also provides it is a kind of used it is described The connection structural bodies of conductive paste and the manufacturing method of connection structural bodies.
Solution for solving technical problems
Wide in range aspect according to the present invention provides a kind of conductive paste, contains: the heat cure as Thermocurable ingredient Property compound and thermal curing agents and multiple scolding tin particles,
Conductive paste -80 DEG C of fusing point of the scolding tin particle at a temperature of viscosity and conductive paste in the scolding tin particle The ratio between viscosity at a temperature of -30 DEG C of fusing point is 1.5 or more, 4 or less.
Exist in the temperature of some particular aspects of conductive paste of the invention, the display lowest melt viscosity of conductive paste More than -30 DEG C of fusing point of the scolding tin particle of temperature ,+20 DEG C of fusing point of temperature humidity province below of the scolding tin particle Domain.
In some particular aspects of conductive paste of the invention, the Thermocurable compound contains at 25 DEG C for solid Thermocurable compound.
In some particular aspects of conductive paste of the invention, the average grain diameter of the scolding tin particle is 1 μm or more, 40 μm Below.
In some particular aspects of conductive paste of the invention, the content of the scolding tin particle is 10 weight % or more, 90 Weight % or less.
Wide in range aspect according to the present invention provides a kind of connection structural bodies comprising: surface has at least one first electricity First connecting object component of pole, surface have the second connecting object component of at least one second electrode, connect described first The interconnecting piece that object Part and the second connecting object component link together is connect, the material of the interconnecting piece is the conduction Paste, the first electrode and the second electrode realize electrical connection by the solder sections in the interconnecting piece.
Wide in range aspect according to the present invention provides a kind of manufacturing method of connection structural bodies comprising:
Using the conductive paste on the surface that surface has the first connecting object component of at least one first electrode The process for configuring the conductive paste；On the surface opposite with the first connecting object component side of the conductive paste, Configuration surface has the second connecting object component of at least one second electrode, and makes the first electrode and second electricity Extremely opposed process；The conductive paste is heated to consolidating for the fusing point of the scolding tin particle or more and the Thermocurable ingredient Change temperature or more, is formed from there through the conductive paste and connect the first connecting object component and second connecting object The interconnecting piece of component, and the first electrode and the second electrode are electrically connected by the solder sections in the interconnecting piece The process connect.
In some particular aspects of the manufacturing method of connection structural bodies of the invention, wherein in second connection of configuration In the process of object Part and the process for forming interconnecting piece, the second connecting object component is applied to the conductive paste Weight, and without pressurization, alternatively,
At least one work in the process and the process for forming interconnecting piece of the second connecting object component of the configuration In sequence, pressurize, also, it is described configuration the second connecting object component process and it is described formed interconnecting piece process this two In a process, the pressure of pressurization is lower than 1MPa.
It is preferred that the second connecting object component is semiconductor chip, resin film, flexible printing substrate, flexible flat cable Or rigid-flexible combination substrate.
Lamination in the connection structural bodies, preferably along the first electrode, the interconnecting piece and the second electrode When the first electrode and the second electrode mutually opposed part are observed in direction, in the first electrode and second electricity 50% or more in the area 100% of extremely mutually opposed part is configured with the solder sections in the interconnecting piece.The connection knot In structure body, preferably seen along the direction vertical with the stack direction of the first electrode, the interconnecting piece and the second electrode It is mutual in the first electrode and the second electrode when examining the first electrode and the mutually opposed part of the second electrode Opposed part is configured with 70% or more of the solder sections in the interconnecting piece.
Invention effect
Conductive paste of the invention contains Thermocurable compound and thermal curing agents as Thermocurable ingredient and contains Multiple scolding tin particles, viscosity and conductive paste of the conductive paste at -80 DEG C of fusing point of the scolding tin particle are in the scolding tin grain The ratio between viscosity at -30 DEG C of fusing point of son is 1.5 or more, 4 hereinafter, therefore, can be with when to being electrically connected between electrode Scolding tin particle efficient is configured on electrode, interelectrode position deviation can be prevented, and interelectrode conducting can be improved Reliability.
Detailed description of the invention
Fig. 1 is to schematically show the connection structural bodies obtained using the conductive paste of an embodiment of the invention Sectional view；
Fig. 2 (a)~(c) is the side for using the conductive paste of an embodiment of the invention to manufacture connection structural bodies The sectional view of each process of one example of method；
Fig. 3 is the sectional view for indicating the variation of connection structural bodies.
Symbol description
1,1X ... connection structural bodies
2 ... first connecting object components
2a ... first electrode
3 ... second connecting object components
3a ... second electrode
4,4X ... interconnecting piece
4A, 4XA ... solder sections
4B, 4XB ... solidfied material portion
11 ... conductive pastes
11A ... scolding tin particle
11B ... Thermocurable ingredient
Specific embodiment
Hereinafter, illustrating details of the invention.
(conductive paste)
Conductive paste of the invention contains the Thermocurable compound and thermal curing agents as Thermocurable ingredient, and contains Multiple scolding tin particles are as Thermocurable ingredient.In conductive paste of the invention, above-mentioned conductive paste is in above-mentioned scolding tin particle Viscosity (η -80) and above-mentioned conductive paste at -80 DEG C of fusing point (DEG C) is at -30 DEG C of the fusing point (DEG C) of above-mentioned scolding tin particle The ratio between viscosity (η -30) (viscosity (η -80)/viscosity (η -30)) is 1.5 or more, 4 or less.
Since conductive paste of the invention uses above structure, it is multiple when to being electrically connected between electrode Scolding tin particle is easy to concentrate between electrode opposite to each other up and down, multiple scolding tin particle efficients can be configured at electrode (line) On.In addition, a part for being less prone to multiple scolding tin particles is configured at the region (interval) of not formed electrode, can largely reduce It is configured at the amount of the scolding tin particle in the region of not formed electrode.It is thus possible to improve interelectrode conducting reliability.Moreover, can Electrical connection on transverse direction to prevent from being not intended to connection between adjacent electrode, and insulating reliability can be improved.In addition, can To prevent interelectrode position deviation.In the present invention, second is overlapped on the first connecting object component for being coated with conductive paste When connecting object component, even if it is inclined that alignment occurs in the electrode of the first connecting object component and the electrode of the second connecting object component In the state of difference, when Lai Chonghe the first connecting object component and the second connecting object component are overlapped, the deviation can also be corrected, it will The electrode of first connecting object component connect (self alignment effect) with the electrode of the second connecting object component.This effect in order to obtain Fruit, the form this point for using conductive paste, the electroconductive particle being used together with Thermocurable compound and thermal curing agents for Scolding tin particle this point and above-mentioned conductive paste it is above-mentioned within the above range than (viscosity (η -80)/viscosity (η -30)) This point is to play a significant role.
It is further efficiently configured on electrode from by scolding tin particle, and it is reliable further to improve interelectrode conducting It is preferably 2 or more than (viscosity (η -80)/viscosity (η -30)) from the viewpoint of property, preferably 2.8 or less.
Viscosity (η -30) of the above-mentioned conductive paste at -30 DEG C of the fusing point (DEG C) of above-mentioned scolding tin particle is preferably 0.1Pas or more, more preferably 0.2Pas or more, preferably 1Pas are hereinafter, more preferably 0.5Pas or less.It is above-mentioned Viscosity (η -30) can make a significant impact mobile on electrode of electroconductive particle.
When above-mentioned viscosity (η -30) is above-mentioned lower limit or more and the above-mentioned upper limit or less, interelectrode conducting reliability and exhausted Edge reliability further improves.
Viscosity (η mp) of the above-mentioned conductive paste under the fusing point (DEG C) of above-mentioned scolding tin particle is preferably 0.2Pas or more, More preferably 0.3Pas or more, preferably 2Pas are hereinafter, more preferably 1Pas or less.Above-mentioned viscosity (η mp) is to scolding tin Portion has a significant impact in interelectrode thickness.When above-mentioned viscosity (η mp) is above-mentioned lower limit or more and the above-mentioned upper limit or less, solder sections It is thickened in interelectrode thickness, thus interelectrode conducting reliability further improves.
Above-mentioned conductive paste is preferably 10Pas or more in 25 DEG C of viscosity (η 25), more preferably 20Pas or more, into One step is preferably 50Pas or more, particularly preferably 80Pas or more, and preferably 600Pas is hereinafter, more preferably 300Pas is hereinafter, further preferably 200Pas or less.Above-mentioned viscosity (η 25) inhibits to be coated on connecting object component The diffusion of the excessive moistening of conductive paste and scolding tin particle, and solidfied material portion and solder sections is inhibited to configure in the region being not intended to.On When stating viscosity (η 25) as more than above-mentioned lower limit and below the above-mentioned upper limit, interelectrode conducting reliability is further increased.Especially If above-mentioned viscosity (η 25) be 80Pas or more, 200Pas hereinafter, if scolding tin particle is further efficiently configured at electricity On extremely, interelectrode conducting reliability is further increased.
It is further efficiently configured on electrode from by scolding tin particle, and further efficiently inhibits interelectrode position inclined Difference, and from the viewpoint of further increasing interelectrode conducting reliability and insulating reliability, preferably above-mentioned conductive paste is shown The temperature of lowest melt viscosity is present in the fusing point of -30 DEG C of fusing point (DEG C) of above-mentioned scolding tin particle or more, above-mentioned scolding tin particle (DEG C)+20 DEG C of temperature regions below, are more preferably the presence of in -30 DEG C of fusing point (DEG C) of above-mentioned scolding tin particle or more, above-mentioned scolding tin Fusing point (DEG C) temperature region below of particle, be further preferably present in -30 DEG C of the fusing point (DEG C) of above-mentioned scolding tin particle with - 5 DEG C of fusing point (DEG C) temperature region below of upper, above-mentioned scolding tin particle.
Rheometer can be used in temperature corresponding to the viscosity and lowest melt viscosity of above-mentioned conductive paste at each temperature (" STRESSTECH " of the manufacture of EOLOGICA Co., Ltd.) etc., in root diameter 20mm, oscillation distortion control, heating rate 10 It is measured under conditions of DEG C/min.In the measurement of above-mentioned lowest melt viscosity, above-mentioned lead can be heated to from room temperature (23 DEG C) Until electric paste curing.
Conductive paste of the invention can compatibly be used in aftermentioned connection structural bodies and connection structural bodies of the invention Manufacturing method.
Above-mentioned conductive paste is preferably anisotropic conductive paste.Above-mentioned conductive paste can suitably be used in electrode Electrical connection.Above-mentioned conductive paste is preferably circuit connection material.
Hereinafter, being illustrated to each ingredient contained by above-mentioned conductive paste.
(scolding tin particle)
Above-mentioned scolding tin particle has scolding tin on electric conductivity outer surface.In above-mentioned scolding tin particle, central part and electric conductivity Outer surface formed by scolding tin.Above-mentioned scolding tin particle is that the outer surface of central part and electric conductivity (conductive part) is weldering The particle of tin.
From the viewpoint of concentrating scolding tin particle efficient on the electrode, the zeta potential of above-mentioned scolding tin particle surface is preferred It is positive.But in the present invention, the zeta potential of above-mentioned scolding tin particle surface can not also be positive.
Zeta potential measures as follows.
The measuring method of zeta potential:
Scolding tin particle 0.05g is put into methanol 10g and carries out ultrasonication etc., it is uniformly dispersed it, is divided Dispersion liquid.Using the dispersion liquid, and " the Delsamax PRO " manufactured using Beckman Coulter company, pass through electrophoretic determination Method measures zeta potential at 23 DEG C.
The zeta potential of scolding tin particle is preferably 0mV or more, more preferably above 0mV, and preferably 10mV is hereinafter, more preferably 5mV Hereinafter, still more preferably for 1mV hereinafter, further preferably 0.7mV is hereinafter, particularly preferably 0.5mV or less.Zeta potential is When below the above-mentioned upper limit, in the conductive paste before use, scolding tin particle is not easy to agglomerate.When zeta potential is 0mV or more, installing When scolding tin particle effectively agglomerate on the electrode.
Due to being easy to be set as the zeta potential on surface just, above-mentioned scolding tin particle preferably has scolding tin particle main body and matches The anionic polymer being placed in above-mentioned scolding tin particle body surfaces.Above-mentioned scolding tin particle is preferably by anionic polymer Or the compound of formation anionic polymer is surface-treated scolding tin particle main body and is obtained.Above-mentioned scolding tin particle is preferably The surface treatment that anionic polymer or the compound for forming anionic polymer carry out.Above-mentioned anionic polymer and formation The compound of above-mentioned anionic polymer can be used alone respectively, can also be applied in combination two or more.
As the method being surface-treated using anionic polymer to scolding tin particle main body, can enumerate using following poly- Object is closed as anionic polymer, makes the side of the carboxyl of anionic polymer and the reaction of the hydroxyl on the surface of scolding tin particle main body Method: for example making (methyl) acrylate copolymer made of the conjunction of (methyl) acrylic acid copolymer, synthesized by dicarboxylic acids and glycol and two ends The polyester polymers with carboxyl are held, are obtained by the intermolecular dehydration condensation of dicarboxylic acids and two ends have carboxyl Polymer is synthesized and polyester polymers of two ends with carboxyl and the modified poly ethylene with carboxyl by dicarboxylic acids and diamines Alcohol (" the Gohsenol T " of Japan's synthesis Chemical Co., Ltd. manufacture) etc..
As the anion part of above-mentioned anionic polymer, above-mentioned carboxyl can be enumerated, in addition to this, can also enumerate toluene Sulfonyl (p-H3CC6H4S (=O)2) and azochlorosulfonate acid ion group (- SO3 -), phosphate ion group (- PO4 -) etc..
In addition, as another method, the following methods can be given: being reacted using having with the hydroxyl of scolding tin particle body surfaces Functional group and also there is compound by the polymerizable functional group of addition condensation reaction, and the compound polymerization is existed On the surface of scolding tin particle main body.Carboxyl and isocyanide can be enumerated as the functional group reacted with the hydroxyl of scolding tin particle body surfaces Perester radical etc. can enumerate hydroxyl, carboxyl, amino and (methyl) propylene as the functional group polymerizeing by addition, condensation reaction Acyl group.
The weight average molecular weight of above-mentioned anionic polymer is preferably 2000 or more, and more preferably 3000 or more, preferably 10000 hereinafter, more preferably 8000 or less.
When above-mentioned weight average molecular weight is above-mentioned lower limit or more and the above-mentioned upper limit or less, it is easy on the surface of scolding tin particle main body Upper configuration anionic polymer is easy for the zeta potential on the surface of scolding tin particle to be set as just, can be further high by scolding tin particle It is configured on electrode to effect.
Above-mentioned weight average molecular weight indicates the dividing equally again with polystyrene conversion by gel permeation chromatography (GPC) measurement Son amount.
Polymer obtained from being surface-treated using the compound for forming anionic polymer to scolding tin particle main body Weight average molecular weight can acquire as follows: the scolding tin in dissolution scolding tin particle utilizes the dilute hydrochloric acid etc. for not causing polymer to decompose It removes scolding tin particle and then measures the weight average molecular weight of remaining polymer.
It is 450 DEG C of metals (low-melting-point metal) below that above-mentioned scolding tin, which is preferably fusing point,.Above-mentioned scolding tin particle preferably fusing point For 450 DEG C of metallics (low-melting-point metal particle) below.Above-mentioned low-melting-point metal particle is the grain containing low-melting-point metal Son.The low-melting-point metal indicates 450 DEG C of metals below of fusing point.The fusing point of low-melting-point metal is preferably 300 DEG C hereinafter, more preferably It is 160 DEG C or less.In addition, above-mentioned scolding tin particle contains tin.In 100 weight % of metal contained by above-mentioned scolding tin particle, tin contains Amount preferably 30 weight % or more, more preferably 40 weight % or more, further preferably 70 weight % or more, particularly preferably 90 weight % or more.When the content of tin in above-mentioned scolding tin particle is above-mentioned lower limit or more, the connection of solder sections and electrode is reliable Property is further improved.
In addition, the content of above-mentioned tin can (hole field makes using high-frequency inductive coupling plasma body emission spectrographic analysis device " ICP-AES " of Co., Ltd., institute manufacture) or the fluorescent x-ray analyzer (" EDX- of Shimadzu Corporation's manufacture 800HS ") etc. be measured.
By using above-mentioned scolding tin particle, scolding tin melting and electrode engagement, solder sections make to be connected between electrode.For example, scolding tin Portion and electrode face contact easy to form, without forming point contact, therefore, connection resistance is reduced.In addition, by using scolding tin grain The bond strength of son, solder sections and electrode is got higher, as a result, is further not likely to produce the removing of solder sections and electrode, effectively Improve conducting reliability and connection reliability.
The low-melting-point metal for constituting above-mentioned scolding tin particle is not particularly limited.The low-melting-point metal is preferably tin or contains The alloy of 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..Since the wetability to electrode is excellent, above-mentioned low-melting-point metal is preferably tin, tin-silver alloy, tin- Ag-Cu alloy, tin-bismuth alloy electroplating, Sn-In alloy, more preferably tin-bismuth alloy electroplating, Sn-In alloy.
In addition, above-mentioned scolding tin particle is preferably based on JIS Z3001: welding terminology, liquidus curve are 450 DEG C of fillings below Metal.As the composition of above-mentioned scolding tin particle, can enumerate such as containing metal group zinc, gold, silver, lead, copper, tin, bismuth, indium At.It is preferred that low melting point and lead-free tin-indium class (117 DEG C of eutectics) or Sn-Bi class (139 DEG C of eutectics).That is, above-mentioned scolding tin grain Son does not preferably contain lead, the scolding tin preferably containing tin and indium or the scolding tin containing tin and bismuth.
In order to further increase the bond strength of above-mentioned solder sections and electrode, above-mentioned scolding tin particle can wrap nickeliferous, copper, The metals such as antimony, aluminium, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, chromium, molybdenum, palladium.In addition, from further increase solder sections and From the viewpoint of the bond strength of electrode, above-mentioned scolding tin particle preferably comprises nickel, copper, antimony, aluminium or zinc.From further increasing scolding tin From the viewpoint of the weld strength of portion and electrode, in 100 weight % of scolding tin particle, for improving these metals of bond strength Content be preferably 0.0001 weight % or more, preferably 1 weight % or less.
The average grain diameter of above-mentioned scolding tin particle is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 3 μm More than, particularly preferably 5 μm or more, preferably 100 μm hereinafter, more preferably 60 μm hereinafter, still more preferably for 40 μm with Under, further preferably 30 μm hereinafter, still more preferably for 20 μm hereinafter, particularly preferably 15 μm hereinafter, most preferably 10 μ M or less.The average grain diameter of above-mentioned scolding tin particle be above-mentioned lower limit more than and the above-mentioned upper limit below when, can by scolding tin particle more into One step is efficiently configured on electrode.The average grain diameter of above-mentioned scolding tin particle is particularly preferably 3 μm or more, 30 μm or less.
" average grain diameter " of above-mentioned scolding tin particle indicates number average bead diameter.The average grain diameter of scolding tin particle is for example electric by utilization Sub- microscope or any 50 scolding tin particles of optical microphotograph sem observation, and calculate average value and acquire.
The coefficient of variation of above-mentioned scolding tin particle diameter is preferably 5% or more, more preferably 10% or more, preferably 40% with Under, more preferably 30% or less.When the coefficient of variation of above-mentioned partial size is above-mentioned lower limit or more and the above-mentioned upper limit or less, can make Scolding tin particle is further efficiently configured on electrode.But the coefficient of variation of above-mentioned scolding tin particle diameter can also be lower than 5%.
The above-mentioned coefficient of variation (CV value) following formula indicates.
CV value (%)=(ρ/Dn) × 100
ρ: the standard deviation of the partial size of scolding tin particle
Dn: the average value of the partial size of scolding tin particle
The shape of above-mentioned scolding tin particle is not particularly limited.The shape of above-mentioned scolding tin particle can be spherical, or Shape other than flat equal ball shape.
In above-mentioned 100 weight % of conductive paste, the content of above-mentioned scolding tin particle is preferably 1 weight % or more, and more preferably 2 Weight % or more, further preferably 10 weight % or more, particularly preferably 20 weight % or more, most preferably 30 weight % with On, preferably 90 weight % hereinafter, more preferably 80 weight % hereinafter, further preferably 60 weight % hereinafter, particularly preferably For 50 weight % or less.When the content of above-mentioned scolding tin particle is above-mentioned lower limit or more and the above-mentioned upper limit or less, scolding tin grain can be made Son is further efficiently configured on electrode, is easy between scolding tin particle is largely configured at electrode, and further increasing conducting can By property.From the viewpoint of further increasing conducting reliability, the content of preferably above-mentioned scolding tin particle is more.
Be formed with the line of part of electrode (L) be 50 μm more than or lower than 150 μm in the case where, led from further increasing From the viewpoint of logical reliability, in above-mentioned 100 weight % of conductive paste, the content of above-mentioned scolding tin particle be preferably 20 weight % with On, more preferably 30 weight % or more, preferably 55 weight % are hereinafter, more preferably 45 weight % or less.
The interval (S) of the part of not formed electrode be 50 μm more than or lower than 150 μm in the case where, from further mentioning From the viewpoint of height conducting reliability, in above-mentioned 100 weight % of conductive paste, the content of above-mentioned scolding tin particle is preferably 30 weights % or more is measured, more preferably 40 weight % or more, preferably 70 weight % are hereinafter, more preferably 60 weight % or less.
Be formed with the line of part of electrode (L) be 150 μm more than or lower than 1000 μm in the case where, from further increasing From the viewpoint of reliability is connected, in above-mentioned 100 weight % of conductive paste, the content of above-mentioned scolding tin particle is preferably 30 weight % More than, more preferably 40 weight % or more, preferably 70 weight % are hereinafter, more preferably 60 weight % or less.
The interval (S) of the part of not formed electrode be 150 μm more than or lower than 1000 μm in the case where, from further mentioning From the viewpoint of height conducting reliability, in above-mentioned 100 weight % of conductive paste, the content of above-mentioned scolding tin particle is preferably 30 weights % or more is measured, more preferably 40 weight % or more, preferably 70 weight % are hereinafter, more preferably 60 weight % or less.
(Thermocurable compound: Thermocurable ingredient)
Above-mentioned Thermocurable compound is the compound that can be cured by heating.As above-mentioned Thermocurable Object is closed, can be enumerated: oxetane compound, epoxide, episulfide compound, (methyl) acyclic compound, benzene Phenolic compounds, amino-compound, unsaturated polyester compound, urethanes, polysiloxane compound and polyimides Close object etc..It is be more good from the curability and viscosity that make conductive paste and from the viewpoint of further increasing connection reliability, it is excellent It is selected as epoxide.Above-mentioned Thermocurable compound can be used alone, and can also be applied in combination two or more.
It is further efficiently configured on electrode from by scolding tin particle, and further efficiently inhibits interelectrode position inclined Difference, and from the viewpoint of further increasing interelectrode conducting reliability and insulating reliability, preferably above-mentioned Thermocurable chemical combination It is 80 DEG C or more, 140 DEG C of Thermocurable compounds below that object, which contains fusing point,.
It is further efficiently configured on electrode from by scolding tin particle, and further increases interelectrode conducting reliability From the point of view of viewpoint, the fusing point of above-mentioned Thermocurable compound is preferably the fusing point (DEG C) of the scolding tin in above-mentioned scolding tin particle hereinafter, more - 20 DEG C of the fusing point of scolding tin in preferably above-mentioned scolding tin particle is hereinafter, scolding tin in further preferably above-mentioned scolding tin particle - 40 DEG C of fusing point or less.
It is further efficiently configured on electrode from by scolding tin particle, and further efficiently inhibits interelectrode position inclined Difference, and from the viewpoint of further increasing interelectrode conducting reliability and insulating reliability, preferably above-mentioned Thermocurable chemical combination Object contains crystallinity Thermocurable compound.Above-mentioned crystallinity Thermocurable compound can be used alone, can also group It closes using two or more.
It is more efficiently configured on electrode from by scolding tin particle, and more efficiently inhibits interelectrode position deviation, And from the viewpoint of further increasing interelectrode conducting reliability and insulating reliability, preferably above-mentioned Thermocurable compound contains Having molecular weight is 200 or more, 800 Thermocurable compounds below, and further preferably molecular weight is 200 or more, 800 below Crystallinity Thermocurable compound.
Above-mentioned molecular weight refers to the case where above-mentioned Thermocurable compound is not polymer and above-mentioned Thermocurable Close object structural formula can determine in the case where, being capable of the calculated molecular weight of formula according to this structure.In addition, above-mentioned Thermocurable Compound be polymer in the case where refer to weight average molecular weight.Above-mentioned weight average molecular weight is by gel permeation chromatography (GPC) The weight average molecular weight of measurement to be converted with polystyrene.
It is more efficiently configured on electrode from by scolding tin particle, and more efficiently inhibits interelectrode position deviation, And from the viewpoint of further increasing interelectrode conducting reliability and insulating reliability, above-mentioned crystallinity Thermocurable compound It is preferred that being solid at 25 DEG C.
It is more efficiently configured on electrode from by scolding tin particle, and more efficiently inhibits interelectrode position deviation, And from the viewpoint of further increasing interelectrode conducting reliability and insulating reliability, above-mentioned crystallinity Thermocurable compound Fusing point be preferably 80 DEG C or more, more preferably 85 DEG C or more, preferably 150 DEG C are hereinafter, more preferably 140 DEG C or less.
It is more efficiently configured on electrode from by scolding tin particle, and more efficiently inhibits interelectrode position deviation, And from the viewpoint of further increasing interelectrode conducting reliability and insulating reliability, above-mentioned crystallinity Thermocurable compound Molecular weight be preferably 300 or more, more preferably 350 or more, preferably 500 hereinafter, more preferably 400 or less.
Above-mentioned molecular weight is the case where above-mentioned Thermocurable compound is not polymer and above-mentioned Thermocurable compound Structural formula can determine in the case where, be the molecular weight that the formula according to this structure that refers to is calculated.In addition, in above-mentioned thermosetting Change property compound be polymer in the case where refer to weight average molecular weight.
As above-mentioned crystallinity Thermocurable compound, epoxide and (methyl) acyclic compound etc. can be enumerated.
As above-mentioned epoxide, aromatic epoxy compound can be enumerated.Wherein, preferably resorcinol type ring aoxidizes Close the crystallinity epoxides such as object, naphthalene type ring oxygen compound, biphenyl type epoxy compound, diphenyl ketone type epoxide. It is solid preferably under room temperature (23 DEG C), and melting temperature is the fusing point epoxide below of scolding tin.Melting temperature is preferred For 100 DEG C hereinafter, more preferably 80 DEG C hereinafter, preferably 40 DEG C or more.By using above-mentioned preferred epoxide, pasting It closes the stage for having connecting object component, viscosity is high, when being applied with acceleration due to the impact such as conveying, can inhibit the first company The position for connecing object Part and the second connecting object component is deviateed, in addition, electroconductive paste can be greatly reduced in heat when passing through solidification The viscosity of agent can efficiently carry out the cohesion of scolding tin particle.
Above-mentioned (methyl) acyclic compound is the compound with (methyl) acryloyl group.As above-mentioned (methyl) propylene Acid compound can enumerate epoxy (methyl) acrylate compounds.Preferably by (methyl) acrylic acid etc. on epoxide Import compound obtained from (methyl) acryloyl group.
In above-mentioned 100 weight % of conductive paste, the content of above-mentioned Thermocurable compound is preferably 20 weight % or more, more Preferably 40 weight % or more, further preferably 50 weight % or more, preferably 99 weight % are hereinafter, more preferably 98 weights % is measured hereinafter, further preferably 90 weight % are hereinafter, particularly preferably 80 weight % or less.From further increasing impact resistance From the viewpoint of, the content of above-mentioned Thermocurable ingredient is The more the better.
In above-mentioned 100 weight % of conductive paste, fusing point is containing for 80 DEG C or more, 140 DEG C Thermocurable compounds below Amount and the content of crystallinity Thermocurable compound are respectively preferably 20 weight % or more, more preferably 40 weight % or more, into One step is preferably 50 weight % or more, and preferably 99 weight % are hereinafter, more preferably 98 weight % are hereinafter, further preferably 90 Weight % is hereinafter, particularly preferably 80 weight % or less.
In addition, fusing point is 80 DEG C or more, 140 DEG C of heat cures below in the 100 weight % of total amount of Thermocurable compound The content of property compound and the content of crystallinity Thermocurable compound are respectively preferably 10 weight % or more, more preferably 30 weights Measure % or more, further preferably 50 weight % or more, particularly preferably 70 weight % or more, preferably 100 weight % or less.
(thermal curing agents: Thermocurable ingredient)
Above-mentioned thermal curing agents make above-mentioned Thermocurable compound that heat cure occur.As above-mentioned thermal curing agents, can enumerate: miaow The polythiol hardeners such as azoles curing agent, amine hardener, phenol cured agent, polythiol curing agent, acid anhydrides, hot cationic initiator (heat Cation curing agent) and hot radical producing agent etc..Above-mentioned thermal curing agents also can be used alone, and can also be applied in combination It is two or more.
Due to that conductive paste can be made at low temperature more rapidly to solidify, it is therefore preferable that imidazole curing agent, thiol-cured Agent or amine hardener.In addition, due to will be by the curability compound being heating and curing and above-mentioned thermal curing agents when, save steady It is qualitative to get higher, it is therefore preferable that latent curing agent.Latent curing agent is preferably latency imidazole curing agent, latency mercaptan Curing agent or latency amine hardener.In addition, above-mentioned thermal curing agents can also be by the high score of polyurethane resin or polyester resin etc. Sub- substance cladding.
Be not particularly limited, can enumerate as above-mentioned imidazole curing agent: 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole trimellitic acid salt, 2,4- diamino -6- [2 '-methylimidazoles Base-(1 ')]-ethyl-s-triazine and 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine isocyanuric acid add At object etc..
As above-mentioned polythiol hardener, polythiol curing agent can be enumerated.As above-mentioned polythiol curing agent, do not limit especially It is fixed, it can enumerate: trimethylolpropane tris -3-thiopropionate, four -3-thiopropionate of pentaerythrite and dipentaerythritol six - 3-thiopropionate etc..
It is not particularly limited, can enumerate as above-mentioned amine hardener: hexamethylene diamine, eight methylene diamines, ten methylenes Bis- (3- aminopropyl) -2,4,8,10- four spiral shell [5.5] hendecanes of base diamines, 3,9-, bis- (4- aminocyclohexyl) methane, Phenylenediamine and diamino diphenyl sulfone etc..
As above-mentioned hot cationic initiator, can enumerate iodine cationoid curing agent, oxygen cationoid curing agent and Sulfonium cationoid curing agent etc..As above-mentioned iodine cationoid curing agent, bis- (4- tert-butyl-phenyl) iodine hexafluoros can be enumerated Phosphate etc..As above-mentioned oxygen cationoid curing agent, trimethyl oxygen tetrafluoroborate etc. can be enumerated.As above-mentioned sulfonium class Cation curing agent can enumerate tri-p-tolylsulfonium hexafluorophosphate etc..
It as above-mentioned hot radical producing agent, is not particularly limited, azo-compound and organic peroxide etc. can be enumerated. As above-mentioned azo-compound, azodiisobutyronitrile (AIBN) etc. can be enumerated.As above-mentioned organic peroxide, two uncles can be enumerated Butylperoxide and methyl-ethyl-ketone peroxide etc..
The reaction start temperature of above-mentioned thermal curing agents is preferably 50 DEG C or more, and more preferably 70 DEG C or more, further preferably Be 80 DEG C or more, preferably 250 DEG C hereinafter, more preferably 200 DEG C hereinafter, further preferably 150 DEG C hereinafter, particularly preferably 140 DEG C or less.When the reaction start temperature of above-mentioned thermal curing agents is above-mentioned lower limit or more and the above-mentioned upper limit or less, by scolding tin particle Further efficiently it is configured on electrode.The reaction start temperature of above-mentioned thermal curing agents be particularly preferably 80 DEG C or more, 140 DEG C with Under.
From the viewpoint of scolding tin is further efficiently configured on electrode, the reaction start temperature of above-mentioned thermal curing agents It is preferred that, more preferably high 5 DEG C or more, further preferably high 10 DEG C or more higher than the fusing point of the scolding tin in above-mentioned scolding tin particle.
The reaction start temperature of above-mentioned thermal curing agents refers to, the temperature of the exothermal peak in DSC begun to ramp up.
The content of above-mentioned thermal curing agents is not particularly limited.It is above-mentioned relative to above-mentioned 100 parts by weight of Thermocurable compound The content of thermal curing agents is preferably 0.01 parts by weight or more, and more than more preferably 1 parts by weight, preferably 200 parts by weight are hereinafter, more Preferably 100 parts by weight are hereinafter, below further preferably 75 parts by weight.When the content of thermal curing agents is above-mentioned lower limit or more When, it is easy to solidify conductive paste sufficiently.When the content of thermal curing agents is the above-mentioned upper limit or less, it is not easy residual after hardening not It participates in solidification and remaining thermal curing agents, and further increases the heat resistance of solidfied material.
(fluxing agent)
Above-mentioned conductive paste preferably comprises fluxing agent.By the use of fluxing agent, scolding tin can be made further efficiently to match It is placed on electrode.As fluxing agent, the fluxing agent commonly used in scolding tin welding etc. can be used.Above-mentioned fluxing agent does not have special limit System.It as above-mentioned fluxing agent, can enumerate for example: zinc chloride, the mixture of zinc chloride and inorganic halides, zinc chloride and inorganic acid Mixture, fuse salt, phosphoric acid, the derivative of phosphoric acid, organohalogen compounds, hydrazine, organic acid and rosin etc..Above-mentioned fluxing agent can be with One kind is used alone, can also be applied in combination two or more.
From the storage stability for effectively improving conductive paste, and between connection electrode when make in addition to scolding tin particle at Divide and be further not easy from the viewpoint of flowing, preferably above-mentioned fluxing agent is solid at 25 DEG C.
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 the organic acid containing more than two carboxyls, rosin.Above-mentioned fluxing agent can be the organic acid containing more than two carboxyls, It can be rosin.By using organic acid, rosin with more than two carboxyls, interelectrode conducting can be further improved Reliability.
Above-mentioned rosin is the rosin using rosin acid as principal component.Fluxing agent is preferably rosin, more preferably rosin acid. By using the preferred fluxing agent, interelectrode conducting reliability is further increased.
The active temperature (fusing point) of above-mentioned fluxing agent is preferably 50 DEG C or more, and more preferably 70 DEG C or more, further preferably It is 80 DEG C or more, preferably 200 DEG C hereinafter, more preferably 190 DEG C hereinafter, still more preferably for 160 DEG C hereinafter, further excellent 150 DEG C are selected as hereinafter, being still more preferably 140 DEG C or less.The active temperature of above-mentioned fluxing agent be above-mentioned lower limit more than and on When stating the upper limit or less, fluxing agent effect is further effectively played, and scolding tin particle is further efficiently configured at electricity On extremely.The active temperature of above-mentioned fluxing agent is preferably 80 DEG C or more and 190 DEG C or less.The active temperature of above-mentioned fluxing agent is especially excellent It is selected as 80 DEG C or more and 140 DEG C or less.
It is 80 DEG C or more and 190 DEG C above-mentioned fluxing agents below as fusing point, can enumerates: succinic acid (186 DEG C of fusing point), penta The dicarboxylic acids such as diacid (96 DEG C of fusing point), adipic acid (152 DEG C of fusing point), pimelic acid (104 DEG C of fusing point), suberic acid (142 DEG C of fusing point), 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 200 DEG C or less.
From the viewpoint of being further efficiently configured at scolding tin on electrode, the fusing point of above-mentioned fluxing agent is preferably than above-mentioned The fusing point of scolding tin particle is high, more preferably high 5 DEG C or more, further preferably high 10 DEG C or more.
From the viewpoint of being further efficiently configured at scolding tin on electrode, the fusing point of above-mentioned fluxing agent is preferably than above-mentioned The reaction start temperature of thermal curing agents is high, more preferably high 5 DEG C or more, further preferably high 10 DEG C or more.
By keeping the fusing point of fluxing agent higher than the fusing point of scolding tin, scolding tin particle can be made effectively to agglomerate in electrode section. This is because, comparing the company of the electrode and electrode perimeter that are formed on connecting object component in the case where assigning heat in engagement When connecing the part of object Part, the pyroconductivity of the connecting object component part of the thermal conductivity ratio electrode perimeter of electrode section Height, the heating of electrode section is quick as a result,.It is being more than the stage of the fusing point of scolding tin particle, the inside dissolution of scolding tin particle, but shape The fusing point (active temperature) for not reaching fluxing agent at the oxide film thereon in surface, it is thus impossible to remove.In this state, electrode Partial temperature first reaches the fusing point (active temperature) of fluxing agent, therefore, can be preferentially by the surface of the scolding tin particle on electrode Oxide film thereon remove, scolding tin particle on the surface of electrode moisten diffusion.Thus, it is possible to agglomerate with making scolding tin particle efficient in On electrode.
Above-mentioned fluxing agent can be scattered in conductive paste, can also be attached on the surface of scolding tin particle.
Above-mentioned fluxing agent releases the fluxing agent of cation preferably by heating.Cation is released using by heating Scolding tin particle further can be efficiently configured on electrode by fluxing agent.
In above-mentioned 100 weight % of conductive paste, the content of above-mentioned fluxing agent is preferably 0.5 weight % or more, and preferably 30 Weight % is hereinafter, more preferably 25 weight % or less.Above-mentioned conductive paste can not contain fluxing agent.The content of fluxing agent is upper When stating lower limit or more and the above-mentioned upper limit or less, further it is not easy to form oxide film thereon on the surface of scolding tin and electrode, also, The oxide film thereon for being formed in scolding tin and electrode surface can effectively further be removed.
(filler)
Filler can be added in above-mentioned conductive paste.Filler can be organic filler, be also possible to inorganic filler.By adding Distance filled, that scolding tin particle can be inhibited to agglomerate, and scolding tin grain is equably agglomerated on entire portion's electrode of substrate Son.
In above-mentioned 100 weight % of conductive paste, the content of above-mentioned filler is preferably 0 weight % or more, preferably 5 weight % Hereinafter, more preferably 2 weight % are hereinafter, further preferably 1 weight % or less.The content of above-mentioned filler is above-mentioned lower limit or more And when below the above-mentioned upper limit, scolding tin particle is further efficiently configured on electrode.
(other ingredients)
Above-mentioned conductive paste can according to need, such as containing: filler, incremental agent, softening agent, plasticizer, polymerization are urged Agent, curing catalysts, colorant, antioxidant, heat stabilizer, light stabilizer, ultraviolet absorbing agent, lubricant, resist it is quiet The various additives such as electric agent and fire retardant.
(manufacturing method of connection structural bodies and connection structural bodies)
Connection structural bodies of the invention includes: the first connecting object component, the table that surface has at least one first electrode Face has the second connecting object component of at least one second electrode, connects above-mentioned first connecting object component and above-mentioned second The interconnecting piece that object Part links together.In connection structural bodies of the invention, the material of above-mentioned interconnecting piece is above-mentioned electroconductive paste Agent.Above-mentioned interconnecting piece is formed by above-mentioned conductive paste.Above-mentioned interconnecting piece is the solidfied material of above-mentioned conductive paste.Connection of the invention In structural body, above-mentioned first electrode and above-mentioned second electrode are electrically connected by the solder sections in above-mentioned interconnecting piece.
The manufacturing method of connection structural bodies of the invention has: using above-mentioned conductive paste, has at least one on surface The process of above-mentioned conductive paste is configured on the surface of first connecting object component of first electrode；Above-mentioned conductive paste with it is upper State the second connecting object portion that configuration surface on the opposite surface of the first connecting object component side has at least one second electrode Part makes above-mentioned first electrode and the opposed process of above-mentioned second electrode；By the way that above-mentioned conductive paste is heated to above-mentioned scolding tin grain More than the fusing point of son and more than the solidification temperature of above-mentioned Thermocurable ingredient, is formed using above-mentioned conductive paste and connected to above-mentioned first The interconnecting piece that object Part and above-mentioned second connecting object component are attached is connect, and passes through the solder sections pair in above-mentioned interconnecting piece The process that above-mentioned first electrode and above-mentioned second electrode are electrically connected.
In the manufacturing method of connection structural bodies and connection structural bodies of the invention of the invention, specific electroconductive paste is used Agent, therefore, multiple scolding tin particles are easy to concentrate between first electrode and second electrode, can by multiple scolding tin particle efficients It is configured on electrode (line).In addition, a part for being less prone to multiple scolding tin particles be configured at not formed electrode region ( Every) the case where, the amount for the scolding tin particle for being configured at the region of not formed electrode can be made considerably less.
It is thus possible to improve the conducting reliability between first electrode and second electrode.Furthermore, it is possible to prevent from being not intended to send out The electrical connection between adjacent electrode on the transverse direction of raw connection, to improve insulating reliability.
In addition, the inventors discovered that, in order to which multiple scolding tin particle efficients are configured on electrode, and make to be configured at non-shape Amount at the scolding tin particle in the region of electrode is considerably less, it is necessary to use conductive paste, and cannot use conductive film.
In the present invention, further multiple scolding tin particle efficients can be concentrated between electrode using other methods.As Multiple scolding tin particle efficients are concentrated on into interelectrode method, the following methods can be used: to the first connecting object component and When conductive paste between second connecting object component heats, the viscosity of conductive paste is reduced due to heat, makes the first company as a result, The conductive paste connect between object Part and the second connecting object component generates convection current etc..It in this method, can enumerate: pass through connection The difference of the thermal capacity of the electrode on object Part surface and surface elements in addition to this generates the method for convection current, by connecting object The moisture of component is made vapor by heat and generates the method for convection current and by the first connecting object component and the second connection The temperature difference of object Part generates the method etc. of convection current.Thus, it is possible to be moved to the scolding tin particle in conductive paste effectively Electrode surface.
It, can also be further using the method agglomerated with making scolding tin particle selection in electrode surface in the present invention.As Agglomerate the method in electrode surface with making scolding tin particle selection, can enumerate: selection is good by the wettability of the scolding tin particle melted The connecting object component that other Facing materials of the wettability difference of the scolding tin particle of good electrode material and melting are formed, and make Up to the melting of electrode surface scolding tin particle selection be attached to electrode, other scolding tin grains are made on the scolding tin particle of the melting The method that son melts and adheres to；Selection is formed by other Facing materials of the good electrode material of heat conductivity and heat conductivity difference Connecting object component relative to other surface elements, improve electrode temperature, as a result, on the electrode selectively when heated The method for melting scolding tin；There is positive charge relative to the negative electrical charge being present on the electrode formed by metal using being processed into Scolding tin particle is agglomerated in the method on electrode with making scolding tin particle selection；And relative to hydrophilic metal surface Resin other than scolding tin particle in conductive paste is adjusted to hydrophobicity, agglomerated with making scolding tin particle selection as a result, by electrode In the method etc. on electrode.
Be preferably 10 μm or more in the thickness of interelectrode solder sections, more preferably 20 μm or more, preferably 100 μm with Under, more preferably 80 μm or less.(scolding tin in area 100% that electrode exposes connects scolding tin wetted area on the surface of electrode The area of touching) be preferably 50% or more, more preferably 60% or more, further preferably 70% or more, preferably 100% with Under.
In the manufacturing method of connection structural bodies of the invention, preferably in the process for configuring above-mentioned second connecting object component and Formed in the process of above-mentioned interconnecting piece, by the weight of above-mentioned second connecting object component be applied on above-mentioned conductive paste without into Row pressurization, or at least one work in the process of above-mentioned the second connecting object of configuration component and the process of the above-mentioned interconnecting piece of formation It pressurizes in sequence, and in the process of above-mentioned the second connecting object of configuration component and is formed in the process both sides of above-mentioned interconnecting piece, The pressure of pressurization is lower than 1MPa.By not applying the moulding pressure of 1MPa or more, the cohesion of scolding tin particle can promote.Connect from inhibition It, can be in configuration above-mentioned second in the manufacturing method of connection structural bodies of the invention from the viewpoint of connecing the warpage of object Part It pressurizes at least one process in the process of connecting object component and the process of the above-mentioned interconnecting piece of formation, and in configuration It states the process of the second connecting object component and forms the process both sides of above-mentioned interconnecting piece, moulding pressure is lower than 1MPa.Added In the case where pressure, can also only it pressurize in the process for configuring above-mentioned second connecting object component, it can be only in formation It states in the process of interconnecting piece and pressurizes, in the process for configuring above-mentioned second connecting object component and above-mentioned connection can also be formed The process both sides in portion pressurize.It includes non-pressurized situation in 1MPa that the pressure of pressurization, which is lower than,.In the case where being pressurizeed, The pressure of pressurization is preferably 0.9MPa hereinafter, more preferably 0.8MPa or less.The situation for being 0.8MPa or less in the pressure of pressurization, Compared with the case where pressure of pressurization is more than 0.8MPa, further promote the cohesion of scolding tin particle significantly.
In the manufacturing method of connection structural bodies of the invention, preferably in the process for configuring above-mentioned second connecting object component and It is formed in the process of above-mentioned interconnecting piece without pressurization, applies the weight of above-mentioned second connecting object component to above-mentioned conductive paste Amount, preferably in the process of the process and the above-mentioned interconnecting piece of formation that configure above-mentioned second connecting object component, not to above-mentioned conduction Paste applies the moulding pressure of the power more than above-mentioned second connecting object component weight.In situations such as these, in multiple scolding tin In portion, the uniformity of soldering tin amount can be further improved.Furthermore it is possible to the thickness of solder sections is further effectively thickened, It is easy to multiple scolding tin particles largely to concentrate between electrode, multiple scolding tin particles further can be efficiently configured at electrode On (line).In addition, a part for being less prone to multiple scolding tin particles is configured at the region (interval) of not formed electrode, can more into One step reduces the amount for being configured at the scolding tin particle in region of not formed electrode.Therefore, interelectrode lead can further be improved Logical reliability.Furthermore, it is possible to further prevent the electrical connection between the adjacent electrode on the transverse direction that cannot be attached, and can Further to improve insulating reliability.
In addition, the present inventors have additionally discovered that, if in the process for configuring above-mentioned second connecting object component and forming above-mentioned company The weight of above-mentioned second connecting object component is applied without pressurization to above-mentioned conductive paste in the process of socket part, then is being formed Before interconnecting piece, the scolding tin particle being configured in the region (interval) of not formed electrode can more easily concentrate on first electrode and Between second electrode, multiple scolding tin particles further can also be efficiently configured on electrode (line).In the present invention, combination Using following technical proposals, this is of great significance for obtaining effect of the invention: using the structure of conductive paste Without using this technical solution of conductive film, to above-mentioned conductive paste apply above-mentioned second connecting object component weight and without It pressurizes this technical solution.
In addition, in WO2008/023452A1, describes from along electrode surface and solder powder and being allowed to is pushed efficiently to move From the point of view of viewpoint, it can be pressurizeed in welding with specified pressure, and describe from the sight that soldering tin is formed more reliably From the point of view of point, moulding pressure is adjusted to such as 0MPa or more, preferably 1MPa or more, also describes even if applying intentionally to jointing tape Pressure be 0MPa, due to the self weight for the component being configured on jointing tape, specified pressure can also be applied to splicing tape. In WO2008/023452A1, describing the pressure applied intentionally to jointing tape can be 0MPa, but be more than 0MPa's to applying The case where pressure and the case where be adjusted to 0MPa between the difference of effect there is no record.In addition, WO2008/023452A1 In, to the conductive paste for using paste rather than the importance of membranaceous conductive film does not have any understanding.
In addition, if non-conductive film, the easy coating weight according to conductive paste adjust interconnecting piece using conductive paste And the thickness of solder sections.On the other hand, there are the following problems in conductive film: for the thickness of variations or modifications interconnecting piece, it is necessary to Prepare the conductive film of different-thickness or prepares the conductive film of specified thickness.In addition, there are the following problems in conductive film: in scolding tin Under melting temperature, the melt viscosity of conductive film cannot be made sufficiently to reduce, and hinder the cohesion of scolding tin particle.
Hereinafter, being described with reference to specific embodiment of the present invention.
Fig. 1 is to schematically show the connection structural bodies obtained using the conductive paste of an embodiment of the invention Sectional view.
Connection structural bodies 1 shown in FIG. 1 has the first connecting object component 2, the second connecting object component 3, connects first Connect the interconnecting piece 4 that object Part 2 and the second connecting object component 3 connect.Interconnecting piece 4 by containing Thermocurable compound, Thermal curing agents and multiple scolding tin particles and the conductive paste containing amine hardener, polythiol hardener or hydrazides curing agent is formed.On It states Thermocurable compound and above-mentioned thermal curing agents is Thermocurable ingredient.
Interconnecting piece 4 includes solder sections 4A made of multiple scolding tin particles are concentrated and are interconnected and Thermocurable ingredient heat Solidfied material portion 4B made of solidification.
There are multiple first electrode 2a on the surface (upper surface) of first connecting object component 2.Second connecting object component 3 Surface (lower surface) on have multiple second electrode 3a.First electrode 2a and second electrode 3a are electrically connected by solder sections 4A. Therefore, the first connecting object component 2 and the second connecting object component 3 realize electrical connection by solder sections 4A.In addition, interconnecting piece In 4, in the region (solidfied material portion 4B part) different from the solder sections 4A concentrated between first electrode 2a and second electrode 3a In, scolding tin is not present.In the region (solidfied material portion 4B part) different from solder sections 4A, there is no the welderings for being detached from solder sections 4A Tin.In addition, if being on a small quantity, then scolding tin can reside in and concentrate on the solder sections between first electrode 2a and second electrode 3a 4A different regions (the solidfied material portion part 4B).
As shown in Figure 1, being concentrated with multiple scolding tin grains between first electrode 2a and second electrode 3a in connection structural bodies 1 Son, after multiple scolding tin pellet meltings, the fusant of scolding tin particle occurs after the wet diffusion of electrode surface and is solidified, thus shape At solder sections 4A.Therefore, the connection area of solder sections 4A and first electrode 2a and solder sections 4A and second electrode 3a becomes larger. That is, by using scolding tin particle, with the case where using the outer surface of electric conductivity to be the electroconductive particle of the metals such as nickel, gold or copper phase Than the contact area of solder sections 4A and first electrode 2a and solder sections 4A and second electrode 3a become larger.Therefore, connection structure Conducting reliability and connection reliability in body 1 improve.In addition, conductive paste can contain fluxing agent.Using fluxing agent In the case of, in general, fluxing agent can gradually be inactivated because of heating.
In addition, solder sections 4A is entirely located between first electrode 2a, second electrode 3a in connection structural bodies 1 shown in FIG. 1 Opposed region.In the connection structural bodies 1X of variation shown in Fig. 3, only interconnecting piece 4X and connection structural bodies 1 shown in FIG. 1 be not Together.Interconnecting piece 4X has solder sections 4XA and solidfied material portion 4XB.Can be as connection structural bodies 1X, a large amount of solder sections 4XA In the region that first electrode 2a, second electrode 3a are opposed, a part of solder sections 4XA is from 3a pairs of first electrode 2a, second electrode The region set is leant out to side.The region opposed from first electrode 2a and second electrode 3a is to the solder sections 4XA that side is exposed A part of solder sections 4XA is not the scolding tin for being detached from solder sections 4XA.It should be noted that in present embodiment, it is possible to reduce It is detached from the amount of the scolding tin of solder sections, but the scolding tin for being detached from solder sections can reside in solidfied material portion.
If reducing the usage amount of scolding tin particle, it is easy to get connection structural bodies 1.If increasing the use of scolding tin particle Amount, then be easy to get connection structural bodies 1X.
From the viewpoint of further increasing conducting reliability, along above-mentioned first electrode, above-mentioned interconnecting piece and above-mentioned the When the stack direction of two electrodes observes above-mentioned first electrode and above-mentioned second electrode mutually opposed part, preferably above-mentioned first In electrode and the area 100% of the opposed part of above-mentioned second electrode 50% or more (more preferably 60% or more, it is further excellent It is selected as 70% or more, particularly preferably 80% or more, most preferably 90% or more) configured with the solder sections in above-mentioned interconnecting piece.
From the viewpoint of further increasing conducting reliability, along with above-mentioned first electrode, above-mentioned interconnecting piece and above-mentioned When the mutually opposed part of above-mentioned first electrode and above-mentioned second electrode is observed in the orthogonal direction of the stack direction of second electrode, It is preferred that in the mutually opposed part of above-mentioned first electrode and above-mentioned second electrode configured with the solder sections in above-mentioned interconnecting piece 70% or more (more preferably 80% or more, further preferably 90% or more, particularly preferably 95% or more, most preferably 99% or more).
Then, using the conductive paste of one embodiment of the present invention, illustrate one that manufactures the method for connection structural bodies 1 Example.
Firstly, preparing the first connecting object component 2 on surface (upper surface) with first electrode 2a.Then, such as Fig. 2 (a) shown in, configuration contains Thermocurable ingredient 11B's and multiple scolding tin particle 11A on the surface of the first connecting object component 2 Conductive paste 11 (first step).Conductive paste is configured on the surface equipped with first electrode 2a of the first connecting object component 2 11.After configuring conductive paste 11, scolding tin particle 11A is configured at the region of first electrode 2a (line) and not formed first electrode 2a (interval) the two regions.
It as the configuration method of conductive paste 11, is not particularly limited, the coating using dispenser progress, silk can be enumerated Wire mark brush and spraying etc. by ink discharge device.
In addition, preparing the second connecting object component 3 on surface (lower surface) with second electrode 3a.Then, such as Fig. 2 (b) shown in, in the conductive paste 11 on the surface of the first connecting object component 2, in conductive paste 11 and the first connecting object The second connecting object component 3 (the second step) is configured on the surface of 2 side opposite side of component.On the surface of conductive paste 11, The second connecting object component 3 is initially configured from the side second electrode 3a.At this point, keeping first electrode 2a and second electrode 3a opposed.
Then, conductive paste 11 is heated to the solidification temperature of the fusing point of scolding tin particle 11A or more and Thermocurable ingredient 11B Du or more (the third step).That is, conductive paste 11 is heated to fusing point than scolding tin particle 11A and Thermocurable ingredient 11B In solidification temperature more than higher temperature.When carrying out the heating, it is present in the scolding tin particle 11A collection in the region of not formed electrode In between first electrode 2a and second electrode 3a (auto-collimation effect).In present embodiment, using conductive paste, without the use of Conductive film, and conductive paste also has specific composition, therefore, scolding tin particle 11A efficiently concentrate on first electrode 2a and Between second electrode 3a.In addition, scolding tin particle 11A is melted and is interconnected.In addition, heat cure occurs for Thermocurable ingredient 11B. It should be as a result, forming the first connecting object component 2 of connection and the second connecting object component using conductive paste 11 as shown in Fig. 2 (c) 3 interconnecting piece 4.Interconnecting piece 4 is formed using conductive paste 11, engagement occurs by multiple scolding tin particle 11A and forms solder sections 4A occurs heat cure by Thermocurable ingredient 11B and forms solidfied material portion 4B.If scolding tin particle 11A is sufficiently moved, from After the mobile beginning of scolding tin particle 11A between first electrode 2a and second electrode 3a, until scolding tin particle 11A is first Mobile end between electrode 2a and second electrode 3a, temperature can not be remained centainly.
For present embodiment, in above-mentioned the second step and above-mentioned the third step, without pressurization.Present embodiment In, apply the weight of the second connecting object component 3 to conductive paste 11.Therefore, when forming interconnecting piece 4, scolding tin particle 11A high Concentrate between first electrode 2a and second electrode 3a to effect.In addition, if in above-mentioned the second step and above-mentioned the third step At least one process in pressurize, then the obstruction of the effect between first electrode and second electrode is concentrated on to scolding tin particle Tendency is got higher.The situation by the inventors discovered that.
In addition, in present embodiment, without pressurization, therefore, in the first connecting object component for being coated with conductive paste When the second connecting object component of upper coincidence, even if with the electricity of the electrode of the first connecting object component and the second connecting object component In the state that the alignment of pole deviates, when the first connecting object component and the second connecting object component are overlapped, it can also repair The just deviation, and make the electrode connection (auto-collimation effect) of the electrode and the second connecting object component of the first connecting object component. This is because, melting of the self-coagulation between the electrode of the first connecting object component and the electrode of the second connecting object component In scolding tin, scolding tin and conductive paste between the electrode of the first connecting object component and the electrode of the second connecting object component its Therefore the smallest side energy stabilization of the area that its ingredient is in contact forms and becomes the connection structure of minimum area i.e. pair The power of quasi- connection structure plays a role.At this point, it is preferred that conductive paste is uncured and in the temperature, time, conductive paste The viscosity of ingredient other than scolding tin particle is substantially low.
As described above, connection structural bodies 1 shown in FIG. 1 can be obtained.In addition, above-mentioned the second step and above-mentioned the third step can To be carried out continuously.Furthermore it is possible to after carrying out above-mentioned the second step, the first connecting object component 2, the conductive paste 11 that make It is transferred to heating element with the laminated body of the second connecting object component 3, carries out above-mentioned the third step.In order to carry out above-mentioned heating, Above-mentioned laminated body can be configured on heating element, and above-mentioned laminated body can also be configured in the space of heating.
As long as more than the fusing point of the heating temperature scolding tin particle in above-mentioned the third step and the solidification of Thermocurable ingredient It more than temperature, is just not particularly limited.Above-mentioned heating temperature is preferably 140 DEG C or more, and more preferably 160 DEG C or more, preferably 450 DEG C hereinafter, more preferably 250 DEG C hereinafter, further preferably 200 DEG C or less.
In addition, by correction position and being repeated for the purpose of manufacturing after above-mentioned the third step, first can be removed from interconnecting piece and connected Connect object Part or the second connecting object component.Heating temperature for carrying out the removing be preferably the fusing point of scolding tin particle with On, more preferably+10 DEG C of the fusing point (DEG C) or more of scolding tin particle.Heating temperature for carrying out the removing can be scolding tin particle + 100 DEG C of fusing point (DEG C) or less.
As the heating means in above-mentioned the third step, can enumerate more than the fusing point of scolding tin particle and Thermocurable ingredient Solidification temperature more than, by connection structural bodies integrally using reflow ovens or the method heated using baking oven, or only partly The method for heating the interconnecting piece of connection structural bodies.
Utensil used in method as local heating can be enumerated: heating plate, assign the heat gun of hot wind, soldering iron and Infrared heater etc..
In addition, preferably forming heating plate upper surface as follows: immediately below interconnecting piece when carrying out local heating using heating plate It is formed using the higher metal of heat conductivity, other positions that preferably do not heated are lower using heat conductivities such as fluororesin Material is formed.
Above-mentioned first, second connecting object component is not particularly limited.As above-mentioned first, second connecting object component, Specifically, can enumerate: the electronics such as semiconductor chip, semiconductor package part, LED chip, LED encapsulation, capacitor and diode Part and resin film, printed base plate, flexible printing substrate, flexble flat's cable, rigid-flexible combination substrate, glass epoxy substrate And electronic component of circuit substrates such as glass substrate etc. etc..Above-mentioned first, second connecting object component is preferably electronic component.
At least one connecting object component in above-mentioned first connecting object component and above-mentioned second connecting object component is excellent It is selected as resin film, flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate.Above-mentioned second connecting object component is preferably Resin film, flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate.Resin film, flexible printing substrate, flexble flat's line Cable and rigid-flexible combination substrate have flexibility height and than the properties of relatively lightweight.Conductive film is being used for this connecting object component In the case where connection, there is scolding tin particle to be difficult to concentrate on the tendency on electrode.In contrast, by using conductive paste, i.e., Using resin film, flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate, by the way that scolding tin particle efficient is concentrated In on electrode, interelectrode conducting reliability can also be sufficiently improved.Using resin film, flexible printing substrate, flexble flat In the case where cable or rigid-flexible combination substrate, compared with the case where having used the other connecting object components such as semiconductor chip, no The improvement effect for the interelectrode conducting reliability pressurizeed is available to be further increased.
There is periphery or face battle array etc. in the form of above-mentioned connecting object component.As the feature of each component, 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 set to above-mentioned connecting object component, can enumerate: gold electrode, nickel electrode, tin electrode, aluminium electrode, copper The metal electrodes such as electrode, molybdenum electrode, silver electrode, SUS electrode and tungsten electrode.It is flexible printing substrate in above-mentioned connecting object component In the case where, above-mentioned electrode is preferably gold electrode, nickel electrode, tin electrode, silver electrode or copper electrode.In above-mentioned connecting object component In the case where for glass substrate, above-mentioned electrode is preferably aluminium electrode, copper electrode, molybdenum electrode, silver electrode or tungsten electrode.In addition, In the case that above-mentioned electrode is aluminium electrode, it is also possible to the electrode only formed by aluminium, is also possible to the table in metal oxide layer The electrode of face lamination aluminium layer.It as the material of above-mentioned metal oxide layer, can enumerate: doped with the oxidation of trivalent metallic element Indium and zinc oxide etc. doped with trivalent metallic element.It as above-mentioned trivalent metallic element, can enumerate: Sn, Al and Ga etc..
Hereinafter, enumerating Examples and Comparative Examples, the present invention is specifically described.The present invention is not limited to implementation below Example.
The synthesis of polymer A:
Bisphenol F (is contained into the 4,4 '-methylene bis-phenols, 2,4 '-methylene bis-phenols and 2,2 '-Asias of 2:3:1 with weight ratio meter Methyl bisphenol) 100 parts by weight, 130 parts by weight of 1,6-HD diglycidyl ether, bisphenol f type epoxy resin (DIC plants of formulas Commercial firm manufactures " EPICLONEXA-830CRP ") 5 parts by weight and (Chemtex plants of Nagase of resorcinol type ring oxygen compound Formula commercial firm manufactures " EX-201 ") 10 parts by weight, it is put into 3 mouthfuls of flasks, under nitrogen flowing, is dissolved with 100 DEG C.Then, addition is made For 0.15 parts by weight of triphenylbut base phosphonium bromide of hydroxyl and the addition reaction catalyst of epoxy group, under nitrogen flowing, with 140 DEG C Polyaddition reaction 4 hours, reactant (polymer A) was obtained as a result,.
Pass through NMR, it is thus identified that polyaddition reaction has occurred, has further acknowledged that reactant (polymer A) has on main chain Hydroxyl and 1,6-HD diglycidyl ether, bisphenol f type epoxy resin and resorcinol type epoxy compound from Bisphenol F Structural unit made of the epoxy group bonding of object, and there is epoxy group in two ends.
Weight average molecular weight by the obtained reactant (polymer A) of GPC is 28000, number-average molecular weight 8000.
Polymer B: two terminal epoxy groups rigid backbone phenoxy resins, Mitsubishi chemical Co., Ltd's manufacture " YX6900BH45 ", weight average molecular weight 16000
Thermocurable compound 1: naphthalene type ring oxygen compound (" HP-4032D " of Dainippon Ink Chemicals's manufacture, molecular weight 272)
Thermocurable compound 2: resorcinol type ring oxygen compound be (manufacture of Nagase Chemtex Co., Ltd. " EX-201 ", molecular weight 222)
Thermocurable compound 3: bisphenol f type epoxy resin compound, Dainippon Ink Chemicals manufacture " EPICLONEXA- 830CRP”
Thermal curing agents 1: pentaerythrite four (3- mercaptobutylate), " the CURRANTS MT of Showa Denko K. K's manufacture PE1”
" Fujicure7000 " of latency epoxy thermosetting agent 1:T&K TOKA Co., Ltd. manufacture
Fluxing agent 1: adipic acid, Wako Pure Chemical Industries, Ltd.'s manufacture, 152 DEG C of fusing point (active temperature)
Fluxing agent 2: succinic acid, Wako Pure Chemical Industries, Ltd.'s manufacture, 186 DEG C of fusing point (active temperature)
The production method of scolding tin particle 1,2:
Scolding tin particle with anionic polymer 1: scolding tin particle main body 200g, adipic acid are weighed in three-necked flask 40g and acetone 70g, then, hydroxyl and adipic acid of the addition Dibutyltin oxide 0.3g as scolding tin particle body surfaces Carboxyl carries out the catalyst of dehydrating condensation, reacts 4 hours at 60 DEG C.Then, it is recycled by filtering scolding tin particle.
Scolding tin particle, adipic acid 50g, toluene 200g, the p-methyl benzenesulfonic acid 0.3g of recycling are weighed in three-necked flask, on one side It is vacuumized and is flowed back, reacted 3 hours at 120 DEG C on one side.At this point, using Dean-Stark extraction element, and on one side The water generated by dehydrating condensation is removed to be reacted on one side.
Then, scolding tin particle is recovered by filtration, utilizes hexane washing and drying.Then, it crushes to obtain using ball mill Scolding tin particle after, carry out sieving make as defined in CV value.
(zeta potential measurement)
In addition, obtained scolding tin particle 0.05g is put into methanol 10g, ultrasonication is carried out, is equably divided as a result, It dissipates, obtains dispersion liquid.Using the dispersion liquid, and " the Delsamax PRO " manufactured using Beckman Coulter company, pass through Electrophoresis assays measure zeta potential.
(weight average molecular weight of anionic polymer)
For the weight average molecular weight of the anionic polymer 1 on the surface of scolding tin particle, the hydrochloric acid of 0.1N, dissolution weldering are used After tin, polymer is recovered by filtration, and acquire by GPC.
(the CV value of the partial size of scolding tin particle)
Utilize laser diffraction formula particle size distribution device (LA-920 that hole field makes the manufacture of Co., Ltd., institute) measurement CV Value.
Using to scolding tin particle 1, (SnBi scolding tin particle, manufactures Co., Ltd., Mitsui Metal Co., Ltd. by 139 DEG C of fusing point " DS10 ") sorted obtained from scolding tin particle main body, carried out be surface-treated and with anionic polymer 1 scolding tin Particle, 13 μm of average grain diameter, CV value: 20%, the zeta potential on surface :+0.48mV, polymer molecular weight: Mw=7000)
Using to scolding tin particle 2, (SnBi scolding tin particle, manufactures " 10- to Co., Ltd., Mitsui Metal Co., Ltd. by 139 DEG C of fusing point 25 ") scolding tin particle main body obtained from being sorted has carried out the scolding tin grain for being surface-treated and having anionic polymer 1 Son, average grain diameter: 25 μm, CV value: 15%, the zeta potential on surface :+0.4mV, polymer molecular weight: Mw=8000)
Electroconductive particle 1: 1 μm of thickness of layers of copper is formed on the surface of resin particle, and on the surface of the layers of copper It is formed with the electroconductive particle of 3 μm of thickness of soldering-tin layer (tin: bismuth=42 weight %:58 weight %)
The production method of electroconductive particle 1:
To 10 μm of average grain diameter of divinylbenzene resin particles (" the microballoon SP- of Sekisui Chemical Co., Ltd's manufacture 210 ") process for electroless nickel plating is carried out, forms 0.1 μm of thickness of substrate nickel coating on the surface of resin particle.Then, to being formed with The resin particle of substrate nickel coating carries out electrolytic copper plating, forms 1 μm of thickness of layers of copper.Further use the electrolysis containing tin and bismuth Plating solution carries out electrolysis plating, forms 3 μm of thickness of soldering-tin layer.Thickness is formed in this way, being produced on the surface of resin particle 1 μm of layers of copper and 3 μm of thickness of soldering-tin layer (tin: bismuth=42 weight %:58 weight %) is formed on the surface of the layers of copper Electroconductive particle 1.
(Examples 1 to 6 and Comparative Examples 1 and 2)
(1) production of anisotropic conductive paste
Ingredient shown in following table 1 is cooperated with use level shown in following table 1, obtains anisotropic conductive paste.
The production of (2) first connection structural bodies (L/S=50 μm/50 μm)
Preparing upper surface has the copper electrode pattern (thickness 12 of copper electrode that L/S is 50 μm/50 μm, electrode length is 3mm μm) glass epoxy substrate (FR-4 substrate) (the first connecting object component).In addition, preparing lower surface there is L/S to be 50 μm/50 μm, electrode length be 3mm copper electrode pattern (12 μm of the thickness of copper electrode) flexible printing substrate (the second connecting object portion Part).
The area of glass epoxy substrate and flexible printing substrates while stacking is set as 1.5cm × 3mm, and the number of electrodes of connection is set as 75 It is right.
In the upper surface of above-mentioned glass epoxy substrate, using metal mask, with the anisotropic conductive paste after production The mode for being 100 μm of thickness on the electrode of glass epoxy substrate, is coated by silk-screen printing, forms anisotropic conductive Paste layer.Then, in the above-mentioned flexible printing substrate of the upper surface lamination of anisotropic conductive paste layer, keep electrode opposite each other. At this point, without pressurization.Apply the weight of above-mentioned flexible printing substrate to anisotropic conductive paste layer.Then, with each to different Property electroconductive paste oxidant layer temperature heated as 190 DEG C of mode, melt scolding tin, and make anisotropic conductive paste layer 190 DEG C and solidify under conditions of 10 seconds, obtain the first connection structural bodies.
The production of (3) second connection structural bodies (L/S=75 μm/75 μm)
Preparing upper surface has the copper electrode pattern (thickness 12 of copper electrode that L/S is 75 μm/75 μm, electrode length is 3mm μm) glass epoxy substrate (FR-4 substrate) (the first connecting object component).In addition, preparing lower surface there is L/S to be 75 μm/75 μm, the flexible printing substrate (the second connecting object component) of the copper electrode pattern (12 μm of the thickness of copper electrode) of electrode length 3mm.
Other than the above-mentioned glass epoxy substrate and flexible printing substrate that use L/S different, with the first connection structural bodies Production as, obtain the second connection structural bodies.
(4) production of third connection structural bodies (L/S=100 μm/100 μm)
Preparing upper surface has the copper electrode pattern (thickness of copper electrode that L/S is 100 μm/100 μm, electrode length is 3mm 12 μm) glass epoxy substrate (FR-4 substrate) (the first connecting object component).In addition, preparing lower surface there is L/S to be 100 μ M/100 μm, electrode length be 3mm copper electrode pattern (12 μm of the thickness of copper electrode) flexible printing substrate (second connection pair As component).
Other than the above-mentioned glass epoxy substrate and flexible printing substrate that use L/S different, with the first connection structural bodies Production as, obtain third connection structural bodies.
(evaluation)
(1) mean aspect ratio of the crystal of crystallinity Thermocurable compound and average major diameter
Using electron microscope observation conductive film, to evaluate the average length and width of the crystallization of crystallinity Thermocurable compound When be averaged major diameter.
(2) viscosity
In anisotropic conductive paste, each temperature (25 DEG C, -80 DEG C of scolding tin particle fusing point, -30 DEG C of scolding tin particle fusing point, Scolding tin particle fusing point) under viscosity and show lowest melt viscosity temperature using rheometer (EOLOGICA Co., Ltd. manufacture " STRESSTECH ") etc., root diameter 20mm, oscillation distortion control, 10 DEG C/min of heating rate under conditions of surveyed It is fixed.
(3) thickness of solder sections
The connection structural bodies obtained by cross-section observation evaluates the thickness of the solder sections between upper/lower electrode.
(4) the configuration precision 1 of the scolding tin on electrode
In obtained connection structural bodies, the stack direction evaluated along first electrode, interconnecting piece and second electrode observes first When electrode and the mutually opposed part of second electrode, in the area 100% of first electrode and the mutually opposed part of second electrode Interconnecting piece in configured with solder sections area ratio X.The configuration precision 1 of scolding tin on electrode is sentenced with following benchmark It is fixed.
[determinating reference of the configuration precision 1 of the scolding tin on electrode]
00: ratio X is 70% or more
Zero: ratio X is 60% or more, lower than 70%
△: ratio X is 50% or more, lower than 60%
×: ratio X is lower than 50%
(5) the configuration precision 2 of the scolding tin on electrode
In obtained connection structural bodies, evaluation is along vertical with the stack direction of first electrode, interconnecting piece and second electrode When first electrode and second electrode mutually opposed part are observed in direction, in the solder sections 100% in interconnecting piece, it is configured at the The ratio Y of one electrode and the solder sections in the interconnecting piece of the mutually opposed part of second electrode.Determined on electrode with following benchmark Scolding tin configuration precision 2.
[determinating reference of the configuration precision 2 of the scolding tin on electrode]
00: ratio Y is 99% or more
Zero: ratio Y is 90% or more, lower than 99%
△: ratio Y is 70% or more, lower than 90%
×: ratio Y is lower than 70%
(6) the conducting reliability between upper/lower electrode
In obtained the first, second, third connection structural bodies (n=15), by each interconnecting piece between upper/lower electrode The connection resistance of position is measured by four-terminal method respectively.Calculate the average value of connection resistance.In addition, according to voltage=electric current A voltage when constant current is flowed through in the relationship of × resistance, measurement, can be in the hope of connection resistance.Reliability will be connected with following benchmark Determined.
[determinating reference of conducting reliability]
00: the average value for connecting resistance is 50m Ω or less
Zero: the average value for connecting resistance is more than 50m Ω and 70m Ω or less
△: the average value for connecting resistance is more than 70m Ω and 100m Ω or less
×: the average value for connecting resistance is more than 100m Ω or generation bad connection
(7) adjacent interelectrode insulating reliability
In obtained the first, second, third connection structural bodies (n=15), placed in 85 DEG C, the atmosphere of humidity 85% After 100 hours, between applying 5V adjacent electrode, and in 25 Site Determination resistance values.Determine that insulation is reliable with following benchmark Property.
[determinating reference of insulating reliability]
00: the average value for connecting resistance is 107Ω or more
Zero: the average value for connecting resistance is 106Ω or more, it is lower than 107Ω
△: the average value for connecting resistance is 105Ω or more, it is lower than 106Ω
×: the average value of resistance is connected lower than 105Ω
(8) position deviation between upper/lower electrode
Following evaluation is carried out to obtained connection structural bodies, along first electrode, the lamination side of interconnecting piece and second electrode When to observation first electrode and the opposed part of second electrode, whether the center line of first electrode and the center line of second electrode are right Together and the distance of position deviation.The position deviation between upper/lower electrode is determined according to following benchmark.
[determinating reference of upper and lower interelectrode position deviation]
00: position deviation is lower than 15 μm
Zero: position deviation is 15 μm or more, is lower than 25 μm
△: position deviation is 25 μm or more, is lower than 40 μm
×: position deviation is 40 μm or more
Details and result are indicated in following table 1,2.
The case where being not only using flexible printing substrate is using resin film, flexble flat's cable and rigid-flexible combination substrate In the case where, it also observed identical trend.

Claims (14)

1. a kind of conductive paste, contains:
As Thermocurable ingredient Thermocurable compound and thermal curing agents and
Multiple scolding tin particles,
Conductive paste -80 DEG C of fusing point of the scolding tin particle at a temperature of viscosity and conductive paste it is molten in the scolding tin particle The ratio between viscosity at a temperature of -30 DEG C of point is 1.5 or more, 4 or less.
2. conductive paste as described in claim 1, wherein
The temperature of the display lowest melt viscosity of conductive paste is present in the temperature of -30 DEG C of fusing point of the scolding tin particle or more, institute State the temperature temperature region below of+20 DEG C of fusing point of scolding tin particle.
3. conductive paste as claimed in claim 1 or 2, wherein
The Thermocurable compound contains the Thermocurable compound at 25 DEG C for solid.
4. conductive paste as claimed in claim 1 or 2, wherein
The average grain diameter of the scolding tin particle is 1 μm or more, 40 μm or less.
5. conductive paste as claimed in claim 1 or 2, wherein
The content of the scolding tin particle is 10 weight % or more, 90 weight % or less.
6. a kind of connection structural bodies comprising:
Surface have at least one first electrode the first connecting object component,
Surface have at least one second electrode the second connecting object component,
The interconnecting piece that the first connecting object component and the second connecting object component are linked together,
The material of the interconnecting piece is conductive paste according to any one of claims 1 to 5,
The first electrode and the second electrode realize electrical connection by the solder sections in the interconnecting piece,
The solder sections are that multiple scolding tin particles are concentrated and are interconnected and formed.
7. connection structural bodies as claimed in claim 6, wherein
The second connecting object component is semiconductor chip, resin film, flexible printing substrate, flexible flat cable or rigid-flexible knot Close substrate.
8. connection structural bodies as claimed in claims 6 or 7, wherein
The first electrode and described is observed along the stack direction of the first electrode, the interconnecting piece and the second electrode When the mutually opposed part of second electrode, the area in the mutually opposed part of the first electrode and the second electrode 50% or more in 100% is configured with the solder sections in the interconnecting piece.
9. connection structural bodies as claimed in claims 6 or 7, wherein
Along described in the direction observation vertical with the stack direction of the first electrode, the interconnecting piece and the second electrode It is mutually opposed in the first electrode and the second electrode when first electrode and the mutually opposed part of the second electrode Part is configured with 70% or more of the solder sections in the interconnecting piece.
10. a kind of manufacturing method of connection structural bodies comprising:
Have the first of at least one first electrode to connect on surface using conductive paste described in any one of Claims 1 to 55 Connect the process that the conductive paste is configured on the surface of object Part；
On the surface opposite with the first connecting object component side of the conductive paste, configuration surface has at least one Second connecting object component of second electrode, and make the first electrode and the opposed process of the second electrode；
By the conductive paste be heated to the solidification temperature of the fusing point of the scolding tin particle or more and the Thermocurable ingredient with On, the company for connecting the first connecting object component and the second connecting object component is formed from there through the conductive paste Socket part, and the work for being electrically connected the first electrode and the second electrode by the solder sections in the interconnecting piece Sequence,
The solder sections are that multiple scolding tin particles are concentrated and are interconnected and formed.
11. the manufacturing method of connection structural bodies as claimed in claim 10, wherein
In the process and the process for forming interconnecting piece of the second connecting object component of the configuration, the conductive paste is applied Add the weight of the second connecting object component, and without pressurization, alternatively,
In at least one process in the process and the process for forming interconnecting piece of the second connecting object component of the configuration, It pressurizes, also, in the process of the second connecting object component of the configuration and described process the two works for forming interconnecting piece In sequence, the pressure of pressurization is lower than 1MPa.
12. the manufacturing method of connection structural bodies as described in claim 10 or 11, wherein
The second connecting object component is semiconductor chip, resin film, flexible printing substrate, flexible flat cable or rigid-flexible knot Close substrate.
13. the manufacturing method of connection structural bodies as described in claim 10 or 11, wherein
Following connection structural bodies is obtained, the connection structural bodies is along the first electrode, the interconnecting piece and described second When the stack direction of electrode observes the first electrode and the second electrode mutually opposed part, in the first electrode and 50% or more in the area 100% of the mutually opposed part of the second electrode is configured with the solder sections in the interconnecting piece.
14. the manufacturing method of connection structural bodies as described in claim 10 or 11, wherein
Obtain following connection structural bodies, the connection structural bodies along with the first electrode, the interconnecting piece and described When the first electrode and the second electrode mutually opposed part are observed in the vertical direction of the stack direction of second electrode, The first electrode and the mutually opposed part of the second electrode configured with the solder sections in the interconnecting piece 70% or more.
CN201580052378.9A 2014-12-26 2015-12-16 The manufacturing method of conductive paste, connection structural bodies and connection structural bodies Active CN106716550B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2014265715 2014-12-26
JP2014-265715 2014-12-26
PCT/JP2015/085195 WO2016104276A1 (en) 2014-12-26 2015-12-16 Electrically conductive paste, connection structure, and production method for connection structure

Publications (2)

Publication Number Publication Date
CN106716550A CN106716550A (en) 2017-05-24
CN106716550B true CN106716550B (en) 2019-04-19

Family

ID=56150301

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201580052378.9A Active CN106716550B (en) 2014-12-26 2015-12-16 The manufacturing method of conductive paste, connection structural bodies and connection structural bodies

Country Status (5)

Country Link
JP (1) JP5966102B1 (en)
KR (1) KR20170102184A (en)
CN (1) CN106716550B (en)
TW (1) TW201629988A (en)
WO (1) WO2016104276A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019203053A1 (en) * 2018-04-18 2019-10-24 積水化学工業株式会社 Electroconductive material, connection structure, and method for manufacturing connection structure
JP7032367B2 (en) * 2019-10-25 2022-03-08 デクセリアルズ株式会社 Manufacturing method of connecting body, anisotropic conductive bonding material, and connecting body
KR102556928B1 (en) * 2021-03-31 2023-07-20 주식회사 노피온 Self-assembly anisotropic conductive adhesive and component mounting method using the same
CN113319454B (en) * 2021-04-29 2022-08-23 中国电子科技集团公司第二十九研究所 Solder presetting method for welding end of surface-mounted self-contained solid solder connector

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102513739A (en) * 2011-12-30 2012-06-27 深圳市晨日科技有限公司 High-temperature lead-free halogen-free solder paste and preparation method thereof
CN102576766A (en) * 2009-10-15 2012-07-11 日立化成工业株式会社 Conductive adhesive, solar cell, method for manufacturing solar cell, and solar cell module
CN103289621A (en) * 2012-02-23 2013-09-11 株式会社田村制作所 Thermosetting resin composition
CN103443868A (en) * 2012-03-26 2013-12-11 积水化学工业株式会社 Conductive material and connecting structure

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090045195A (en) * 2006-08-25 2009-05-07 스미토모 베이클리트 컴퍼니 리미티드 Adhesive tape, joint structure, and semiconductor package
JP2010040893A (en) * 2008-08-07 2010-02-18 Sumitomo Bakelite Co Ltd Method of connecting terminals to each other, method of manufacturing semiconductor device using the same, and method of coagulating conductive particle
JP5540916B2 (en) * 2010-06-15 2014-07-02 デクセリアルズ株式会社 Method for manufacturing connection structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102576766A (en) * 2009-10-15 2012-07-11 日立化成工业株式会社 Conductive adhesive, solar cell, method for manufacturing solar cell, and solar cell module
CN102513739A (en) * 2011-12-30 2012-06-27 深圳市晨日科技有限公司 High-temperature lead-free halogen-free solder paste and preparation method thereof
CN103289621A (en) * 2012-02-23 2013-09-11 株式会社田村制作所 Thermosetting resin composition
CN103443868A (en) * 2012-03-26 2013-12-11 积水化学工业株式会社 Conductive material and connecting structure

Also Published As

Publication number Publication date
JP5966102B1 (en) 2016-08-10
KR20170102184A (en) 2017-09-08
JPWO2016104276A1 (en) 2017-04-27
WO2016104276A1 (en) 2016-06-30
CN106716550A (en) 2017-05-24
TW201629988A (en) 2016-08-16

Similar Documents

Publication Publication Date Title
CN107148653B (en) The manufacturing method of conductive paste, connection structural bodies and connection structural bodies
CN106463200B (en) The manufacturing method of conductive paste, connection structural bodies and connection structural bodies
CN105493201B (en) The manufacturing method of conductive paste, connection structural bodies and connection structural bodies
CN105849820B (en) The manufacturing method of conductive paste, the manufacturing method of conductive paste, connection structural bodies and connection structural bodies
CN105900180B (en) The manufacturing method of conductive paste, connection structural bodies and connection structural bodies
CN105493207B (en) The manufacturing method of connection structural bodies
CN106716550B (en) The manufacturing method of conductive paste, connection structural bodies and connection structural bodies
JP6557591B2 (en) Conductive film, connection structure, and manufacturing method of connection structure
KR102456447B1 (en) Electrically conductive paste, connection structure, and production method for connection structure
JP6592350B2 (en) Anisotropic conductive material, connection structure, and manufacturing method of connection structure
JP2016126878A (en) Conductive paste, connection structure and method for producing connection structure
TWI663900B (en) Manufacturing method of connection structure
JP2016126877A (en) Conductive paste, connection structure and method for producing connection structure
JP6514610B2 (en) Method of manufacturing connection structure
JP6514615B2 (en) Method of manufacturing connection structure
WO2016035637A1 (en) Method of manufacturing connection structure
JP6514614B2 (en) Method of manufacturing connection structure and connection structure
JP2016066614A (en) Conductive paste, connection structure and method for producing connection structure
JP2016066615A (en) Conductive paste, connection structure and method for producing connection structure
JP2016126876A (en) Conductive material, connection structure and method for producing connection structure
JP2016076354A (en) Manufacturing method of connection structure, and connection structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant