CN107148653B - 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

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Publication number
CN107148653B
CN107148653B CN201580057986.9A CN201580057986A CN107148653B CN 107148653 B CN107148653 B CN 107148653B CN 201580057986 A CN201580057986 A CN 201580057986A CN 107148653 B CN107148653 B CN 107148653B
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electrode
scolding tin
mentioned
conductive paste
connecting object
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CN107148653A (en
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石泽英亮
上野山伸也
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/11—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive 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
    • H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Conductive Materials (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Non-Insulated Conductors (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)

Abstract

The present invention provides a kind of conductive paste, interval that can accurately between coordination electrode, scolding tin particle can also be efficiently configured on electrode, and interelectrode conducting reliability can be improved.Conductive paste of the invention is used to have the second connecting object component of second electrode to be attached with the first connecting object component of first electrode and surface on surface, and above-mentioned first electrode and above-mentioned second electrode are electrically connected, the conductive paste contains multiple spacers that Thermocurable ingredient, multiple scolding tin particles and fusing point are 250 DEG C or more, and the average grain diameter of above-mentioned spacer is bigger than the average grain diameter of above-mentioned scolding tin particle.

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.With regard to above-mentioned each For 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, a kind of jointing tape is disclosed in following patent documents 1, 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 having used above-mentioned jointing tape is also disclosed in patent document 1.Specifically, to the first base Plate, splicing tape, the second substrate, splicing tape and third substrate start successively to carry out lamination from below, to obtain laminated body.This When, make the first electrode for being set to first substrate surface and opposed set on the second electrode on the second substrate surface.In addition, making to be set to The second electrode on the second substrate surface and third electrode contraposition set on third substrate surface.Moreover, with specified temperature to folded Layer body is heated and is bonded.Connection structural bodies is obtained as a result,.
In addition, disclosing a kind of bonding agent of anisotropic conductive in following patent documents 2, make as the first electronics zero The electrode of electrode, that is, first electrode of the interconnecting piece of part and the interconnecting piece as the second electronic component, that is, second electrode electrical connection.On The bonding agent for stating anisotropic conductive contains insulating polymers resin, engagement particle and spacer particle.Above-mentioned engagement grain Son is melted by the heat that the ultrasonic wave applied by the bonding agent to above-mentioned anisotropic conductive generates.Above-mentioned spacer grain Son has the fusing point higher than above-mentioned engagement particle.As above-mentioned engagement particle, scolding tin particle can be enumerated.
Existing technical literature
Patent document
Patent document 1:WO2008/023452A1
Patent document 2: Japanese Unexamined Patent Application Publication 2012-532979 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 effectively configured In on electrode (line).For example, a part of solder powder is easily configurable at no shape in jointing tape documented by patent document 1 At the region (interval) of electrode.It is configured at and does not form the solder powder of electrode zone and do not contribute to interelectrode conducting.
Even solder powder can not be efficiently configured to sometimes in addition, the anisotropic conductive paste containing solder powder On electrode (line).In addition, in the case where having used the anisotropic conductive paste containing solder powder, after conductive connection, easily It is uneven in being generated in interelectrode interval.In addition, even if can not be incited somebody to action sometimes in the bonding agent documented by patent document 2 The engagement particle such as scolding tin particle is efficiently configured on electrode (line).In addition, such as the record of patent document 2, even if with scolding tin grain The engagement particle such as son separately uses spacer particle, and engagement particle can not be efficiently configured on electrode (line) sometimes.
The object of the present invention is to provide a kind of conductive paste, interval that can accurately between coordination electrode may be used also Scolding tin particle to be efficiently configured on electrode, and interelectrode conducting reliability can be improved.The present invention also provides one kind The connection structural bodies of the conductive paste and the manufacturing method of connection structural bodies are used.
For solving the technical solution of technical problem
Wide in range aspect according to the present invention provides a kind of conductive paste, be used to have first electrode to surface first There is the second connecting object component of second electrode to be attached for connecting object component and surface, and to the first electrode and institute It states second electrode to be electrically connected, wherein the conductive paste contains Thermocurable ingredient, multiple scolding tin particles and fusing point and is The average grain diameter of 250 DEG C or more of multiple spacers, the spacer is bigger than the average grain diameter of the scolding tin particle.
In some particular aspects of conductive paste of the invention, the spacer is insulating properties particle.
In some particular aspects of conductive paste of the invention, the conductive paste is connected with the spacer and described first Connect object Part and mode that the second connecting object component this both sides connect come using.
In some particular aspects of conductive paste of the invention, the conductive paste uses as follows: to first electricity When pole and the second electrode are electrically connected, the conductive paste is heated to the fusing point of the scolding tin particle or more and described More than the solidification temperature of Thermocurable ingredient, make multiple scolding tin particle coacervations and integration.
In some particular aspects of conductive paste of the invention, the average grain diameter of the spacer and the scolding tin particle The ratio between average grain diameter is 1.1 or more, 15 or less.
In some particular aspects of conductive paste of the invention, the content of the spacer is 0.1 weight % or more, 10 weights Measure % or less.
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, 80 Weight % or less.
In some particular aspects of conductive paste of the invention, the content of the scolding tin particle in terms of weight % unit with The ratio between content of the spacer in terms of weight % unit is 2 or more, 100 or less.
Wide in range aspect according to the present invention provides 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 connected,
The material of the interconnecting piece is the conductive paste, and the first electrode and the second electrode pass through the company Solder sections in socket part realize electrical connection, the spacer and the first connecting object component and second connecting object This both sides of component contact.
Wide in range aspect according to the present invention provides a kind of manufacturing method of connection structural bodies comprising:
There is the surface of the first connecting object component of at least one first electrode on surface using the conductive paste The process of the upper configuration conductive paste；
On the surface opposite with the first connecting object component side of the conductive paste, configuration surface has at least Second connecting object component of one second electrode, and make the first electrode and the opposed process of the second electrode；
The conductive paste is heated to the solidification temperature of the fusing point of the scolding tin particle or more and the Thermocurable ingredient Degree or more, it is formed from there through the conductive paste and connects the first connecting object component and the second connecting object component The interconnecting piece being connected together, and the first electrode and the second electrode are realized by the solder sections in the interconnecting piece Electrical connection, the work for contacting the spacer and the first connecting object component and the second connecting object component this both sides Sequence.
In some particular aspects of the manufacturing method of connection structural bodies of the invention, wherein
When being electrically connected to the first electrode and the second electrode, the conductive paste is heated to the weldering More than the fusing point of tin particle and more than the solidification temperature of the Thermocurable ingredient, make multiple scolding tin particle coacervations and integrated Change.
In some particular aspects of the manufacturing method of connection structural bodies of the invention, in the second connecting object portion of the configuration In the process of part and the process for forming interconnecting piece, apply the weight of the second connecting object component to the conductive paste Amount, and without pressurization.
The second connecting object component is preferably resin film, flexible printing substrate, flexible flat cable or rigid-flexible combination Substrate.
The effect of invention
It is 250 DEG C or more multiple that conductive paste of the invention, which contains Thermocurable ingredient, multiple scolding tin particles and fusing point, Therefore spacer has the second of second electrode to connect on surface with the first connecting object component of first electrode and surface It connects object Part to be attached, and in the case where being electrically connected the first electrode and the second electrode, it can be accurately Scolding tin particle can also be efficiently configured on electrode by the interval between coordination electrode, and it is reliable that interelectrode conducting can be improved Property.
Detailed description of the invention
Fig. 1 is to schematically show cuing open for the connection structural bodies obtained using the conductive paste of one embodiment of the present invention View；
Fig. 2 (a)~Fig. 2 (c) is for using the conductive paste of one embodiment of the present invention to manufacture connection structural bodies The cross-sectional view of each process of one example of method；
Fig. 3 is the cross-sectional view for indicating the variation of connection structural bodies；
Fig. 4 is the cross-sectional view for indicating the variation of connection structural bodies.
Description of symbols
1,1X, 1Y ... connection structural bodies
2, the first connecting object of 2Y ... component
2a ... first electrode
The first protrusion 2y ...
3, the second connecting object of 3Y ... component
3a ... second electrode
The second protrusion 3y ...
4,4X, 4Y ... interconnecting piece
4A, 4XA, 4YA ... solder sections
4B, 4XB, 4YB ... solidfied material portion
5,5X, 5Y ... spacer
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 is used to having surface the first connecting object component of first electrode and surface with the Second connecting object component of two electrodes is attached, and is electrically connected to above-mentioned first electrode and above-mentioned second electrode.This The conductive paste of invention contains Thermocurable ingredient, multiple scolding tin particles, multiple spacers that fusing point is 250 DEG C or more.
In conductive paste of the invention, the average grain diameter of above-mentioned spacer is bigger than the average grain diameter of above-mentioned scolding tin particle.
In conductive paste of the invention, using the above structure, therefore, between being electrically connected electrode, Ke Yigao Interval of the precision ground between coordination electrode.In addition, being substantially ensured up and down when concentrating on scolding tin particle between electrode using spacer The interval of electrode, thus, it is easy to can have multiple scolding tin particles between multiple scolding tin particles are concentrated on electrode opposite to each other up and down It is configured on electrode (line) to effect.In addition, a part of multiple scolding tin particles be not easy to be configured at do not formed electrode region ( Every), the amount for being configured at the scolding tin particle in the region for not forming electrode can be largely reduced.It is thus possible to improve interelectrode Reliability is connected.Furthermore, it is possible to prevent interelectrode electrical connection adjacent on not attachable transverse direction, and insulation can be improved Reliability.In the present invention, by cooperating spacer, scolding tin particle can be efficiently configured on electrode.In addition, of the invention In, do not cooperate spacer only, and the average grain diameter of spacer and scolding tin particle is set to specific range, it therefore, can Scolding tin particle to be efficiently configured on electrode.The use of spacer with specific average grain diameter substantially facilitates to connect The amount of the upper and lower interelectrode scolding tin connect and the raising for configuring precision.
Bigger than the average grain diameter of above-mentioned scolding tin particle by the average grain diameter of above-mentioned spacer, scolding tin particle moves on the electrode When dynamic, ensure that scolding tin particle is able to carry out mobile interval between the first connecting object component and the second connecting object component, Promote the movement of scolding tin particle.As a result, the interelectrode scolding tin quantitative change above and below being configured at is more, and therefore, interelectrode conducting Reliability improves.
In addition, finding in the present invention, by the use of spacer, spacer is not only facilitated between limitation upper/lower electrode Every, and spacer helps to improve the coherency of scolding tin particle.
Also, in the present invention, interelectrode location dislocation can be prevented.In the present invention, it is being coated with the of conductive paste When being overlapped the second connecting object component on one connecting object component, even if connecting with the electrode of the first connecting object component and second Connect the electrode of object Part calibration misplace in the state of, the first connecting object component and the second connecting object component overlapping In the case where, the dislocation can also be corrected, the electrode of electrode and the second connecting object component to the first connecting object component connects Connect (self calibration effect).
In addition, the use of have not being the substrate particle formed by scolding tin and the scolding tin on the surface for being configured at substrate particle In the case that the electroconductive particle of layer is without the use of above-mentioned scolding tin particle, electroconductive particle is not easy to concentrate on electrode, electric conductivity The mutual scolding tin zygosity of particle is lower, and therefore, the electroconductive particle moved on the electrode is be easily moved to outside electrode.Therefore, The inhibitory effect of interelectrode location dislocation also reduces.
In order to which scolding tin particle is further efficiently configured on electrode, viscosity (η of the above-mentioned conductive paste at 25 DEG C It 25) is preferably 10Pas or more, more preferably 50Pas or more, further preferably 100Pas or more, preferably 800Pas hereinafter, more preferably 600Pas hereinafter, further preferably 500Pas or less.
Above-mentioned viscosity (η 25) can be according to the type and use level appropriate adjustment of gradation composition.In addition, being made by filler With viscosity can be made higher.
Above-mentioned viscosity (η 25) can be used such as E type viscosimeter (Toki Sangyo Co., Ltd.'s manufacture)
It is measured under conditions of 25 DEG C and 5rpm.
Conductive paste of the invention can be preferred for the system of aftermentioned connection structural bodies of the invention and connection structural bodies Make method.
From the viewpoint of it is further improve conducting reliability, above-mentioned conductive paste is to above-mentioned first electrode and above-mentioned When second electrode is electrically connected, it is heated to the solidification temperature of the fusing point of above-mentioned scolding tin particle or more and above-mentioned Thermocurable ingredient More than, make multiple above-mentioned scolding tin particle coacervations and integration uses.By the integration of multiple scolding tin particles, more large area is formed Solder sections.In 1 solder sections, integration preferably is carried out to more than two scolding tin particles in conductive paste, more preferably Integration is carried out to 3 or more scolding tin particles in conductive paste, further preferably to 5 s' or more in conductive paste Scolding tin particle has carried out integration.
Above-mentioned conductive paste is preferred for the electrical connection of electrode.Above-mentioned conductive paste is preferably circuit connection material.
Hereinafter, illustrating 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 the central part of above-mentioned scolding tin particle and the outer surface of electric conductivity is The particle of scolding tin.
From the viewpoint of effectively concentrating scolding tin particle on the electrode, the zeta potential of above-mentioned scolding tin particle surface is preferably Just.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:
By being put into methanol 10g by scolding tin particle 0.05g and carrying out ultrasonication etc., it is uniformly dispersed it, is obtained To dispersion liquid.It, can be at 23 DEG C using the dispersion liquid, and using Beckman Coulter company manufacture " Delsamax PRO " Zeta potential is measured by electrophoresis assays down.
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 that the adjustment of the zeta potential on surface is positive, above-mentioned scolding tin particle preferably have scolding tin particle main body and The anionic polymer being configured in above-mentioned scolding tin particle body surfaces.Above-mentioned scolding tin particle is preferably by anionic polymerisation Object or compound as anionic polymer, which are surface-treated scolding tin particle main body, to be obtained.Above-mentioned scolding tin particle is preferred The surface treatment carried out for the compound by anionic polymer or as anionic polymer.Above-mentioned anionic polymer and Compound as 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- The method that object is reacted as anionic polymer, the hydroxyl of the carboxyl and scolding tin particle body surfaces that make anionic polymer is closed, The polymer is (methyl) acrylate copolymer made of for example closing (methyl) acrylic acid copolymer, by dicarboxylic acids and glycol conjunction At and two ends there are the polyester polymers of carboxyl, obtained by the intermolecular dehydration condensation of dicarboxylic acids and two ends have There is the polymer of carboxyl, synthesized by dicarboxylic acids and diamines and polyester polymers of two ends with carboxyl and changing with carboxyl Property polyvinyl alcohol (Japan synthesis Chemical Co., Ltd. manufacture " GOHSENX T ") 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 sulfonate ion group (- SO3 -), phosphate anion 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 adjustment on the surface of scolding tin particle to be positive, scolding tin particle can be made further It is efficiently configured on electrode.
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 as anionic polymer to scolding tin particle main body Weight average molecular weight can acquire as follows, dissolve scolding tin particle in scolding tin, utilize will not cause polymer decompose dilute hydrochloric acid Then the weight average molecular weight of remaining polymer is measured Deng scolding tin particle is removed.
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 is preferably molten Point is 450 DEG C of metallics (low-melting-point metal particle) below.Above-mentioned low-melting-point metal particle is containing low-melting-point metal Particle.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 excellent It is selected as 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 Content is preferably 30 weight % or more, more preferably 40 weight % or more, further preferably 70 weight % or more, particularly preferably For 90 weight % or more.The content of tin in above-mentioned scolding tin particle be above-mentioned lower limit more than when, further improve solder sections with The connection reliability of electrode.
In addition, the content of above-mentioned tin can utilize high-frequency inductive coupling plasma body emission spectrographic analysis device (Co., Ltd. Hole field production manufactured " ICP-AES ") or the fluorescent x-ray analyzer (" EDX- of Shimadzu Scisakusho Ltd's manufacture 800HS ") etc. be measured.
By using above-mentioned scolding tin particle, scolding tin carries out melting and electrode engagement, and solder sections make to be connected between electrode.Example Such as, solder sections and electrode are easy to carry out face contact without point contact, and therefore, connection resistance reduces.In addition, passing through scolding tin grain The bond strength of the use of son, solder sections and electrode is got higher, as a result, it is further not likely to produce the removing of solder sections and electrode, And effectively improve conducting reliability and connection reliability.
The metal (low-melting-point metal) for constituting above-mentioned scolding tin particle is not particularly limited.The low-melting-point metal be preferably tin, Or the alloy containing tin.The alloy can be enumerated: tin-silver alloy, tin-copper alloy, tin-silver-copper alloy, tin-bismuth alloy electroplating, tin-zinc Alloy, Sn-In alloy etc..Since the wetability to electrode is excellent, above-mentioned low-melting-point metal is preferably tin, Xi-silver conjunction Gold, tin-silver-copper 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 perspective 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 perspective 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 less than 80 μm, still more preferably for 75 μm hereinafter, It is still more preferably 60 μm hereinafter, being still more preferably 40 μm hereinafter, being still more preferably 30 μm hereinafter, further excellent Be selected as 20 μm hereinafter, particularly preferably 15 μm hereinafter, most preferably 10 μm or less.The average grain diameter of above-mentioned scolding tin particle is above-mentioned When more than lower limit and below the above-mentioned upper limit, scolding tin particle can be further efficiently configured on electrode.Above-mentioned scolding tin grain The average grain diameter of son is particularly preferably 3 μm or more and 30 μm or less.
" average grain diameter " of above-mentioned scolding tin particle indicates number average particle diameter.The average grain diameter of scolding tin particle passes through using for example Electron microscope or any 50 scolding tin particles of optical microphotograph sem observation, and calculate average value or carry out laser diffraction formula granularity point Cloth is measured and is acquired.
The coefficient of alteration of the partial size of above-mentioned scolding tin particle is preferably 5% or more, and more preferably 10% or more, preferably 40% Hereinafter, more preferably 30% or less.It, can be with when the coefficient of alteration of above-mentioned partial size is above-mentioned lower limit or more and the above-mentioned upper limit or less It is efficiently configured to scolding tin particle further on electrode.But the coefficient of alteration of the partial size of above-mentioned scolding tin particle can also be with Lower than 5%.
Above-mentioned coefficient of alteration (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 80 weight % hereinafter, more preferably 60 weight % hereinafter, further preferably 50 weight % or less.Above-mentioned scolding tin When the content of particle is above-mentioned lower limit or more and the above-mentioned upper limit or less, scolding tin particle can be made further to be efficiently configured to electricity It on extremely, is easy between scolding tin particle is largely configured at electrode, and further improves conducting reliability.It is led from further raising From the perspective of logical 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, improved from further From the perspective of reliability is connected, in above-mentioned 100 weight % of conductive paste, the content of above-mentioned scolding tin particle is preferably 20 weight % More than, more preferably 30 weight % or more, preferably 55 weight % are hereinafter, more preferably 45 weight % or less.
Do not formed the interval of part of electrode (S) be 50 μm more than or lower than 150 μm in the case where, from further From the perspective of improving 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 mentioning From the perspective 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.
Do not formed the interval of part of electrode (S) be 150 μm more than or lower than 1000 μm in the case where, Cong Gengjin mono- From the perspective of step improves conducting reliability, in above-mentioned 100 weight % of conductive paste, the content of above-mentioned scolding tin particle is preferably 30 Weight % or more, more preferably 40 weight % or more, preferably 70 weight % are hereinafter, more preferably 60 weight % or less.
(spacer)
Above-mentioned spacer preferably with above-mentioned first connecting object component and above-mentioned this both sides' phase of second connecting object component The mode connect uses.Therefore, conductive paste of the invention is preferably with above-mentioned spacer and above-mentioned first connecting object component and upper The mode that second connecting object component this both sides connect is stated to use.Above-mentioned spacer preferably with above-mentioned first connecting object component Above-mentioned first electrode (region equipped with above-mentioned first electrode) and the above-mentioned second electrode of above-mentioned second connecting object component (set Having the region of above-mentioned second electrode) mode that connects of this both sides uses.Above-mentioned spacer with above-mentioned first further preferably to connect pair As component the region for being not provided with above-mentioned first electrode and above-mentioned second connecting object component be not provided with it is above-mentioned second electricity The mode that this both sides of the region of pole connect uses.When being conductively connected, by the way that scolding tin is concentrated on interelectrode effect, it is spaced Object is easy to mobile to the region of not set electrode.On the other hand, above-mentioned spacer is configured between electrode sometimes.
The fusing point of above-mentioned spacer is 250 DEG C or more.In the electrical connection of first electrode and second electrode, set higher Fusing point melts above-mentioned spacer not.The upper limit of the fusing point of above-mentioned spacer is not particularly limited.The fusing point of above-mentioned spacer It can be 400 DEG C or less.
From the viewpoint of the melting for further preventing spacer, the fusing point of above-mentioned spacer is preferably 300 DEG C or more, More preferably 350 DEG C or more.
Above-mentioned spacer can be resin particle.It as the material of resin particle, such as can enumerate: polyolefin resin, third Olefin(e) acid resin, phenolic resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturation Polyester resin, polyethylene terephthalate, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyethers ether Ketone, polyether sulfone, divinyl benzene polymers and vinyl benzene-styrol copolymer or divinylbenzene-(methyl) acrylate Divinylbenzenes analog copolymer such as copolymer etc..The hardness of above-mentioned resin particle can easily be controlled into range appropriate, because This, the material of above-mentioned resin particle is preferably the one or more kinds of polymerizations for the polymerizable monomer for making to have olefinic unsaturated group Made of polymer.Particularly preferably divinyl benzene polymers, polyimides or polyamidoimide.
In addition, the material as above-mentioned spacer can also be enumerated other than resin: silica, glass, quartz, Silicon, metal and metal oxide etc..The material of above-mentioned spacer can not be metal.The material of above-mentioned spacer is preferably set Rouge, more preferably divinylbenzene analog copolymer.Above-mentioned divinylbenzene analog copolymer for example contains divinylbenzene as altogether Polymeric composition.
Sometimes configuration space object between the electrode abutted in the transverse direction, therefore, from further raising insulating reliability Viewpoint is set out, and above-mentioned spacer is preferably insulating properties particle.
The average grain diameter of above-mentioned spacer is preferably 10 μm or more, more preferably 20 μm or more, further preferably 25 μm More than, preferably 100 μm hereinafter, more preferably 75 μm hereinafter, still more preferably be 50 μm or less.Above-mentioned spacer is averaged When partial size is above-mentioned lower limit or more and the above-mentioned upper limit or less, can the further accurately interval between coordination electrode, and can Scolding tin particle to be further efficiently configured on electrode.
" average grain diameter " of above-mentioned spacer indicates number average particle diameter.The average grain diameter of spacer, which passes through, utilizes such as electronics Microscope or any 50 spacers of optical microphotograph sem observation, and calculate average value or carry out the measurement of laser diffraction formula size distribution And it acquires.
From between accurately coordination electrode, and from the perspective of scolding tin is efficiently configured on electrode, above-mentioned spacer Average grain diameter it is bigger than the average grain diameter of above-mentioned scolding tin particle.
From further accurately between coordination electrode, and scolding tin is further efficiently configured to the viewpoint on electrode It sets out, the ratio between average grain diameter of the average grain diameter of above-mentioned spacer and above-mentioned scolding tin particle (average grain diameter of spacer/scolding tin grain The average grain diameter of son) it is preferably 1.1 or more, more preferably 1.5 or more, further preferably 2 or more, preferably 15 hereinafter, more Preferably 10 hereinafter, further preferably 8 or less.From further accurately controlling electrode, and more by scolding tin From the perspective of being effectively further configured on electrode, the average grain diameter of above-mentioned spacer is relative to the flat of above-mentioned scolding tin particle The ratio (average grain diameter of spacer/scolding tin particle average grain diameter) of equal partial size is preferably 1.0 or more, and more preferably 1.5 or more, Preferably 15 hereinafter, more preferably 10 or less.
The coefficient of alteration of the particle diameter of above-mentioned spacer is preferably 3% or more, and more preferably 5% or more, preferably 30% Hereinafter, more preferably 20% or less.It, can be with when the coefficient of alteration of above-mentioned particle diameter is above-mentioned lower limit or more and the above-mentioned upper limit or less Interval between further accurately coordination electrode.
Above-mentioned coefficient of alteration (CV value) following formula indicates.
CV value (%)=(ρ/Dn) × 100
ρ: the standard deviation of the particle diameter of spacer
Dn: the average value of the particle diameter of spacer
From further accurately between coordination electrode, and scolding tin is further efficiently configured to the viewpoint on electrode Set out, the content (in 100 weight % of conductive paste) in terms of weight % unit of above-mentioned scolding tin particle and above-mentioned spacer with (content (weight %)/spacer of scolding tin particle contains the ratio between content (in 100 weight % of conductive paste) of weight % unit meter Measure (weight %)) it is preferably 2 or more, more preferably 5 or more, further preferably 10 or more, preferably 100 hereinafter, more preferably For 80 hereinafter, further preferably 70.
From further accurately controlling electrode, and scolding tin is further efficiently configured on electrode From the perspective of, the 10%K value (modulus of elasticity in comperssion when 10% compression) of above-mentioned spacer is preferably 2000N/mm2Above more Preferably 3500N/mm2More than, preferably 8000N/mm2Hereinafter, more preferably 6000N/mm2Below.In addition, above-mentioned spacer 10%K value when being above-mentioned lower limit or more and the above-mentioned upper limit or less, can this be double in spacer and first electrode and second electrode After side connects, prevents the transition of spacer mobile, the cohesion of scolding tin particle can also be promoted, prevent first electrode and second electrode Location dislocation, and conducting reliability can be improved.
The 10%K value of above-mentioned spacer can be such as following measurement.
It is right with the smooth pressure head end face of cylinder (50 μm of diameter, diamond fabrication) at 25 DEG C using micro-compression tester Maximum test load 90mN compresses spacer under conditions of carrying out load 30 seconds.Measure load value (N) at this time and compression displacement (mm).It, can be in the hope of modulus of elasticity in comperssion by following formula according to obtained measured value.As above-mentioned micro-compression tester, example " the Fischer scope H-100 " of the manufacture of Fischer Co., Ltd. such as can be used.
K value (N/mm2)=(3/21/2)·F·S-3/2·R-1/2
F: spacer carries out the load value (N) when 10% compressive deformation
S: spacer carries out the compression displacement (mm) when 10% compressive deformation
R: the radius (mm) of spacer
From further accurately controlling electrode, and scolding tin is further efficiently configured on electrode From the perspective of, the compression recovery of above-mentioned spacer is preferably 30% or more, more preferably 40% or more, preferably 80% with Under, more preferably 70% or less.In addition, the compression recovery of above-mentioned spacer is above-mentioned lower limit or more and the above-mentioned upper limit or less When, the transition of spacer can be prevented mobile, can also be promoted after spacer and first electrode and second electrode this both sides connect Into the cohesion of scolding tin particle, to prevent the location dislocation of first electrode and second electrode, and conducting reliability can be improved.
Above-mentioned compression recovery can be such as following measurement.
Spacer is spread on sample table.The spacer spread for 1 is (straight with cylinder using micro-compression tester 100 μm of diameter, diamond fabrication) smooth pressure head end face, assign load (reversion load along the center position of spacer at 25 DEG C Value), until 40% compressive deformation occurs for spacer.Then, it carries out except lotus is until origin load value (0.40mN).It can measure Load-compression displacement of this period, and compression recovery is acquired according to the following formula.In addition, load speed is set as 0.33mN/ seconds.Make For above-mentioned micro-compression tester, such as usable Fischer Co., Ltd. manufacture " Fischer scope H-100 " etc..
Compression recovery (%)=[(L1-L2)/L1] × 100
L1: the compression displacement from origin load value when assigning load until inverting load value
L2: lotus displacement is removed from rebound load value when discharging load until origin load value
In above-mentioned 100 weight % of conductive paste, the content of above-mentioned spacer is preferably 0.1 weight % or more, more preferably 0.5 weight % or more, further preferably 1 weight % or more, preferably 10 weight % hereinafter, more preferably 5 weight % hereinafter, Further preferably 4 weight % are hereinafter, particularly preferably 3 weight % or less.The content of above-mentioned spacer is above-mentioned lower limit or more And when below the above-mentioned upper limit, further accurately interelectrode interval can be controlled, can on the electrode more into One step effectively configures scolding tin particle, is easy between electrode largely to configure scolding tin particle, and conducting reliability further improves.
(Thermocurable compound: Thermocurable ingredient)
Above-mentioned Thermocurable compound is by heating curable compound.It, can as above-mentioned Thermocurable compound It enumerates: oxetane compound, epoxide, episulfide compound, (methyl) acyclic compound, phenol chemical combination Object, amino-compound, unsaturated polyester compound, urethanes, polysiloxane compound and polyimide compound etc.. From the viewpoint of the curability and viscosity for making conductive paste further good and further raising connection reliability, preferably For epoxide.
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.Impact resistance is improved from further From the perspective of property, the content of above-mentioned Thermocurable ingredient is The more the better.
(thermal curing agents: Thermocurable ingredient)
Above-mentioned thermal curing agents make above-mentioned Thermocurable compound heat cure.As above-mentioned thermal curing agents, can enumerate: imidazoles is solid The polythiol hardeners such as agent, amine hardener, phenol cured agent, polythiol curing agent, acid anhydrides, hot cationic initiator (heat sun from Sub- curing agent) and hot radical producing agent etc..Above-mentioned thermal curing agents can be used alone, can also be applied in combination two kinds with On.
Conductive paste can be made further rapidly to solidify at low temperature, it is therefore preferable that imidazole curing agent, thiol-cured Agent or amine hardener.In addition, when mixing is by the curable curability compound of heating and above-mentioned thermal curing agents, storage stability It gets higher, it is therefore preferable that being latent curing agent.Latent curing agent is preferably that latency imidazole curing agent, latency mercaptan are solid Agent or latency amine hardener.In addition, above-mentioned thermal curing agents can be by the polymer of polyurethane resin or polyester resin etc. Matter 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..
It is not particularly limited, can enumerate as above-mentioned polythiol curing agent: trimethylolpropane tris -3- mercaptopropionic acid Six -3-thiopropionate of ester, four -3-thiopropionate of pentaerythrite and dipentaerythritol 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 Sulphur cationoid curing agent etc..As above-mentioned iodine cationoid curing agent, bis- (4- tert-butyl-phenyl) iodine six can be enumerated Fluorophosphate etc..As above-mentioned oxygen cationoid curing agent, trimethyl oxygen tetrafluoroborate etc. can be enumerated.As above-mentioned sulfonium Cationoid 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 it is efficiently configured on electrode.The reaction start temperature of above-mentioned thermal curing agents is particularly preferably 80 DEG C or more and 140 DEG C or less.
From the viewpoint of further being efficiently configured on electrode by scolding tin, the reaction of above-mentioned thermal curing agents starts temperature The fusing point spent preferably than above-mentioned scolding tin particle is high, more preferably high 5 DEG C or more, further preferably high 10 DEG C or more.
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 used for solidifying after hardening Remaining thermal curing agents be not easy to remain, and further improve solidfied material heat resistance.
(fluxing agent)
Above-mentioned conductive paste preferably comprises fluxing agent.By the use of fluxing agent, scolding tin can be made further effectively It is configured on electrode.As fluxing agent, the fluxing agent commonly used in scolding tin combination 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.
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, further improving interelectrode conducting can By property.
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 improved.
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 made further to be efficiently configured to 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 further being efficiently configured on electrode by scolding tin, the fusing point of above-mentioned fluxing agent is preferably than upper The fusing point for stating 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 further being efficiently configured on electrode by scolding tin, the fusing point of above-mentioned fluxing agent is preferably than upper The reaction start temperature for stating 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, connection in the case where assigning heat in engagement, to the electrode and electrode perimeter that are formed on connecting object component When the part of object Part is compared, the heat of the connecting object component part of the thermal conductivity ratio electrode perimeter of electrode section is passed Conductance is high, causes being rapidly heated for electrode section as a result,.It is being more than the stage of the fusing point of scolding tin particle, the inside of scolding tin particle Dissolution, but the oxide film thereon for being formed in surface does not reach the fusing point (active temperature) of fluxing agent, it is thus impossible to be removed.At this Under state, the temperature of electrode section first reaches the fusing point (active temperature) of fluxing agent, therefore, can be preferentially on self-electrode in future The oxide film thereon on the surface of scolding tin particle removes, and scolding tin particle moistens diffusion on the surface of electrode.Thus, it is possible to make scolding tin grain Son is effectively agglomerated on electrode.
Above-mentioned fluxing agent can also 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 by using based on heating Fluxing agent, scolding tin particle can be made further to be efficiently configured on electrode.
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 further be removed effectively.
(filler)
Filler can be added in above-mentioned conductive paste.Filler can be organic filler, be also possible to inorganic filler.By filling out The addition of material, the distance that scolding tin particle can be inhibited to agglomerate, and make scolding tin particle on the entire electrode of substrate equably Cohesion.
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 has: on surface at least one first electrode the first connecting object component, The second connecting object component on surface at least one second electrode, by above-mentioned first connecting object component and above-mentioned second The interconnecting piece that connecting object component links together.In connection structural bodies of the invention, above-mentioned interconnecting piece is by above-mentioned electroconductive paste Dosage form is at being the solidfied material of above-mentioned conductive paste.In connection structural bodies of the invention, the material of above-mentioned interconnecting piece is above-mentioned Conductive paste.In connection structural bodies of the invention, above-mentioned first electrode and above-mentioned second electrode pass through the weldering in above-mentioned interconnecting piece Tin portion is electrically connected.Preferably this is double with above-mentioned first connecting object component and above-mentioned second connecting object component for above-mentioned spacer Side's contact.
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, and make 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 More than the fusing point of particle and more than the solidification temperature of above-mentioned Thermocurable ingredient, formed using above-mentioned conductive paste by above-mentioned first The interconnecting piece that connecting object component and above-mentioned second connecting object component link together, and pass through the scolding tin in above-mentioned interconnecting piece The process that portion is electrically connected above-mentioned first electrode and above-mentioned second electrode.It is preferred that connecting above-mentioned spacer with above-mentioned first Object Part and this both sides of above-mentioned second connecting object component contact.
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 be by multiple scolding tin particles effectively It is configured on electrode (line).In addition, a part of multiple scolding tin particles is not easy to be configured at the region (interval) for not forming electrode, The amount for the scolding tin particle for being configured at the region for not forming electrode can be made considerably less.It is thus possible to improve first electrode and Conducting reliability between two electrodes.Furthermore, it is possible to being electrically connected between preventing the adjacent electrode on the transverse direction that cannot be attached It connects, insulating reliability can be improved.
From the viewpoint of further raising conducting reliability, to above-mentioned first electrode and the progress of above-mentioned second electrode When electrical connection, it is preferably heated to the solidification temperature of the fusing point of above-mentioned scolding tin particle or more and above-mentioned Thermocurable ingredient or more, is made Multiple above-mentioned scolding tin particle coacervations and integration.
In addition, it was found by the inventors of the present invention that in order to which multiple scolding tin particles are efficiently configured on electrode, and make to configure It is considerably less in the amount of the scolding tin particle in the region for not forming electrode, conductive film is not used, and need using conductive paste.
In the present invention, interelectrode other methods effectively further can be concentrated on using by multiple scolding tin particles.Make For multiple scolding tin particles are effectively concentrated interelectrode method, the following methods can be used: to the first connecting object component and When conductive paste between second connecting object component assigns heat, the viscosity of conductive paste is reduced by heat, generates the as a result, The convection current etc. of conductive paste between one connecting object component and the second connecting object component.It in this method, can enumerate: pass through company The method for connecing the difference of the thermal capacity between the electrode and surface elements in addition to this on object Part surface and generating convection current；It is logical Overheat the method that vapor is made in the moisture of connecting object component and generates convection current；And by the first connecting object component and Temperature difference between second connecting object component generates the method etc. of convection current.Thus, it is possible to make the scolding tin particle in conductive paste Effectively it is moved to electrode surface.
It, can be further using the method agglomerated with making scolding tin particle selection in electrode surface in the present invention.As making Agglomerate to scolding tin particle selection the method in electrode surface, can enumerate: selection is good by the wettability of the scolding tin particle melted Electrode material and melting scolding tin particle wettability difference the connecting object component that is formed of other Facing materials, and make to reach It is attached to the scolding tin particle selection of the melting of electrode surface electrode, relative to the scolding tin particle of the melting, makes other scolding tin Pellet melting and the method adhered to；Select other Facing material shapes by the good electrode material of heat conductivity and heat conductivity difference At connecting object component, assign heat when, electrode temperature is increased relative to other surface elements, as a result, selecting property in electrode The method of upper choosing melting scolding tin；Using treated scolding tin particle, make scolding tin particle relative in the electrode formed by metal Present on negative electrical charge have positive charge, agglomerate in the method on electrode with making scolding tin particle selection；And relative to having Resin other than scolding tin particle in conductive paste is set as hydrophobicity, makes scolding tin grain as a result, by the electrode on hydrophilic metal surface Son is selectively agglomerated 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 forms the two works of the process of above-mentioned interconnecting piece In sequence, the pressure of pressurization is lower than
1MPa.The pressure pressurizeed by not applying 1MPa or more, can promote the cohesion of scolding tin particle.From inhibition connecting object From the perspective of the warpage of component, in the manufacturing method of connection structural bodies of the invention, above-mentioned second connection pair can configured As pressurizeing at least one process in the process of component and the process of the above-mentioned interconnecting piece of formation, and in configuration above-mentioned second It the process of connecting object component and is formed in the two processes of the process of above-mentioned interconnecting piece, the pressure of pressurization is lower than 1MPa.Into In the case where row pressurization, can only it pressurize in the process for configuring above-mentioned second connecting object component, it can also be only in shape It pressurizes, in the process for configuring above-mentioned second connecting object component and can also be formed above-mentioned in process at above-mentioned interconnecting piece In the two processes of the process of interconnecting piece, pressurize.It includes non-pressurized situation in 1MPa that the pressure of pressurization, which is lower than,.Carry out In the case where pressurization, the pressure of pressurization is preferably 0.9MPa hereinafter, more preferably 0.8MPa or less.It is in the pressure of pressurization In 0.8MPa situation below, compared with the case where pressure of pressurization is more than 0.8MPa, further promote scolding tin grain significantly The cohesion of son.
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.And it is possible to the thickness of solder sections is further effectively thickened, It is easy to concentrate on multiple scolding tin particles largely between electrode, multiple scolding tin particles can be further efficiently configured to electrode On (line).In addition, a part of multiple scolding tin particles is not easy to be configured at the region (interval) for not forming electrode, it can be more into one Step reduces the amount for being configured at the scolding tin particle in the region for not forming 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 Without pressurization in the process of socket part, and apply the weight of above-mentioned second connecting object component to above-mentioned conductive paste, then in shape Before interconnecting piece, be configured at do not formed the region (interval) of electrode scolding tin particle be further easy to concentrate on first electricity Between pole and second electrode, multiple scolding tin particles can be further efficiently configured on electrode (line).In the present invention, group It closes and is of great significance using following constitute to obtaining effect of the invention: using the composition of conductive paste, without the use of leading Electrolemma applies the composition of the weight of above-mentioned second connecting object component to above-mentioned conductive paste, and without pressurization.
In addition, in WO2008/023452A1, describes from along electrode surface pushing solder powder and move with being effective Viewpoint is set out, and can be pressurizeed in welding with specified pressure, and describe from the sight that soldering tin is formed more reliably Point sets out, and 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 There is no record for the difference of the case where pressure and effect the case where be adjusted to 0MPa.In addition, in WO2008/023452A1, It is not membranaceous but the importance of the conductive paste of paste does not have any understanding to using.
In addition, if not using conductive film, and use conductive paste, then it is easy the coating weight according to conductive paste, adjustment The thickness of interconnecting piece and solder sections.On the other hand, there are the following problems in conductive film: for the thickness of variations or modifications interconnecting piece Degree, it is necessary to prepare the conductive film of different-thickness or prepare the conductive film of specified thickness.In addition, there are the following problems in conductive film: Under the melting temperature of scolding tin, the melt viscosity of conductive film cannot be made sufficiently to reduce, to 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 cuing open for the connection structural bodies obtained using the conductive paste of one embodiment of the present invention View.
Connection structural bodies 1 shown in FIG. 1 has: the first connecting object component 2, the second connecting object component 3 connect first Connect the interconnecting piece 4 that object Part 2 and the second connecting object component 3 link together.Interconnecting piece 4 is by containing Thermocurable chemical combination Object, thermal curing agents, multiple scolding tin particles and multiple spacers 5 conductive paste formed.Above-mentioned Thermocurable compound and above-mentioned Thermal curing agents are Thermocurable ingredient.
Solder sections 4A made of there are interconnecting piece 4 multiple scolding tin particles to concentrate and be interconnected, keep Thermocurable ingredient hot The solidfied material portion 4B and spacer 5 being solidified to form.
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 realizes electricity by solder sections 4A Connection.Therefore, the first connecting object component 2 and the second connecting object component 3 realize electrical connection by solder sections 4A.In addition, In interconnecting piece 4, in region (the solidfied material portion 4B different from the solder sections 4A concentrated between first electrode 2a and second electrode 3a Part) in, scolding tin is not present.In the region (solidfied material portion 4B part) different from solder sections 4A, there is no be detached from solder sections The scolding tin of 4A.In addition, if being on a small quantity, then scolding tin be can reside in and be concentrated between first electrode 2a and second electrode 3a Solder sections 4A different regions (the solidfied material portion part 4B).
The second electrode 3a of the first electrode 2a and the second connecting object component 3 of spacer 5 and the first connecting object component 2 This both sides connects.Using spacer 5, the interval of the first connecting object component 2 and the second connecting object component 3 is limited, and is limited The interval of first electrode 2a and second electrode 3a.Spacer 5 can be with the first electrode that is not provided with the first connecting object component 2 It the region of 2a and is not provided with the two regions of the region of second electrode 3a of the second connecting object component 3 and connects.
As shown in Figure 1, multiple scolding tin particles are assembled between first electrode 2a and second electrode 3a in connection structural bodies 1, After multiple scolding tin pellet meltings, the fusant wetting electrode surface of scolding tin particle simultaneously solidifies after spreading, so as to form scolding tin Portion 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, passing through Use scolding tin particle, compared 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, scolding tin The contact area of portion 4A and first electrode 2a and solder sections 4A and second electrode 3a becomes larger.Therefore, in connection structural bodies 1 Reliability is connected and connection reliability improves.In addition, conductive paste can contain fluxing agent.Using fluxing agent, In general, fluxing agent can gradually be inactivated due to 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, solidfied material portion 4XB and spacer 5X.It can be a large amount of to weld as connection structural bodies 1X Tin portion 4XA is located at the opposed region first electrode 2a, second electrode 3a, and a part of solder sections 4XA is from first electrode 2a, second Expose to side in electrode 3a opposed region.The scolding tin that the region opposed from first electrode 2a and second electrode 3a is exposed to side Portion 4XA is a part of solder sections 4XA, is not the scolding tin for being detached from solder sections 4XA.In addition, in present embodiment, it is possible to reduce de- The amount of scolding tin from 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.As long as scolding tin can also be in addition, scolding tin moistens diffusion on the surface of electrode It not necessarily concentrates between upper and lower electrode.
Furthermore it is possible to which connection structural bodies 1Y as shown in Figure 4 is such, connected using the first connecting object component 2Y and second The surface of object Part 3Y, the first connecting object component 2Y have first electrode 2a, and do not have in the side first electrode 2a The region of first electrode 2a has the first protrusion 2y, and the surface of the second connecting object component 3Y has second electrode 3a, and There is the second protrusion 3y in the region without second electrode 3a of the side second electrode 3a.First protrusion 2y is more prominent than first electrode 2a Out.Second protrusion 3y is more prominent than second electrode 3a.The interval of first protrusion 2y and the second protrusion 3y are than first electrode 2a and The interval of two electrode 3a is narrow.In connection structural bodies 1Y, interconnecting piece 4Y has solder sections 4YA, solidfied material portion 4YB and spacer 5Y.In connection structural bodies 1Y, spacer 5Y and the first protrusion 2y and second protrusion 3y this both sides are contacted.As a result, the first electricity The interval of pole 2a and second electrode 3a are limited by spacer 5Y.
From the viewpoint of it is further improve conducting reliability, along above-mentioned first electrode, above-mentioned interconnecting piece and above-mentioned When the stack direction of second electrode observes above-mentioned first electrode and above-mentioned second electrode opposed part, preferably in above-mentioned first electricity 50% or more (preferably 60% or more, more preferably 70% in the area 100% of pole and the opposed part of above-mentioned second electrode More than, further preferably 80% or more, particularly preferably 90% or more) configured with the solder sections in above-mentioned interconnecting piece.
From the viewpoint of it is further improve conducting reliability, preferably along with above-mentioned first electrode, above-mentioned interconnecting piece The opposite part of above-mentioned first electrode, above-mentioned second electrode is observed with the vertical direction of the stack direction of above-mentioned second electrode When, 70% of the solder sections in above-mentioned interconnecting piece is configured in the above-mentioned first electrode part opposite with above-mentioned second electrode More than.
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, on the surface of the first connecting object component 2 configuration containing Thermocurable ingredient 11B and multiple scolding tin particle 11A, The conductive paste 11 (first step) of spacer 5.It is configured on the surface equipped with first electrode 2a of the first connecting object component 2 Conductive paste 11.After configuring conductive paste 11, scolding tin particle 11A is configured at first electrode 2a (line) and does not form first electrode Region (interval) of 2a the two regions.
It as the configuration method of conductive paste 11, is not particularly limited, the coating using dispenser progress, silk screen can be enumerated Printing and the spraying etc. for passing through 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 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 It is more than the lower temperature in solidification temperature.In the heating, it is present in and does not form the scolding tin particle 11A in the region of electrode and exist (self-coagulation effect) is concentrated between first electrode 2a and second electrode 3a.In present embodiment, using conductive paste, without the use of Conductive film, therefore, conductive paste also have specific composition, and scolding tin particle 11A is between first electrode 2a and second electrode 3a Effectively agglomerate.In addition, scolding tin particle 11A is melted and is be combined with each other.In addition, Thermocurable ingredient 11B carries out heat cure.The knot Fruit forms the first connecting object component 2 of connection and the second connecting object component 3 using conductive paste 11 as shown in Fig. 2 (c) Interconnecting piece 4.Interconnecting piece 4 is formed using conductive paste 11, solder sections 4A is formed by multiple scolding tin particle 11A combination, is passed through Thermocurable ingredient 11B carries out heat cure and forms solidfied material portion 4B.If scolding tin particle 11A is sufficiently moved, from being located at the After the mobile beginning of scolding tin particle 11A between one electrode 2a and second electrode 3a, until scolding tin particle 11A is moved to the first electricity Terminate between pole 2a and second electrode 3a, temperature can not be kept into 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 has Concentrate between first electrode 2a and second electrode 3a to effect.In addition, interconnecting piece 4X have solder sections 4XA, solidfied material portion 4XB and Spacer 5.By the aggregation of scolding tin particle 11A, it is readily extruded spacer 5.When forming interconnecting piece 4, spacer 5 can be with One connecting object component 2 and second this both sides of connecting object component 3 contact.Specifically, when forming interconnecting piece 4, spacer 5 It can be contacted with first electrode 2a and second electrode 3a this both sides.In addition, if in above-mentioned the second step and above-mentioned the third step In at least one party pressurize, then the tendency for the effect for hindering scolding tin particle to concentrate between first electrode and second electrode It gets 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 The state of the calibration dislocation of pole can also repair in the case where being overlapped the first connecting object component and the second connecting object component The just dislocation, and make the electrode connection (self calibration effect) of the electrode and the second connecting object component of the first connecting object component. This is because, between the electrode of the first connecting object component and the electrode of the second connecting object component the melting of self-coagulation weldering In tin, scolding tin and conductive paste between the electrode of the first connecting object component and the electrode of the second connecting object component it is other The smallest energy stabilization of area of ingredient contact, therefore, the connection after becoming the calibration as the connection structure of minimum area The power of structure plays a role.At this point, it is preferred that conductive paste does not carry out solidification and in the temperature, time, the scolding tin grain of conductive paste The viscosity of ingredient other than son is substantially low.
Spacer is present between the first connecting object component and the second connecting object component, it is possible thereby to substantially ensure The distance between the electrode of the electrode of one connecting object component and the second connecting object component.Thus, it can be ensured that scolding tin particle is solidifying Poly- space, and the coherency of scolding tin particle can be improved.Furthermore it is possible to connect in the electrode of the first connecting object component and second Connecing ensures sufficient soldering tin amount between the electrode of object Part, therefore, even if in the case where opposite malposition of electrode overlapping, from Calibration effect is also easy to show.About the magnitude of misalignment of the preferred electrode after conductive connection, the case where electrode width is set as L Under, preferably 0L or more (0 or more), preferably 0.9L are hereinafter, more preferably 0.75L or less.In addition, about excellent after electrical connection The magnitude of misalignment X of choosing, in the case where the particle diameter of spacer is set as R, preferably 0R or more (0 or more), preferably 3R hereinafter, More preferably 2R or less.
The viscosity of conductive paste under the melting temperature of scolding tin is preferably 50Pas hereinafter, more preferably
10Pas hereinafter, further preferably 1Pas hereinafter, preferably 0.1Pas or more, more preferably 0.2Pa S or more.If it is specified viscosity hereinafter, then scolding tin particle can be made effectively to agglomerate, more than specified viscosity, It can inhibit the gap of interconnecting piece, and conductive paste is inhibited to be spilled over to other than interconnecting piece.
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 part with the laminated body of the second connecting object component 3, carries out above-mentioned the third step.It, can in order to carry out above-mentioned heating To configure above-mentioned laminated body on heating element, 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 not particularly limited.Above-mentioned heating temperature is preferably 140 DEG C or more, and more preferably 160 DEG C or more, preferably For 450 DEG C hereinafter, more preferably 250 DEG C hereinafter, further preferably 200 DEG C or less.
Before the third step, in order to make the cohesion homogenization of the scolding tin particle before melting, heating process can be set.On Stating the heating temperature in heating process is preferably 60 DEG C or more, and more preferably 80 DEG C or more, preferably 130 DEG C are hereinafter, more preferably It under the conditions of 120 DEG C of temperature below, preferably remains 5 seconds or more, preferably remains 120 seconds or less.Pass through the heating process, thermosetting The property changed ingredient passes through heat lowering viscousity, scolding tin particle coacervation before melting, thus, it is possible to form eyed structure, and in third When scolding tin pellet melting agglomerates in process, uncongealed scolding tin particle is reduced.
In the third step, preferably more than the fusing point (DEG C) of scolding tin, more preferably+5 DEG C of the fusing point (DEG C) or more of scolding tin is excellent + 20 DEG C of the fusing point (DEG C) of scolding tin is selected as hereinafter, preferably remaining more preferably at+10 DEG C of fusing point (DEG C) temperature below of scolding tin 10 seconds or more, after preferably remaining 120 seconds or less, the solidification temperature of Thermocurable ingredient can be warming up to.Thus, it is possible in thermosetting The property changed ingredient solidify before, in the state that the viscosity of Thermocurable ingredient is lower, the cohesion of end scolding tin particle can carry out The cohesion of further uniform scolding tin particle.
Heating rate in the third step, about the heating from 30 DEG C to the fusing point of scolding tin particle, preferably 50 DEG C/sec with Under, more preferably 20 DEG C/sec hereinafter, further preferably 10 DEG C/sec hereinafter, preferably 1 DEG C/sec or more, more preferably 5 DEG C/ Second or more.When heating rate is above-mentioned lower limit or more, the cohesion of scolding tin particle is further uniform.When heating rate is above-mentioned When below the upper limit, excess stickiness caused by the solidification growth of Thermocurable ingredient is inhibited to rise, is not easy to hinder the solidifying of scolding tin particle It is poly-.
In addition, for the purpose of the repeatability of the amendment of position and manufacture, can be removed from interconnecting piece after above-mentioned the third step First connecting object component or the second connecting object component.Heating temperature for carrying out the removing is preferably the molten of scolding tin particle Or more, 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 + 100 DEG C of fusing point (DEG C) of particle 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, using reflow ovens or use oven, to the method that connection structural bodies is integrally heated, or only partly The method that the interconnecting piece of connection structural bodies is heated.
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 zero such as semiconductor chip, semiconductor packages, 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 The electronic component etc. of the circuit substrates such as glass substrate 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, even if using resin film, flexibility Printed base plate, flexble flat's cable or rigid-flexible combination substrate, can also be such that scolding tin particle effectively collects by using conductive paste In on electrode, to sufficiently improve interelectrode conducting reliability.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.
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 can be the electrode only formed by aluminium, be also possible on the surface of metal oxide layer Electrode made of lamination aluminium layer.It as the material of above-mentioned metal oxide layer, can enumerate: doped with the oxygen of trivalent metallic element Change indium and the zinc oxide etc. doped with trivalent metallic element.It as above-mentioned trivalent metallic element, can enumerate: Sn, Al and Ga etc..
Above-mentioned first electrode and above-mentioned second electrode are preferably with face battle array or periphery configuration.By electrode with face battle array, periphery simultaneously In the case where configuring according to face, effect of the invention is more effectively played.Face battle array is the electrode configuration in connecting object component On face, the structure of electrode is configured to clathrate.Periphery is the structure in the peripheral part configuration electrode of connecting object component.Will be electric In the case where the structure arranged to pole comb type, as long as scolding tin particle is agglomerated along the direction vertical with comb, phase therewith It is right, in above structure, need equably to agglomerate scolding tin particle in the entire surface of configuration electrode, therefore, in the existing method, Soldering tin amount is easy unevenly, in contrast, in method of the invention, more effectively to play effect of the invention.
Hereinafter, enumerating Examples and Comparative Examples, the present invention is specifically described.The present invention is not limited to implementation below Example.
Polymer A:
The reactant (polymer A) of Bisphenol F and 1,6-HD diglycidyl ether and bisphenol f type epoxy resin Synthesis:
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 and (DIC plants of bisphenol f type epoxy resin Formula commercial firm manufactures " EPICLON EXA-830CRP ") 5 parts by weight, (Chemtex plants of Nagase of resorcinol type ring oxygen compound Formula commercial firm manufacture " EX-201 ") 10 parts by weight are put into 3 mouthfuls of flasks, under nitrogen flowing, dissolved with 100 DEG C.Then, conduct is added 0.15 parts by weight of triphenylbut base phosphonium bromide of hydroxyl and the addition reaction catalyst of epoxy group are added under nitrogen flowing with 140 DEG C At polymerization reaction 4 hours, reactant (polymer A) was obtained as a result,.
By NMR, confirmation has carried out polyaddition reaction, further acknowledges that reactant (polymer A) has to come on main chain It is tied made of being bonded from the hydroxyl of Bisphenol F with the epoxy group of 1,6-HD diglycidyl ether and bisphenol f type epoxy resin Structure unit, and there is epoxy group in two ends.
Weight average molecular weight by the obtained reactant (polymer A) of GPC is 28000, and number average molecular weight is 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: resorcinol type ring oxygen compound, Nagase Chemtex Co., Ltd. manufacture " EX- 201”
Thermocurable compound 2: epoxide, Dainippon Ink Chemicals manufacture " EXA-4850-150 ", molecular weight 900, ring Oxygen equivalent 450g/eq
Thermal curing agents 1: trimethylolpropane tris (3-thiopropionate), SC organic chemistry Co., Ltd. manufacture " TMMP "
Latency epoxy thermosetting agent 1:T&KTOKA Co., Ltd. manufactures " Fujicure7000 "
Fluxing agent 1: glutaric acid, Wako Pure Chemical Industries, Ltd.'s manufacture, 96 DEG C of fusing point (active temperature)
The production method of scolding tin particle 1~3:
Scolding tin particle with anionic polymer 1: weigh scolding tin particle main body 200g, adipic acid in three-necked flask 40g, acetone 70g then add 0.3g Dibutyltin oxide as the hydroxyl of scolding tin particle body surfaces and the carboxyl of adipic acid The catalyst for carrying out dehydrating condensation, reacts 4 hours at 60 DEG C.Then, it is recycled by filtering scolding tin particle.
Weigh scolding tin particle, adipic acid 50g, toluene 200g, the p-methyl benzenesulfonic acid 0.3g of recycling 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, select sieve become specified CV value.
(zeta potential measurement)
In addition, obtained scolding tin particle, the scolding tin particle 0.05g with anionic polymer 1 are put into methanol 10g, And ultrasonication is carried out, it is uniformly dispersed as a result, obtains dispersion liquid.Using the dispersion liquid, and use Beckman " the Delsamax PRO " of Coulter company manufacture, measures zeta potential by electrophoresis assays.
(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 scolding tin particle)
CV value utilizes laser diffraction formula particle size distribution device (" LA-920 " of Horiba Ltd's manufacture) It is measured.
Scolding tin particle 1 (SnBi scolding tin particle, 139 DEG C of fusing point, using " ST-3 " that Co., Ltd., Mitsui Metal Co., Ltd. is manufactured into Go scolding tin particle main body obtained from sorting, and the scolding tin particle with surface treated anionic polymer 1, it is average 4 μm of partial size, CV value 7%, the zeta potential on surface :+0.65mV, polymer molecular weight Mw=6500)
Scolding tin particle 2 (SnBi scolding tin particle, 139 DEG C of fusing point, using " DS10 " that Co., Ltd., Mitsui Metal Co., Ltd. is manufactured into Gone sorting scolding tin particle main body, and with surface treated anionic polymer 1 scolding tin particle, average grain diameter 13 μm, CV value 20%, the zeta potential on surface :+0.48mV, polymer molecular weight Mw=7000)
(SnBi scolding tin particle, uses " 10-25 " manufactured to Co., Ltd., Mitsui Metal Co., Ltd. to scolding tin particle 3 by 139 DEG C of fusing point The scolding tin particle main body sorted, and the scolding tin particle with surface treated anionic polymer 1, average grain diameter 25 μm, CV value 15%, the zeta potential on surface :+0.4mV, polymer molecular weight Mw=8000)
Scolding tin particle 4 (SnBi scolding tin particle, 139 DEG C of fusing point, using " ST-3 " that Co., Ltd., Mitsui Metal Co., Ltd. is manufactured into Go scolding tin particle main body obtained from sorting, and the scolding tin particle with surface treated anionic polymer 1, it is average 3 μm of partial size, CV value 7%, the zeta potential on surface :+0.65mV, polymer molecular weight Mw=6500)
Electroconductive particle 1: the layers of copper with a thickness of 1 μm is formed on the surface of resin particle, and on the surface of the layers of copper On be formed with 3 μm of thickness soldering-tin layer (tin: bismuth=43 weight %:57 weight %) electroconductive particle
The production method of electroconductive particle 1:
To (the Sekisui Chemical Co., Ltd's manufacture of 10 μm of average grain diameter of divinylbenzene resin particles " MICROPEARL SP-210 ") process for electroless nickel plating is carried out, 0.1 μm of thickness of substrate nickel plating is formed on the surface of resin particle Layer.Then, electrolytic copper plating is carried out to the resin particle for being formed with substrate nickel coating, forms 1 μm of thickness of layers of copper.It further uses Electrolysis plating solution containing tin and bismuth carries out electrolysis plating, forms 3 μm of thickness of soldering-tin layer.In this way, being produced on resin particle It is formed on surface and is formed with 3 μm of thickness of soldering-tin layer (tin: bismuth=43 on the layers of copper with a thickness of 1 μm and the surface in the layers of copper Weight %:57 weight %) electroconductive particle 1.
Spacer 1 (20 μm of average grain diameter, CV value 5%, 330 DEG C of softening point, Sekisui Chemical Co., Ltd's manufacture, two Vinyl benzene crosslinked particle, 10%K value 4400N/mm2, compression recovery 55%)
Spacer 2 (30 μm of average grain diameter, CV value 5%, 330 DEG C of softening point, Sekisui Chemical Co., Ltd's manufacture, two Vinyl benzene crosslinked particle, 10%K value 4200N/mm2, compression recovery 54%)
Spacer 3 (50 μm of average grain diameter, CV value 5%, 330 DEG C of softening point, Sekisui Chemical Co., Ltd's manufacture, two Vinyl benzene crosslinked particle, 10%K value 4100N/mm2, compression recovery 54%)
Phenoxy resin (Nippon Steel & Sumitomo Metal Corporation manufactures " YP-50S ")
(Examples 1 to 10)
(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).
Glass epoxy substrate and the area of flexible printing substrate overlapping are set as 1.5cm × 3mm, and the number of electrodes of connection is set as 75 It is right.
Be coated using metal mask by silk-screen printing in the upper surface of above-mentioned glass epoxy substrate, formed it is each to Anisotropic electroconductive paste oxidant layer, making the anisotropic conductive paste after just making is 100 μm of thickness on the electrode of glass epoxy substrate. 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, not It pressurizes.Apply the weight of above-mentioned flexible printing substrate to anisotropic conductive paste layer.Then, carrying out heating on one side makes respectively The temperature of anisotropy electroconductive paste oxidant layer becomes 190 DEG C, melts scolding tin on one side, and make anisotropic conductive paste layer at 190 DEG C It is lower solidify within 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 it is same, 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.
(comparative example 1)
Ingredient shown in following table 1 is cooperated with use level shown in following table 1, obtains anisotropic conductive paste Agent.Other than the anisotropic conductive paste used, in the same manner as in Example 1, the first connection structural bodies, the second company are obtained Connect structural body, third connection structural bodies.
(comparative example 2)
Ingredient shown in following table 1 is cooperated with use level shown in following table 1, obtains anisotropic conductive paste Agent.Other than the pressure for applying 1MPa in addition to the anisotropic conductive paste that uses and when heated, in the same manner as in Example 1, Obtain the first connection structural bodies, the second connection structural bodies, third connection structural bodies.
(comparative example 3)
Phenoxy resin (Nippon Steel & Sumitomo Metal Corporation's manufacture " YP-50S ") is set to be dissolved in methyl ethyl ketone (MEK) In, so that solid component is become 50 weight %, obtains lysate.By shown in following table 1 remove phenoxy resin ingredient according to Use level shown in following table 1 and the total amount of above-mentioned lysate are cooperated, using planetary stirring machine with 2000rpm stirring 5 It after minute, is coated on demoulding PET (polyethylene terephthalate) film using rod coater, the thickness after making it dry It is 30 μm.By being dried in vacuo at room temperature, MEK is removed, obtains anisotropic conductive film as a result,.
Other than using anisotropic conductive film, in the same manner as in Example 1, the first connection structural bodies, the second connection are obtained Structural body, third connection structural bodies.
(comparative example 4,5)
Ingredient shown in following table 1 is cooperated with use level shown in following table 1, obtains anisotropic conductive paste Agent.Other than the anisotropic conductive paste used, in the same manner as in Example 1, the first connection structural bodies, the second company are obtained Connect structural body, third connection structural bodies.
(evaluation)
(1) viscosity
Using E type viscosimeter (Toki Sangyo Co., Ltd.'s manufacture), anisotropy is measured under conditions of 25 DEG C and 5rpm Viscosity (η 25) of the conductive paste at 25 DEG C.
(2) thickness of solder sections
Cross-section observation is carried out to obtained connection structural bodies, evaluates the thickness of the solder sections between upper and lower electrode.
(3) self-correcting parasexuality
In addition in the production of third connection structural bodies by the electrode of the electrode of glass epoxy substrate and flexible printing substrate Magnitude of misalignment be set as 25 μm (the 4th connection structural bodies use), 50 μm of (the 5th connection structural bodies use), 75 μm of (the 6th connection structural bodies With), 90 μm (the 7th connection structural bodies with) be overlapped other than, similarly disengaging operation, obtains the 4th~the 7th connection structure Body.
Measure the electrode of the glass epoxy substrate of the 4th~the 7th obtained connection structural bodies and the electricity of flexible printing substrate The magnitude of misalignment of pole.25 the 4th~the 7th connection structural bodies are made, the electrode for being located at each connection structural bodies both ends, measurement are utilized The magnitude of misalignment of upper/lower electrode acquires the average value of its measured value.Self-correcting parasexuality is determined with following benchmark.
00: the average value of magnitude of misalignment is lower than 10 μm
Zero: the average value of magnitude of misalignment is 10 μm or more, is lower than 25 μm
△: the average value of magnitude of misalignment is 25 μm or more, is lower than 50 μm
×: the average value of magnitude of misalignment is 50 μm or more
(4) the configuration precision 1 of the scolding tin on electrode
In obtained the first connection structural bodies, the second connection structural bodies, third connection structural bodies, evaluation is along the first electricity Pole, interconnecting piece and second electrode the stack direction observation first electrode part opposite with second electrode when, first electrode and The ratio X of area in the area 100% of the opposite part of second electrode, in interconnecting piece configured with solder sections.Below State the configuration precision 1 for the scolding tin that benchmark determines on electrode.
[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 the first connection structural bodies, the second connection structural bodies, third connection structural bodies, evaluation is along with first Electrode, the interconnecting piece part opposite with second electrode with the stack direction of second electrode vertical direction observation first electrode When, in the solder sections 100% in interconnecting piece, the weldering that is configured in the interconnecting piece of the first electrode part opposite with second electrode The ratio Y in tin portion.The configuration precision 2 of the scolding tin on electrode is determined with following benchmark.
[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) interelectrode conducting reliability up and down
Obtained the first connection structural bodies, the second connection structural bodies in third connection structural bodies (n=15), pass through four Terminal method is respectively measured the connection resistance of each upper and lower interelectrode connecting portion.Calculate being averaged for connection resistance Value.In addition, a voltage when constant current is flowed through in measurement according to voltage=electric current × resistance relationship, it can be in the hope of connection resistance. Conducting reliability is determined with following benchmark.
[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) insulating reliability between adjacent electrode
Obtained the first connection structural bodies, the second connection structural bodies, in third connection structural bodies (n=15), 85 DEG C, After being placed 100 hours in the atmosphere of humidity 85%, between applying 5V adjacent electrode, and in 25 Site Determination resistance values.With Following benchmark determine insulating reliability.
[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) interelectrode location dislocation up and down
Obtained the first connection structural bodies, the second connection structural bodies, in third connection structural bodies, along first electrode, even When the stack direction of socket part and second electrode observes first electrode and second electrode opposed part, the center of first electrode is evaluated Whether line and the center line of second electrode are aligned and the distance of location dislocation.It is wrong with the position between upper/lower electrode with following benchmark Position is determined.
[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 shown in following table 1, in 2.
Not only using flexible printing substrate, resin film, flexble flat's cable and rigid-flexible combination base are being used In the case where plate, identical tendency is seen.

Claims (12)

1. a kind of conductive paste is used to have the second electricity with the first connecting object component of first electrode and surface to surface Second connecting object component of pole is attached, and is electrically connected to the first electrode and the second electrode, wherein
The conductive paste contains multiple spacers that Thermocurable ingredient, multiple scolding tin particles and fusing point are 250 DEG C or more,
The Thermocurable ingredient contains Thermocurable compound and thermal curing agents,
In the 100 weight % of conductive paste, the content of the Thermocurable compound is 20 weight % or more and 98 weight % Hereinafter,
Relative to 100 parts by weight of Thermocurable compound, the content of the thermal curing agents is 0.01 parts by weight or more and 200 Parts by weight hereinafter,
In the 100 weight % of conductive paste, the content of the scolding tin particle be 1 weight % or more and 70 weight % hereinafter,
In the 100 weight % of conductive paste, the content of the spacer be 0.1 weight % or more and 10 weight % hereinafter,
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 use, and the conductive paste is for making multiple when being electrically connected to the first electrode and the second electrode The scolding tin particle coacervation is simultaneously integrated and melts the spacer,
The average grain diameter of the spacer is bigger than the average grain diameter of the scolding tin particle, the average grain diameter of the spacer with it is described The ratio between average grain diameter of scolding tin particle is 10 or less.
2. conductive paste as described in claim 1, wherein
The spacer is insulating properties particle.
3. conductive paste as claimed in claim 1 or 2, wherein
The side being in contact with the spacer and the first connecting object component and the second connecting object component this both sides Formula is come using the conductive paste.
4. conductive paste as claimed in claim 1 or 2, wherein
The ratio between the average grain diameter of the spacer and the average grain diameter of the scolding tin particle are 1.1 or more, 10 or less.
5. 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.
6. conductive paste as claimed in claim 1 or 2, wherein
The content of the scolding tin particle is 10 weight % or more, 80 weight % or less.
7. conductive paste as claimed in claim 1 or 2, wherein
The ratio between the content of the content of the scolding tin particle in terms of weight % unit and the spacer in terms of weight % unit It is 2 or more, 100 or less.
8. 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 connected,
The material of the interconnecting piece is conductive paste according to any one of claims 1 to 7,
The first electrode and the second electrode realize electrical connection by the solder sections in the interconnecting piece,
The solder sections be multiple scolding tin particle coacervations and integration and formed,
The spacer and the first connecting object component and the second connecting object component this both sides contact.
9. connection structural bodies as claimed in claim 8, wherein
The second connecting object component is resin film, flexible printing substrate, flexible flat cable or rigid-flexible combination substrate.
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 claim 1~7 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 The second electrode side of second connecting object component of second electrode, the second connecting object component is configured at the electroconductive paste On the surface opposite with the first connecting object component side of agent, as a result, in the first connecting object component and described The conductive paste is configured between two connecting object components, and the first electrode and the second electrode are led across described The opposed process of electric paste；
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, it is formed from there through the conductive paste and is connected to the first connecting object component and the second connecting object component Interconnecting piece together, and the first electrode and the second electrode are realized and be electrically connected by the solder sections in the interconnecting piece It connects, the process for contacting the spacer and the first connecting object component and the second connecting object component this both sides, Wherein,
The solder sections be multiple scolding tin particle coacervations and integration and formed,
In the process for configuring the conductive paste, there is the area of the first electrode in the formation of the first connecting object component The conductive paste is configured on the surface in both domain and the region for not forming the first electrode,
When being electrically connected to the first electrode and the second electrode, make multiple scolding tin particle coacervations and integrated Change, and melts the spacer.
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.
12. the manufacturing method of connection structural bodies as described in claim 10 or 11, wherein
The second connecting object component is resin film, flexible printing substrate, flexible flat cable or rigid-flexible combination substrate.
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