CN106947409A - Conductive adhesive composition, conductive adhesive film, adhesive method and circuit base plate - Google Patents

Conductive adhesive composition, conductive adhesive film, adhesive method and circuit base plate Download PDF

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Publication number
CN106947409A
CN106947409A CN201610849680.3A CN201610849680A CN106947409A CN 106947409 A CN106947409 A CN 106947409A CN 201610849680 A CN201610849680 A CN 201610849680A CN 106947409 A CN106947409 A CN 106947409A
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Prior art keywords
conductive adhesive
resin
adhesive composition
type epoxy
base plate
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CN201610849680.3A
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CN106947409B (en
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岩井靖
寺田恒彦
柳善治
山本祥久
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Tatsuta Electric Wire and Cable Co Ltd
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Tatsuta Electric Wire and Cable Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/04—Epoxynovolacs
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
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    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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    • C09J2463/00—Presence of epoxy resin

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Structure Of Printed Boards (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Combinations Of Printed Boards (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

【Problem】The physical property height and the superior conductive adhesive composition of processing characteristics and the conductive adhesive film for having used the conductive adhesive composition of a kind of adhesive-layer after crosslink density height, hardening are provided.【Solution】A kind of conductive adhesive composition, it is characterised in that：The conductive adhesive composition contains：It is the bisphenol-type epoxy resin of solid under each molecule epoxy radicals containing two or more and normal temperature（A）, under each molecule epoxy radicals containing two or more and normal temperature be solid phenolic resin varnish type epoxy resin（B）, containing containing carboxy resin（C）And electroconductive stuffing (D), wherein, containing carboxy resin（C）It is made up of at least one of following material：Polyurethane resin containing carboxyl（C‑1）With acid resin containing carboxylated polypropylene（C‑2）.

Description

Conductive adhesive composition, conductive adhesive film, adhesive method and circuit base plate
The application be Patent No. 201380033353.5, the applying date be on June 28th, 2013, entitled " conducting resinl group Into thing, conductive adhesive film, adhesive method and circuit base plate " the application for a patent for invention submitted by same applicant divisional application.
Technical field
The present invention relates to a kind of conductive adhesive composition, conductive adhesive film, adhesive method and circuit base plate.
Background technology
In flexible printed wiring board, often using conductive adhesive composition and the conductive adhesive film being consequently formed.It is this to lead Electric glue contains hardening resin and electroconductive stuffing.
In recent years, for the viewpoint for improving physical property, requirement to the physical property of above-mentioned conducting resinl also more and more higher. Specifically, such as the requirement to a variety of physical properties heat resistance, physical strength, water resistance, moisture-proof, electrical property increasingly It is high.
Patent document 1 ~ 3 discloses one kind and contains polyurethane polyureas carbamide resin（polyurethane polyurea resin） And epoxy（Epoxy, similarly hereinafter）The hardening polyurethane-polyurea of base（polyurethane polyurea）Adhesive composition. Need further to improve above-mentioned physical property in this adhesive composition, while needing fully control processing characteristics.
In order to obtain good heat resistance, physical strength, water resistance, moisture-proof and resistive performance, the method that can be used If any：Improve the crosslink density of the film after hardening.In order to obtain the resin of high crosslink density, it is necessary to increase reactive site, from this One viewpoint is considered, it is necessary to use functional group（Functional group, similarly hereinafter）The many epoxides of amount.But function base unit weight is more Molecular weight of epoxy resin it is general all relatively low, if being used as conductive adhesive film, easily overflow（bleed out）, exist and be difficult to The problem of processing.That is, now need to be binded as illustrated in fig. 2, if overflow problem, resin can be such as Fig. 3 It is shown to flow out to bonding portion of external.
For improving the method for above mentioned problem if any while using two or more epoxy resin, making point of one of which Son amount is higher, and alternative molecular weight is relatively low.But the mixture of this epoxy resin be difficult integrally occur with epoxy resin it is homogeneous Reaction, it is impossible to improve overall crosslink density.If in addition, having used the low molecular weight epoxy compound containing compared with polyepoxy If, the epoxy reaction that the epoxide of the low molecule amount most starts is most fast, since second, the 3rd, reaction speed Degree is gradually slack-off, so easily remaining unreacted epoxy radicals, the raising degree of crosslink density can not reach theoretical value.Cause This, remaining functional group can cause physical property low on the contrary.
Documents 1 have used two kinds of epoxy resin simultaneously.But selection resin is not for same with above-mentioned viewpoint herein Consideration, but in order to which using the low resin and the high resin of softening point of softening point, bending is produced with this simultaneously.Therefore, it is right Do not studied, the purpose of the documents 1 to improve the crosslink density of hardening thing as in the present invention than document 1 Not solve above-mentioned problem.
In addition, there is way as described in Patent Document 4, i.e. bind electric conductivity stiffening plate by conducting resinl, make ground plane Electronics connection is carried out between stiffening plate, makes stiffening plate that there is electromagnetic wave shielding ability with this.
Fig. 4 is one of this circuit base plate.When for such a purposes, to above-mentioned various physical properties, processing characteristics Requirement it is higher.
Prior art literature
Patent document
Patent document 1:JP（Japanese Patent Publication）2010-143981 Patent Document 2:International Publication 2007/ No. 032463 Patent Document 3:JP（Japanese Patent Publication）2007-189091 Patent Document 4:JP （Japanese Patent Publication）2005-317946 publications.
Brief summary of the invention
The invention problem to be solved
The present invention is in view of above-mentioned problem, and its object is to provide a kind of the physical of the adhesive-layer after crosslink density height, hardening Matter height and the superior conductive adhesive composition of processing characteristics and conductive adhesive film.
The means to solve the problem
The present invention provides a kind of conductive adhesive composition, it is characterised in that：
The conductive adhesive composition contains：
Each molecule has the bis-phenol under more than two epoxy radicals and normal temperature for solid（bisphenol）Type epoxy resin （A）、
Each molecule has the novolaks under more than two epoxy radicals and normal temperature for solid（Novolac）Type epoxy resin （B）、
Containing carboxyl（carboxyl group）Resin（C）And
Electroconductive stuffing (D),
Wherein, containing carboxyl（carboxyl group）Resin（C）Contain at least one material in following group：By containing carboxyl （carboxyl group）Polyurethane resin（C-1）With containing carboxyl（carboxyl group）Polyacrylic acid（polyacrylic） Resin（C-2）The group of composition.
Above-mentioned bis-phenol（bisphenol）Type epoxy resin（A）With above-mentioned novolaks（Novolac）Type epoxy resin（B） Ratio be preferably：Weight compares 85：15~99：1.
Above-mentioned bis-phenol（bisphenol）Type epoxy resin（A）Middle epoxide equivalent（epoxy equivalent）Preferably 800 ~10000.
Above-mentioned novolaks（Novolac）Type epoxy resin（B）Middle epoxide equivalent（epoxy equivalent）Preferably 90~300.
Above-mentioned electroconductive stuffing（D）It is preferably selected from least one in following group：By silver powder, silver-coated copper powder, copper powder structure Into group.
Electroconductive stuffing（D）Average grain diameter be preferably 3 ~ 50 μm.
In addition, the conductive adhesive composition of the present invention is characterised by：Bis-phenol is not contained（bisphenol）Type epoxy resin （A）, novolaks（Novolac）Type epoxy resin（B）And containing carboxyl（carboxyl group）Resin（C）Hardening in addition Agent.
Moreover, it relates to which a kind of conductive adhesive film, the conductive adhesive film is the conduction using above-mentioned conductive adhesive composition What glue-line and protective layer were laminated.
Now, the thickness of above-mentioned conductive adhesive composition is preferably 15 ~ 100 μm.
The conductive adhesive film of the present invention is characterised by：First use forcing press（press machine）It is tentatively binded, cross 1 Zhou Houzai carries out hot pressing bonding, and peel strength now is in more than 10N/cm.
The present invention relates to a kind of adhesive method, this method is made up of following steps：
Step（1）：Above-mentioned conductive adhesive film is first binded as by bonding base material（X）Electric conductivity stiffening plate or flexible base plate On,
Step（2）：Passing through step（1）Obtain have conductive adhesive film by bonding base material（X）Upper superposition is as by bonding base Material（Y）Flexible base plate or electric conductivity stiffening plate carry out hot pressing.
The invention further relates to a kind of circuit base plate, it is characterised in that：At least a portion of the circuit base plate has by soft The position that substrate, conductive adhesive layer and electric conductivity stiffening plate are laminated according to this statement order, wherein, conductive adhesive layer is by described Conductive adhesive film formation.
Face of the flexible base plate surface in addition to stiffening plate is preferably coated with electromagnetic shielding film in above-mentioned circuit base plate.
Invention effect
The conductive adhesive composition of the present invention has good heat resistance, physical strength, water resistance, moisture-proof, an electrical property, and by Press after step, the composition in film is not in overflow problem.In addition, using the invention in the stickup of the base material with difference of height When, good bonding can be carried out.In addition, in the case of being preserved for a long time after preliminary bonding, can also bind and walk in hot pressing Good cement properties are kept in rapid.
Brief description of the drawings
Fig. 1 be embodiment in peel strength assay method schematic diagram.
Fig. 2 is one of interconnection resistance determination sample in embodiment.
Fig. 3 be embodiment in resin mobility status schematic diagram.
Fig. 4 is one of the circuit base plate obtained using the conducting resinl in the present invention.
Embodiment
The following detailed description of the present invention.
Conductive adhesive composition in the present invention is characterised by：The conductive adhesive composition contains：Each molecule has two It is the bis-phenol of solid under epoxy radicals above and normal temperature（bisphenol）Type epoxy resin（A）, each molecule have two with On epoxy radicals and normal temperature under be solid novolaks（Novolac）Type epoxy resin（B）, containing carboxyl（carboxyl group）Resin（C）And electroconductive stuffing (D), wherein, containing carboxyl（carboxyl group）Resin（C）Containing selected from At least one material in lower group：By containing carboxyl（carboxyl group）Polyurethane resin（C-1）With containing carboxyl（carboxyl group）Polyacrylic acid（polyacrylic）Resin（C-2）The group of composition.Formed by this conductive adhesive composition of the invention Crosslink density after bonding coat hardening is homogeneous, and can obtain higher crosslink density.Therefore, it is possible to form moisture-proof, it is water-fast All very superior bonding coats such as property, heat resistance, physical strength, electrical property.In addition, the problems such as being not in spilling during processing, and Good processing characteristics can be obtained.In addition, in the case of being preserved for a long time after preliminary bonding, also step can be binded in hot pressing It is middle to keep good cement properties.
（Bis-phenol（bisphenol）Type epoxy resin（A）And novolaks（Novolac）Type epoxy resin（B））
The epoxy resin used in the present invention（A）It is that each molecule has under more than two epoxy radicals and normal temperature for solid Bis-phenol（bisphenol）Type epoxy resin.Under normal temperature for solid be meant that presented not at 25 °C and in the state of solvent-free Solid state with mobility.If above-mentioned bonding coat is only by novolaks（Novolac）If type epoxy resin is constituted, meeting The problem of there is adhesion property and bad filming performance, it is therefore necessary to have bis-phenol（bisphenol）Type epoxy resin（A）.This Outside, good processing characteristics is obtained, it is necessary to use the material under normal temperature being solid.
Above-mentioned bis-phenol（bisphenol）Type epoxy resin（A）It is not particularly limited, for example, can is bis-phenol （bisphenol）A types epoxy resin, bis-phenol（bisphenol）F types epoxy resin, bis-phenol（bisphenol）S types epoxy resin, Tetrabromobisphenol（tetrabromobisphenol）A type epoxy resin etc..Above-mentioned epoxy resin can be used alone one kind, also may be used It is two or more to be applied in combination.Wherein, from the viewpoint of high adhesion, heat resistance, with bis-phenol（bisphenol）A type epoxies Resin or bis-phenol（bisphenol）F type epoxy resin is advisable.
Above-mentioned bis-phenol（bisphenol）Type epoxy resin（A）The type that epoxide equivalent is 800 ~ 10000 is preferred.This Sample can further improve the cohesive force with stiffening plate, more suitably.The lower limit of above-mentioned epoxide equivalent is 1000 more preferable, preferably 1500.The upper limit of above-mentioned epoxide equivalent is 5000 more preferable, preferably 3000.
It can act as above-mentioned bis-phenol（bisphenol）Type epoxy resin（A）Commercial epoxy resins have EPICLON4050, 7050th, HM-091, HM-101（Trade name, Dainippon Ink Chemicals's production）、jER1003F、1004、1004AF、1004FS、 1005F、1006FS、1007、1007FS、1009、1009F、1010、1055、1256、4250、4275、4004P、4005P、 4007P、4010P（Trade name, Mitsubishi chemical Co., Ltd's production）Deng.
Above-mentioned novolaks（novolac）Type epoxy resin（B）Be a kind of each molecule have more than two epoxy radicals, And the novolaks under normal temperature for solid（novolac）Type epoxy resin.Novolaks（novolac）The epoxy of type epoxy resin Resin density is high, and good with the Combination of other epoxy resin, and the reaction sex differernce between epoxy radicals is smaller, so can make painting The overall crosslink density of film is not only homogeneous but also height.
Above-mentioned novolaks（novolac）Type epoxy resin is not particularly limited, if any cresol novolak（cresol novolac）Type epoxy resin, phenol novolacs（phenol novolac）Type epoxy resin, alpha-Naphthol novolaks（α- naphthol novolac）Type epoxy resin, brominated phenol novolaks（brominated phenol novolac）Type asphalt mixtures modified by epoxy resin Fat etc..Wherein, from the viewpoint of high adhesion, heat resistance, with phenol novolacs（phenol novolac）Type asphalt mixtures modified by epoxy resin Fat or cresol novolak（cresol novolac）Type epoxy resin is advisable.
Above-mentioned novolaks（novolac）Type epoxy resin（B）Epoxide equivalent be advisable with 90 ~ 300.It can so improve The heat resistance of resin.The lower limit of above-mentioned epoxide equivalent is 150 more preferably preferably 170.The upper limit of above-mentioned epoxide equivalent is 250 more It is good, preferably 230.
It can act as above-mentioned novolaks（novolac）Type epoxy resin（B）Commercial epoxy resins if any EPICLONN-660, N-665, N-670, N-673, N-680, N-695, N-655-EXP-S, N-662-EXP- S, N-665-EXP, N-665-EXP-S, N-672-EXP, N-670-EXP-S, N-685-EXP, N-673- 80M, N-680-75M, N-690-75M, N-740, N-770, N-775, N-740-80M, N-770-70M, N- 865th, N-865-80M（Trade name, Dainippon Ink Chemicals's production）jER152、154、157S70（Trade name, Mitsubishi Chemical's strain formula Commercial firm produces）YDPN-638, YDCN-700, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN- 700-7, YDCN-700-10, YDCN-704, YDCN-700-A（Trade name, Nippon Steel Chemical Co., Ltd's production）Deng.
The above-mentioned bis-phenol contained in the conductive adhesive layer of conductive adhesive composition in the present invention（bisphenol）Type epoxy resin （A）And novolaks（novolac）Type epoxy resin（B）Weight ratio preferably 85：15~99：1.It is set to above-mentioned ratio Example, it can be ensured that the cohesive force between stiffening plate, and can be in actual installation parts Reflow Soldering (reflow）Step It is middle to ensure enough heat resistances.On aforementioned proportion, if bis-phenol（bisphenol）Type epoxy resin（A）Ratio be more than 99： If 1, in actual installation parts, possibly Reflow Soldering (reflow can not be born）, so being not suitable for using.And if phenolic aldehyde Varnish（novolac）Type epoxy resin（B）Ratio be more than 85：15, then with being attached to body（Ni-SUS, SUS, gold-plated electrode, Polyimides（polyimide）Resin etc.）Cohesive force can reduce, therefore be not suitable for use.
Epoxide equivalent in this specification is the numerical value measured by constant-current titration.
（Containing carboxyl（carboxyl group）Resin（C））
The conductive adhesive composition of the present invention is preferably also containing at least one material in following group：By containing carboxyl （carboxyl group）Polyurethane resin（C-1）With containing carboxyl（carboxyl group）Polyacrylic acid（polyacrylic） Resin（C-2）The group of composition.
That is, carboxyl is passed through（carboxyl group）Reaction with epoxy radicals is hardened, so can improve heat-resisting Property, it is possible to increase with the cohesive force being attached between body.
In addition, carboxyl（carboxyl group）Both can also serve as side chain in the end of chain, but using side chain as Preferably.
（Containing carboxyl（carboxyl group）Polyurethane resin（C-1））
It is just above-mentioned below to contain carboxyl（carboxyl group）Polyurethane resin（C-1）Illustrate.
Containing carboxyl（carboxyl group）Polyurethane resin（C-1）It is that one kind contains carboxyl in intramolecular（carboxyl group）Resin, it can by make contain carboxyl（carboxyl group）Polyalcohol（polyol）Compound（1）, polyalcohol （polyol）（2）, short-chain diol（diol））Compound（3）（As needed）, polyamine（polyamine）Compound（4）（According to Need）, PIC（polyisocyanate）Compound（5）Reaction is obtained.When so being reacted, polyalcohol （polyol）Compound（1）Using with carboxyl（carboxyl group）Material, can thus obtain well containing carboxyl （carboxyl group）Polyurethane resin（C-1）.
" polyurethane " in this specification is polyurethane and polyurethane-urea（polyurethane-urea）General name.Must When wanting, " polyurethane ", which can also be, make amine as needed（amine）Composition reacted obtained by material.In this specification " containing active hydrogen-based " refers to energy and NCO（isocyanate group）React, the functional group containing reactive hydrogen. This " containing active hydrogen-based " is specifically if any hydroxyl（Hydroxyl hydroxyl group）, sulfydryl（mercapto group）, carboxylic Base（carboxyl group）, amino etc..
Containing carboxyl（carboxyl group）Polyalcohol（polyol）Compound（1）It is at least containing a carboxyl （carboxyl group）With two or more hydroxyl（hydroxyl group）Compound.It is specific if any：Dihydromethyl propionic acid （dimethylol propanoic acid）, dimethylolpropionic acid（dimethylol butanoic acid）Deng dihydroxymethyl Alkyl acid（dimethylol alkanoic acid）；Dihydroxymethyl alkyl acid（dimethylol alkanoic acid）Alkene Change oxygen（alkylene oxide）Low mol adduct（adduct）（The quantitative institute's number average molecular weight of terminal functional group is less than 500）；Dihydroxymethyl alkyl acid（dimethylol alkanoic acid）6-caprolactone（ε-caprolactone）It is low to rub That adduct（adduct）（The quantitative institute's number average molecular weight of terminal functional group is less than 500）；Dihydroxymethyl alkyl acid （dimethylol alkanoic acid）In acid anhydrides（acid anhydride）And glycerine（glycerin）It is derivative （derived from）The half ester gone out（half ester）Class；Dihydroxymethyl alkyl acid（dimethylol alkanoic acid） Hydroxyl, the monomer with unsaturated bond（Monomer, similarly hereinafter）, with carboxyl（carboxyl group）With unsaturated bond Compound obtained by monomer progress radical reaction etc..Wherein, from being readily obtained, be easily adjusted from the point of view of acid value etc., Dihydromethyl propionic acid（dimethylol propanoic acid）And dimethylolpropionic acid（dimethylol butanoic acid）Deng dihydroxymethyl alkyl acid（dimethylol alkanoic acid）It is more suitable.Set polyurethane resin（C- 1）In polyalcohol（polyol）Compound（1）Content when, resulting polyurethane resin should be ensured（C-1）With epoxy Crosslinking can improve heat resistance, durability, ensure flexibility and adhesion again.Specifically, in setting reacted constituent Polyalcohol（polyol）Compound（1）Content when, preferably make resulting polyurethane resin（C-1）Acid value for 3 ~ 100mgKOH/g。
Above-mentioned polyalcohol（polyol）（2）It is the composition with more than two hydroxyls, it is preferred to use number-average molecular weight is 500 ~ 3000 material.Above-mentioned polyalcohol（polyol）（2）Only refer to and be not belonging to above-mentioned polyalcohol（polyol）Compound（1）Thing Matter.
Above-mentioned polyalcohol（polyol）（2）It is not particularly limited, can use is used for synthesizing amino Ethyl formate in the past （urethane）Known polyalcohol（polyol）.Polyalcohol（polyol）（2）Specific example if any polyester （polyester）Polyalcohol（polyol）, polyethers（Polyether, similarly hereinafter）Polyalcohol（polyol）, makrolon （polycarbonate）Polyalcohol（polyol）And other polyalcohols（polyol）Deng.
Polyester（polyester）Polyalcohol（polyol）For example there are following substances to pass through the material obtained by polycondensation reaction： Aliphatic dicarboxylic acid（Dicarboxylic acid, similarly hereinafter）（For example, butanedioic acid, adipic acid（Adipic acid, similarly hereinafter）, the last of the ten Heavenly stems Diacid（Sebacic acid, similarly hereinafter）, glutaric acid（Glutaric acid, similarly hereinafter）, azelaic acid（Azelaic acid, similarly hereinafter） Deng）And/or aromatic dicarboxylic acid（For example, M-phthalic acid（Isophthalic acid, similarly hereinafter）, terephthalic acid (TPA) （Terephthalic acid, similarly hereinafter）Deng）And low molecular weight diols（glycol）（For example, ethylene glycol（ethylene glycol）, 1,2-PD（1,2-propylene glycol）, 1,3-PD（1,3-propylene glycol）, BDO（Isosorbide-5-Nitrae-butylene glycol）, 1,6- hexylene glycols（1,6-hexamethylene glycol）, neopentyl glycol（neopentyl glycol）, Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane（Isosorbide-5-Nitrae-Bis ( hydroxymethyl)cyclohexane）Deng）.
Above-mentioned polyester（polyester）Polyalcohol（polyol）Specific example if any：Polyethylene glycol adipate glycol （poly ethylene adipate diol）, polybutylene glyool adipate（poly butylene adipate diol）, polyhexamethylene adipate glycol（poly hexamethylene adipate diol）, polyadipate neopentyl glycol Esterdiol（poly neopentyl adipate diol）, polyadipate second/butyl glycol ester diol（poly ethylene/ butylene adipate diol）, the new penta/hexylene glycol esterdiol of polyadipate（poly neopentyl/ hexyl adipate diol）, polyadipate -3- methyl the eleventh of the twelve Earthly Branches glycol esterdiols（Poly-3-methylpentane adipate diol）, poly- isophthalic acid butyl glycol ester diol（poly butylene isophthalate diol）, polycaprolactone glycol （poly caprolactone diol）, poly- 3- methyl valerolactone glycol（Poly-3-methyl valerolactone diol）Deng.
PPG（polyol）Specific example if any：Polyethylene glycol（poly ethylene glycol）, poly- third Glycol（poly propylene glycol）, poly- tetramethylene glycol（poly tetramethylene glycol）And it is above-mentioned Random/block copolymer of material etc..
Polycarbonate polyol（polyol）Specific example if any：Polytetramethylene carbonate diol glycol（poly tetramethylene carbonate diol）, poly- neopentyl glycol carbonate esterdiol（poly Pentamethylene carbonate diol）, poly- carbonic acid neopentyl glycol esterdiol（poly neopentyl carbonate diol）, poly- carbonic acid oneself Glycol esterdiol（poly hexamethylene carbonate diol）, the poly- cyclohexanedimethanoester ester glycol of carbonic acid 1,4 （Poly Isosorbide-5-Nitrae-cyclohexane dimethylene carbonate diol）And random/block of above-mentioned substance is common Polymers etc..
Other polyalcohols（polyol）Specific example if any：Dimer（dimer）Glycol（diol）, polybutadiene polyol Alcohol（poly butadiene polyol）And its hydrogen addition product, polyisoprene polyol（poly isoprene polyol） And its hydrogen addition product, acrylic polyol（acrylic polyol）, epoxy polyol（epoxy polyol）, polyether ester it is polynary Alcohol（polyether‐ester polyol）, silicone-modified polyalcohol（siloxane modified polyol）, α, ω- Polymethyl methacrylate（α, ω-poly methyl methacrylate）Glycol（diol）, α, ω-polymethylacrylic acid Butyl glycol ester diol（α, ω-polybutylmethacrylate diol）Deng.
Polyalcohol（polyol）（2）Number-average molecular weight（Mn, quantitatively obtained by terminal functional group）It is not particularly limited, But it is advisable with 500 ~ 3,000.Polyalcohol（polyol）（2）Number-average molecular weight（Mn）If 3,000, urethanes Key（urethane bond）Cohesiveness be difficult to show, mechanical performance is on a declining curve.In addition, number-average molecular weight is more than 3,000 Crystallinity polyalcohol（polyol）Cause albefaction sometimes when as overlay film.Polyalcohol（polyol）（2）Both can be independent Using one kind, it can also be used in combination of two or more.
In addition, for obtaining polyurethane resin（C-1）Reacted constituent preferably based on needing to use short-chain diol（diol） Composition（3）, as needed using polyamine（polyamine）Composition（4）.So be easier to control polyurethane resin hardness, Viscosity etc..Short-chain diol（diol）Composition（3）Specific example if any：Ethylene glycol（ethylene glycol）, 1,2- the third two Alcohol（1,2-propylene glycol）, 1,3-PD（1,3-propylene glycol）, BDO（1, 4-butylene glycol）, 1,6- hexylene glycols（1,6-hexamethylene glycol）, neopentyl glycol（neopentyl glycol）Deng aliphatic diol（glycol）And its alkylene oxide（alkylene oxide）Low mol adduct（adduct） （The number-average molecular weight that terminal functional group quantitatively obtains is less than 500）；1,4 cyclohexane dimethanol（Isosorbide-5-Nitrae-Bis hydroxymethyl cyclohexane）, 2- methyl isophthalic acids, 1- cyclohexanedimethanols（2-methyl-1,1- cyclohexane dimethanol）Deng alicyclic diol（glycol）And its alkylene oxide（alkylene oxide）Low mole adds Compound（adduct）（Number-average molecular weight be less than 500, ibid）；Benzene dimethanol（xylylene glycol）Deng aromatic diol （glycol）And its alkylene oxide（alkylene oxide）Low mol adduct（adduct）（Number-average molecular weight is less than 500, same On）；Bis-phenol（bisphenol）A, bisphenol sulfide（thiobisphenol）, sulfonated bis phenol（sulfone bisphenol）Deng double Phenol（bisphenol）And its alkylene oxide（alkylene oxide）Low mol adduct（adduct）（Number-average molecular weight is less than 500th, ibid）；C1 ~ C18 alkyldiethanolamine（alkyl diethanolamine）Deng alkyl dialkanol amine（alkyl dialkanolamine）Deng.
Polyamine（polyamine）Compound（4）Specific example it is as follows：Short chain has：Methylene diamine （methylenediamine）, ethylenediamine（ethylenediamine）, propane diamine（trimethylene diamine）, oneself two Amine（hexamethylenediamine）, octamethylenediamine（octamethylene diamine）Deng aliphatic diamine（diamine）Change Compound；Phenylenediamine（phenylene diamine）, 3,3 '-two chloro- 4,4 '-MDAs（3,3 '-dichloro - 4,4 '-diaminodiphenyl methane）, 4,4 '-two（Aminobenzene）Methane（4,4 '-methylenebis （phenylamine））, 4,4 '-diaminodiphenyl ether（4,4 '-diaminodiphenyl ether）, 4,4 '-diaminourea hexichol Sulfone（4,4 '-diaminodiphenylsulfone）Deng aromatic diamine（diamine）Compound；Cyclopenta diamines （cyclopentyl diamine）, cyclohexyl diamine（cyclohexyl diamine）, 4,4 '-diamino-dicyclohexyl methane （4,4 '-Diaminodicyclohexyl methane）, Isosorbide-5-Nitrae-diaminocyclohexane（Isosorbide-5-Nitrae-diamino cyclohexane）, IPD（isophorone diamine）Deng alicyclic diamine（diamine）Compound etc..This Outside, can also be by hydrazine（hydrazine）, carbazide（carbodihydrazide）, adipic dihydrazide（Adipic acid dihydrazide）, sebacic dihydrazide（Sebacic acid dihydrazide）, phthalic acid（phthalic acid）Two hydrazides（dihydrazide）Deng hydrazine（hydrazine）Class is used as diamines（diamine）Compound（4）.Long-chain has： Long-chain alkylene diamines（alkylenediamine）, polyoxy alkylene diamines（polyoxy alkylenediamine）, end Amino polyamide（amine polyamide）, it is silicone-modified（siloxane modified）Polyamine（polyamine）Class etc.. Above-mentioned polyamine（polyamine）Compound（4）Both one kind is can be used alone, can also be used in combination of two or more.
PIC（polyisocyanate）Compound（5）Manufacture polyurethane in the past can be used （polyurethane）When the known PIC that uses（polyisocyanate）.PIC （polyisocyanate）（5）Specific example if any：Toluene-2,4-diisocyanate, 4- diisocyanates（Toluene-2,4- diisocyanate）, 4- methoxyl group -1,3- phenylene diisocyanates（4-Methoxy-1,3-phenylene diisocyanate）, 4- isopropyl -1,3- phenylene vulcabonds（4-Isopropyl-1,3-phenylene diisocyanate）, the chloro- 1,3- phenylene vulcabonds of 4-（4-chlor-1,3-phenylene diisocyanate）, 4- butoxy -1,3- phenylene vulcabonds（4-butoxy-1,3-phenylene diisocyanate）, 2,4- diisocyanate diphenyl ether（2,4-diisocyanate diphenyl ether）, 4,4 '-it is sub- Methyl-diphenylene isocyanide ester（4,4 '-methylene bis（phenylene isocyanate））（MDI）, tetramethyl For benzene to support diisocyanate（Durylene diisocyanate）, tolidine diisocyanate（tolidine diisocyanate）, XDI（Xylylene diisocyanate）（XDI）, the isocyanic acid of 1,5- naphthalenes two Ester（1,5-naphthalenediisocyanate）, benzidine diisocyanate（benzidine diisocyanate）, it is o- Nitrobenzidine diisocyanate（O-nitrobenzidinediisocyanate）, 4,4 '-dibenzyl diisocyanate（4, 4 '-diisocyanatedibenzyl）Deng aromatic diisocyanate（diisocyanate）；Methylene diisocyanate （methylenediisocyanate）, Isosorbide-5-Nitrae-tetramethylene diisocyanate（1,4-tetramethylene diisocyanate）, 1,6- hexa-methylene diisocyanates（1,6-hexamethylene diisocyanate）, 1,10- ten Methylene diisocyanate（1,10-Decamethylene diisocyanate）Deng aliphatic diisocyanate （diisocyanate）；1,4- cyclohexyl diisocyanates（Isosorbide-5-Nitrae-cyclohexylene diisocyanate）, 4,4- methylenes Base two（Cyclohexyl isocyanate）（4,4-methylenebis（cyclohexyl isocyanate））, 1,5- naphthanes two it is different Cyanate（1,5-tetrahydro naphthalenediisocyanate）, IPDI（isophorone diisocyanate）, hydrogenation（hydrogenation）MDI, hydrogenation（hydrogenation）The alicyclic diisocyanates such as XDI （diisocyanate）；Above-mentioned diisocyanate（diisocyanate）With the polyalcohol of low molecule amount（polyol）Or polyamine （polyamine）Carrying out reaction makes end turn into isocyanates（isocyanate）Polyurethane resulting afterwards （polyurethane）Prepolymer etc..If obtaining the polymer composition with preferable weatherability, it is preferred to use Aliphatic diisocyanate（diisocyanate）And alicyclic diisocyanate（diisocyanate）.
PIC（polyisocyanate）Compound（5）NCO（isocyanate group）With it is upper State containing carboxyl（carboxyl group）Polyalcohol（polyol）Compound（1）, polyalcohol（polyol）（2）, short-chain diol （diol）Compound（3）（As needed）, polyamine（polyamine）Compound（4）（As needed）Deng active hydrogen-based（But no Including（1）Carboxyl（carboxyl group））Equivalent proportion be preferably 0.5~1.5.It can obtain within the above range heat-resisting Property, mechanical strength all very high urethanes（urethan）, it is more suitable with this.
There can also be the structure of closing base using end section.That is, can also be using the structure being obtained as below：In isocyanic acid Ester group（isocyanate group）Reacted under conditions of surplus, isocyanates is formed with this（isocyanate）End, Make its isocyanates（isocyanate）End is reacted with monofunctional compound, and the structure of endcapped is obtained with this.
（Polyurethane（polyurethane）Resin（C-1）Manufacture method）
Polyurethane（polyurethane）Resin（C-1）Known polyurethane can be used（polyurethane）Manufacture method To manufacture.Specifically, first, presence or absence of intramolecular without reactive hydrogen organic solvent under conditions of, make by containing Carboxyl（carboxyl group）Polyalcohol（polyol）Compound（1）, polyalcohol（polyol）（2）, as desired as chain The short-chain diol that growing agent is selected（diol）Compound（3）, polyamine（polyamine）Compound（4）（As needed）, poly- isocyanide Acid esters（polyisocyanate）（5）The reacted constituent of composition is reacted, and obtains reactant（Such as prepolymer）.On reaction The composition of composition, in general, as long as can be formed with terminal isocyanate group（isocyanate group）It is pre- Polymers.In addition, using a Completion Techniques during reaction（one shot method）Or multistep processes, temperature is generally set to 20 ~150 °C, it is set to 60~110 °C more preferably, reaction is to reaching theoretical isocyanate（isocyanate）%.
On resulting reactant（Prepolymer）, it is necessary to when, polyamine can also be made（polyamine）Compound（4）Ginseng With reaction, increase chain, with the molecular weight needed.Again, it is preferred to be reacted under the following conditions：PIC （polyisocyanate）Compound（5）NCO（isocyanate group）（2）With containing carboxyl（carboxyl group）Polyalcohol（polyol）Compound（1）, polyalcohol（polyol）（2）, short-chain diol（diol）Compound（3）And it is poly- Amine（polyamine）Compound（4）Total active hydrogen-based（Compound（1）Carboxyl（carboxyl group）Except）Work as Amount is than being 0.5 ~ 1.5.
The polyurethane being obtained as described above（polyurethane）Resin（C-1）Weight average molecular weight（Mw）Preferably 1,000 ~ 1, 000,000, because now polyurethane（polyurethane）The characteristic meeting such as flexibility, adhesion, heat resistance and coating performance More effectively play.In addition, " the weight average molecular weight in this specification（Mw）" and " number-average molecular weight（Mn）" do not saying especially Refer to use gel permeation chromatography in the case of bright（GPC）The polystyrene measured（polystyrene ）The value of conversion.
In the present invention, synthesizing amino Ethyl formate（urethane）When can use catalyst as needed.For example have Dibutyl tin laurate（DIBUTYLTIN LAURATE）, dioctyltin laurate（dioctyltin laurate）, octanoic acid it is sub- Tin（stannous octoate）, zinc octoate, tetra-n-butyl titanate（Tetra n-butyl titanate）Deng metal and having Machine acid, the salt of inorganic acid and Organometallic derivatives, triethylamine（Triethylamine）Deng organic amine, 1,8- diazas two Carbon -7- the alkene of ring [5.4.0] 11（Diazabicycloundecene）Class catalyst etc..
Polyurethane（polyurethane）Resin（C-1）Both it can also can not be closed by solvent synthesis by organic solvent Into.Organic solvent can be used for NCO（isocyanate group）Inert organic solvent, or make With compared with reacted constituent for NCO（isocyanate group）In the organic solvent of low activity.Organic solvent Specific example if any：Acetone（acetone）, methyl ethyl ketone（methyl ethyl ketone）, methyl iso-butyl ketone (MIBK) （methyl isobutyl ketone）, cyclohexanone（cyclohexanone）Deng ketone（ketone）Class solvent；Toluene （toluene）, dimethylbenzene（xylene）、Swasol（Trade name, the production of cosmo oil Co., Ltd.）、Solvesso（Commodity Name, the production of EXXON KCCs）Deng fragrant same clan hydro carbons（hydrocarbons）Solvent；N-hexane（N-hexane） Deng aliphatic category hydro carbons（hydrocarbons）Solvent；Methanol（methanol）, ethanol（ethanol）, isopropanol （Isopropylalcohol）Deng alcohol（alcohol）Class solvent；Dioxanes（dioxane）, tetrahydrofuran （tetrahydrofuran）Deng ether（ether）Class solvent；Ethyl acetate（ethyl acetate）, butyl acetate（Butyl acetate）, isobutyl acetate（isobutyl acetate）Deng ester（ester）Class solvent；Ethyl cellosolve acetate （ethyleneglycolethyl ether acetate）, propylene glycol methyl ether acetate（propylene glycolmethyl ether acetate）, 3- methyl -3- methoxybutyl acetic acid esters（3-methyl-3-Methoxybutyl acetate）、 Ethyl -3- ethoxy-c acid esters（Ethyl-3-ethoxy propionate）Deng glycol ether-ether（glycolether ester） Class solvent；Dimethylformamide（dimethylformamide）, dimethylacetylamide（Dimethylacetamide）Deng acid amides （Amide）Class solvent；METHYLPYRROLIDONE（N-methyl-2-Pyrrolidone）Deng lactams（lactam）Class Solvent etc..
In synthesizing amino Ethyl formate（urethane）When, if NCO（isocyanate group）Remain in Polymer ends, preferably carry out NCO（isocyanate group）End capping reaction（Termination）.Isocyanates Base（isocyanate group）End capping reaction（Termination）Can by with NCO（isocyanate group）Compound with reactivity is carried out.This compound can be enumerated：Monohydric alcohol（monoalcohol）, monoamine （monoamine）Deng monofunctional compounds；With to isocyanates（isocyanate）Two kinds of different functional groups of reactivity Compound.The specific example of this compound if any：Methanol（methyl alcohol）, ethanol（ethyl alcohol）, just Propyl alcohol（N-propyl alcohol）, isopropanol（Isopropylalcohol）, n-butanol（N-butyl alcohol）、 Isobutanol（isobutyl alcohol）, the tert-butyl alcohol（tert-butyl alcohol）Deng monohydric alcohol（monoalcohol）；One second Amine（monoethylamine）, n-propylamine（N-propylamine）, diethylamine（Diethylamine）, di-n-propylamine（Di- N-propylamine）, di-n-butylamine（Di-n-Butylamine）Deng monoamine（monoamine）；MEA （monoethanolamine）, diethanol amine（diethanolamine）Deng alkanolamine（alkanolamine）Deng.Wherein, alkanol Amine（alkanolamine）Reaction controlling it is relatively simple, therefore suitable use.
（Acrylic resin（acrylic resin）（C-2））
The acrylic resin that can be used in the present invention（acrylic resin）（C-2）It is that intramolecular contains carboxyl（carboxyl group）Resin, itself and epoxy（epoxy）Resin crosslinks reaction.The acrylic resin（acrylic resin）（C-2） It is obtained as below：Make to contain carboxyl by the typical polymerization method such as radical polymerization, cationic polymerization and anionic polymerisation（carboxyl group）Polymerizable monomer（6）With other polymerizable monomers（7）Polymerization.
Containing carboxyl（carboxyl group）Polymerizable monomer（6）Acrylic acid can be used（acrylic acid）, methyl Acrylic acid（methacrylic acid）, containing carboxyl（carboxyl group）Acrylate（acrylic acid ester）、 Such as 2- acrylyl oxy-ethyls-butanedioic acid（2-acryloyloxyethyl Succinic acid）, 2- acryloyl-oxy second Base hexahydro-phthalic acid ester（2-acryloyloxyethyl hexahydrophthalate）, 2- acryloyl-oxy second Base-phthalic acid（2-acryloyloxyethyl phthalic acid）, containing carboxyl（carboxyl group）Methyl Acrylate（methacrylic acid ester）, such as 2- methylacryoyloxyethyls-butanedioic acid（2- methacryloyloxyethyl Succinic acid）, 2- methylacryoyloxyethyl hexahydro-phthalic acid esters（2- methacryloyloxyethylhexahydrophthalate）, 2- methylacryoyloxyethyl phthalic acids（2- Methacryloyloxyethyl-phthalic acid）Deng, wherein, factor of from reactivity and easily starting with etc. considers, with third Olefin(e) acid（acrylic acid）And methacrylic acid（methacrylic acid）It is advisable（Below sometimes by " acryloyl group （acryl）" and " methylacryloyl（methacryl）" be written as together "（Methyl）Acryloyl group（(meth)acryl）”）.
Other polymerizable monomers（7）Many kinds of substance can be used, wherein with（Methyl）Acrylic acid（（meth）acrylic acid）Class monomer is advisable.It is above-mentioned（Methyl）Acrylic acid（（meth）acrylic acid）The specific example of class monomer if any：（First Base）Methyl acrylate（methyl（meth）acrylate）、（Methyl）Ethyl acrylate（ethyl（meth）acrylate）、（First Base）N-propyl（N-propyl（meth）acrylate）、（Methyl）Isopropyl acrylate（Isopropyl（meth） acrylate）、（Methyl）N-butyl acrylate（N-butyl（meth）acrylate）、（Methyl）Isobutyl acrylate （isobutyl（meth）acrylate）、（Methyl）Sec-butyl acrylate（Sec-butyl（meth）acrylate）、（Methyl） Tert-butyl acrylate（tert-butyl（meth）acrylate）、（Methyl）Amyl acrylate（amyl（meth）acrylate）、 （Methyl）Isoamyl acrylate（Isoamyl（meth）acrylate）、（Methyl）Heptylacrylate（Heptyl（meth） acrylate）、（Methyl）N-octyl（N-octyl（meth）acrylate）、（Methyl）Isooctyl acrylate monomer（iso- octyl（meth）acrylate）、（Methyl）Acrylic acid-2-ethyl caproite（2-ethylhexyl（meth）acrylate ）、 （Methyl）Cyclohexyl acrylate（cyclohexyl （meth）acrylate）、（Methyl）Acrylic acid nonyl ester（nonyl（meth） acrylate）、（Methyl）The different nonyl ester of acrylic acid（Isononyl （meth）acrylate）、（Methyl）Isodecyl acrylate （isodecyl（meth）acrylate）、（Methyl）Dodecyl acrylate（Dodecyl（meth）acrylate）、（Methyl）Propylene Sour 13 esters（tridecyl（meth）acrylate）、（Methyl）Positive ten diester of acrylic acid（N-lauryl（meth） acrylate）、（Methyl）N-stearyla crylate（N-Stearyl（meth）acrylate）、（Methyl）Acrylic acid different 18 Ester（isostearyl（meth）acrylate）、（Methyl）The ring pentyl ester of acrylic acid two（DICYCLOPENTANYL （meth） acrylate）、（Methyl）Isobornyl acrylate（isobornyl（meth）acrylate）、（Methyl）Phenoxyethyl acrylate （Phenoxyethyl（meth）acrylate）、N-（Methyl）Acrylyl oxy-ethyl hexahydro phthalimide（N- （meth）acryloyloxyethyl hexahydrophthalimide）Deng.In addition, other polymerizable monomers（7）It can use Styrene（styrene）Class monomer or acrylonitrile（acrylonitrile）Class monomer.Above-mentioned monomer both can be used alone one kind It can also be applied in combination two or more.
Acrylic resin（acrylic resin）（C-2）Acid value it is higher, crosslinking points are more, and heat resistance is higher.But with acid The too high acrylic resin of valency（acrylic resin）（C-2）For composition obtain conductive adhesive composition exist it is really up to the mark cause it is soft Soft reduction, or carboxyl（carboxyl group）Can not be with epoxy resin（epoxy）Deng complete reaction, what durability declined Problem.Therefore, acrylic resin（acrylic resin）（C-2）Acid value be advisable with 3 ~ 100mgKOH/g.
If with（Methyl）Acrylic acid（（meth）acrylic acid）And long-chain alcohol（alcohol）Ester（ester）Make For polymerizable monomer, resulting acrylic resin（acrylic resin）（C-2）Glass transition point（Tg）It can drop It is low.Use this glass transition point（Tg）Low acrylic resin（acrylic resin）（C-2）, flexibility can be obtained With all good conductive adhesive composition of adhesion.And if with（Methyl）Acrylic acid（（meth）acrylic acid）And short chain alcohol （alcohol）Ester（ester）、（Methyl）Acrylic acid（（meth）acrylic acid）, styrene（styrene）Or propylene Nitrile（acrylonitrile）As polymerizable monomer, resulting acrylic resin（acrylic resin）（C-2）'s Glass transition point（Tg）It can raise.Use this glass transition point（Tg）High acrylic resin（acrylic resin） （C-2）If, all good conductive adhesive composition of heat resistance and durability can be obtained.That is, the species of selective polymerization composition, ratio When, make acrylic resin（acrylic resin）（C-2）Glass transition point（Tg）For appropriate numerical value, it can thus obtain Flexibility, adhesion, heat resistance, durability.Specifically, it is most handy two or more（Methyl）Acrylic acid（（meth） acrylic acid）Class monomer is used as the composition containing double bond.In addition, acrylic resin（acrylic resin）（C-2）Glass Glass transition point（Tg）Preferably -20 ~ 30 °C.Acrylic resin（acrylic resin）（C-2）Glass transition point （Tg）If 30 °C, flexibility and adhesion can be reduced.And if acrylic resin（acrylic resin）（C-2）'s Glass transition point（Tg）If -20 °C, heat resistance and durability can decline.
（Acrylic resin（acrylic resin）（C-2）Manufacture method）
For example, making to contain carboxyl with known polymerizations such as emulsion polymerization, suspension polymerisation, polymerisation in solution or block polymerizations （carboxyl group）Polymerizable monomer（6）With other polymerizable monomers（7）It is polymerize, with this with regard to acrylic acid tree can be obtained Fat（acrylic resin）（C-2）.For example, in polymerisation in solution, it is only necessary to appropriate under conditions of it there is polymerization initiator Solvent in polymerize polymeric composition.
The solvent species used in polymerisation in solution is not particularly limited, as long as will not be had undesirable effect to polymerisation .The specific example of solvent if any：Water；Methanol（methanol）, ethanol（ethanol）, isopropanol （Isopropylalcohol）, normal propyl alcohol（N-propyl alcohol）, n-butanol（N-butyl alcohol）, isobutyl Alcohol（isobutyl alcohol）, the tert-butyl alcohol（tert-butyl alcohol）, n-amyl alcohol（N- pentyl alcohol）、 Ethyl cellosolve（ethylcellosolve）, butyl cellosolve（butyl cellosolve）, propylene glycol monomethyl ether （propylene glycolmonomethyl ether）, ethylene glycol（ethyleneglycol）, propane diols（propylene glycol）, diethylene glycol (DEG)（diethylene glycol）Deng alcohol（alcohol）Class solvent；Petroleum ether（petroleum ether）、 Hexane（hexane）, heptane（heptane）Deng aliphatic hydrocarbon（hydrocarbons）Class solvent；Benzene（benzene）, toluene （toluene）, dimethylbenzene（xylene）Deng aromatic hydrocarbon（hydrocarbons）Class solvent；Diethyl ether（diethyl ether）、 Butyl oxide（dibutyl ether）, tetrahydrofuran（tetrahydrofuran）（THF）, dioxanes（dioxane）Deng ether （ether）Class solvent；Methyl ethyl ketone（methyl ethyl ketone）, 2 pentanone（2-pentanone）, propione（3- pentanone）, 2-HEPTANONE（2-heptanone）, 3- heptanone（3-heptanone）, methyln-hexyl ketone（2-octanone）, hexamethylene Ketone（cyclohexanone）, cyclopentanone（cyclopentanone）, methyl iso-butyl ketone (MIBK)（methyl isobutyl ketone） Deng ketone（ketone）Class solvent；Ethyl acetate（ethyl acetate）, propyl acetate（propyl acetate）, butyl acetate （Butyl acetate）Deng ester（ester）Class solvent；N,N-dimethylformamide（N, N-dimethylformamide） (DMF), DMAC N,N' dimethyl acetamide（N, N-Dimethylacetamide）, 1-METHYLPYRROLIDONE（N- methylpyrrolidone）（NMP）Deng acid amides（Amide）Class solvent.
The usage amount of solvent is suitably set according to the condition of polymerisation.As a rule, the mass ratio with polymeric composition exists 0.1 ~ 100 times or so more suitable, and 0.2 ~ 20 times or so more preferably.Above-mentioned solvent both can be used alone one kind, can also be by two Combination of the above is planted to use.
Polymerization initiator can use known species.The specific example of polymerization initiator if any：Benzoyl peroxide first Acyl（benzoyl peroxide）, dibutyl peroxide（Dibutyl Peroxide）, cumyl hydroperoxide（cumene hydroPeroxide）Deng peroxide；Azodiisobutyronitrile（azobisisobutyronitrile）, azo it is double（2,4- bis- Methyl valeronitrile）（azobis（2,4-dimethylvaleronitrile））Deng azo（azo）Type of Collective initiator.Above-mentioned polymerization Initiator can be used alone one kind, can also be used in combination of two or more.The usage amount of polymerization initiator is not limited especially It is fixed, it is 0.1 ~ 10 mass % or so for the quality of polymeric composition as a rule.
The temperature of polymerisation is suitably set according to reaction condition.As a rule, as long as temperature is in room temperature（25°C）~ Below the boiling point of used solvent.In addition, in order to adjust resulting acrylic resin（acrylic resin）（C-2） The degree of polymerization, mercaptan can also be added in polymerisation class material（mercaptan）The chain-transferring agents such as class or hydroquinones （hydroquinone）Deng polymerization inhibitor.
In order to meet adhesion, heat resistance, durability, intermiscibility（compatibility）, the various property such as coating performance Can, the acrylic resin as above obtained（acrylic resin）（C-2）Weight average molecular weight（Mw）For 1,000 ~ 1,500,000 It is relatively appropriate, between 5,000 ~ 1,000,000 more preferably.
（Epoxy（epoxy ）Resin is with containing carboxyl（carboxyl group）The mixing ratio of resin）
In the present invention, bis-phenol（bisphenol）Type epoxy（epoxy ）Resin（A）And novolaks（Novolac）Type epoxy （epoxy）Resin（B）Mixture and polyurethane（polyurethane）Resin（C-1）And acrylic resin（acrylic resin）（C-2）Mixing ratio be preferably 70：30~30：70.It is disposed within above range, good film-forming property, and heat resistance It is easy to adjustment, thus it is more suitable.
（Other compositions）
On the conductive adhesive composition in the present invention, except above-mentioned（A）、（B）、（C）In addition, participation hardening had better not be added anti- The composition answered.I.e., it is generally the case that had better not contain and epoxy（epoxy）The epoxy that compound is used together（epoxy）Firmly Agent.
The conductive adhesive composition of the present invention is particularly suitable in soft circuit base plate binding substrate and electric conductivity supporting material. When using it for the purposes, it is preferred to use do not contain above-mentioned epoxy（epoxy）The type of curing agent.
On purposes, it will hereafter be discussed in greater detail., it is necessary to be binded by hot pressing after preliminary bonding has been carried out, but Due to manufacturing step, taken care of for a long time after preliminary bonding sometimes（More than one week）, hot pressing is then carried out again. Now, heating stepses when may tentatively bind can cause sclerous reaction to proceed by, and sclerous reaction progress is fast during keeping Speed, enough bonding strengths can not be obtained by thus causing hot pressing to be binded in step.
Under the circumstances, without using above-mentioned epoxy（epoxy）Curing agent, is not in thus above mentioned problem, i.e., Making to take care of peel strength that a very long time carries out after hot pressing bonding, bonding step again after preliminary bonding also can be in 10N/cm More than, good cement properties can be kept, thus it is more suitable.
The curing agent that should not be used in the present invention refers to be used to promote polyurethane（polyurethane）Resin and epoxy （epoxy）The reaction of resin promotes epoxy（epoxy）The material of reaction between resin.This curing agent if any：Isocyanic acid Ester（isocyanate）Compound, contain hydroxyl（hydroxyl group）Compound, carbodiimides （carbodiimide）Compound, oxazolines（oxazoline）Compound, silanol（silanol）Compound, aziridine （Aziridine）Compound, acid anhydrides（acid anhydride）Compound, tertiary amine（tertiary amine）Compound, phosphatization Hydrogen（phosphine）Compound, imidazoles（imidazole）Compound etc., but not limited to this.As long as in addition, possessing the present invention's Feature, as long as the peel strength after above-mentioned hot pressing bonding step can be met if more than 10N/cm, can also be added above-mentioned Curing agent.Usage amount for example now relative to（A）~（C）The total amount of composition is in below 0.1 weight %.
（Electroconductive stuffing（D））
The conductive adhesive composition of the present invention contains electroconductive stuffing（D）.Above-mentioned electroconductive stuffing（D）It is not particularly limited, for example Metal packing, coating metal resin extender, carbon can be used（carbon）Filler and its mixture.Above-mentioned metal packing has copper Powder, silver powder, nickel powder, silver-coated copper powder, golden copper-clad powder, silver coated nickel powder, golden nickel coat powder, above-mentioned metal powder can pass through electrolysis, mist Change method（atomization method）, reducing process obtains.
In addition, in order that being easier to contact between filler, the average grain diameter of electroconductive stuffing is preferably 3 ~ 50 μm.In addition, The shape of electroconductive stuffing is if any spherical, sheet, dendroid, threadiness etc..
Consider from viewpoints such as interconnection resistance, costs, above-mentioned electroconductive stuffing（D）Be preferably selected from by silver powder, silver-coated copper powder, At least one in the group of copper powder composition.
On above-mentioned electroconductive stuffing（D）Content, preferably for the total amount of conductive adhesive composition be 40 ~ 90 weights Measure %.
In addition, silane coupler can also be added in conductive adhesive composition（silane coupling agent）, it is anti-oxidant Agent, pigment, dyestuff, tackifier resins（tackifier resin）, plasticizer, ultra-violet absorber, defomaing agent, leveling agent （leveling agent）, filler, fire retardant etc., as long as being controlled do not make reflux-resisting welded (reflow）Property deterioration model In enclosing.
（Conductive adhesive composition）
On the conductive adhesive composition of the present invention, above-mentioned each composition is reacted and is obtained after conductive adhesive composition, be coated on Film is formed on base material, can serve as conducting resinl with this uses.When conductive adhesive composition is coated on into formation film on base material, Following preparation methods can be used：Dissolving or dispersed electro-conductive glue constituent, are then coated on base material in a solvent, according to Need to be dried, form film.
（Conductive adhesive film）
The conductive adhesive film of the present invention can pass through the coating on mould release membrance（coating）Conducting resinl and be made.Coating（coating） Method is not particularly limited, and can use with die coating（die-coating）, die lip coating（lip coating ）, scraper Formula is coated with（comma coating）For the coating of representative（coating）Machine known to machine etc..In addition, being applied by conducting resinl Plating（coating）To after mould release membrance, it can be dried as needed.Drying condition now can be from the viewpoint of productivity ratio The condition that setting of setting out is best suitable for.
Mould release membrance can use the film being obtained as below：In PET（polyethyleneterephtha late）, PEN（polyethylenenaphthalate）Deng on basement membrane, by silicon（silicon）Class is non- Silicon（silicon）Class releasing agent is coated on the surface for being formed with conductive adhesive layer side.The thickness of mould release membrance is not set especially, can Suitably to be set from the viewpoint of easy to use.
The thickness of the conductive adhesive layer formed on mould release membrance is preferably 15 ~ 100 μm.If less than embeddability at 15 μm not It is good, and then cost can be raised more than 100 μm, and the requirement of filming can not be met.Its thickness is set to above range, when When there are bumps on base material, recess can be filled out by appropriate flowing, so deformed, can closely binded, Therefore it is more suitable.
（Adhesive method）
Illustrate the application method of the conductive adhesive film of the present invention below.The purposes of the conductive adhesive film is not particularly limited, for example can be with Use it for binding stiffening plate on circuit base plate.Particularly when stiffening plate is electric conductivity stiffening plate, except binding the metal Beyond stiffening plate processed, it can be also used for making being powered between the ground electrode in circuit base plate main body and the metal stiffening plate.
The material of circuit base plate main body is not particularly limited, as long as with insulating properties and the material of insulating barrier can be formed Material, its representation example is if any polyimides（polyimide）Resin etc..
Metallic plate is preferred in the stiffening plate of electric conductivity, and metallic plate can use stainless steel plate, iron plate, copper coin or aluminium sheet Deng.Wherein it is advisable with stainless steel plate.Also there are enough strength support electronics zero if using stainless steel plate, during the thinner thickness of plate Part.The thickness of electric conductivity stiffening plate is not particularly limited, and is advisable with 0.025 ~ 2mm, and 0.1 ~ 0.5mm is more preferably.Electric conductivity reinforcement Plate within the range when, simply can be built in small machines, and with enough strength support actual installations Electronic component.
Described electronic component is if any chip parts such as connector, IC, resistor, capacitor etc. herein.
The adhesive method of the present invention is made up of following steps：Step（1）, the tentatively bonding of above-mentioned conductive adhesive film is being binded Base material（X）--- on stiffening plate or flexible base plate；Step（2）, in step（1）Obtained have conductive adhesive film by bonding base Material（X）Upper superposition is as by bonding base material（Y）Flexible base plate or stiffening plate, carry out hot pressing.
Above-mentioned conductive adhesive film is particularly suitable for use in soft circuit base plate binding flexible base plate and stiffening plate.That is, as contrasted Described in file 4, using metallic plate of electric conductivity etc. as stiffening plate, binded with conductive adhesive composition to soft circuit base plate On, electromagnetic wave shielding function is obtained by stiffening plate.
When binding stiffening plate by the above method, the conductive adhesive film in the present invention has good cement properties, effect It is excellent.That is, when taking care of certain time after preliminary bonding, sclerous reaction can be very slow, therefore is formally being sticked by hot pressing It is not in the situation that cement properties decline during conjunction.
In the adhesive method of the present invention, conductive adhesive film is tentatively binded by bonding base material first（X）On.By bonding base Material（X）Both it can be that stiffening plate can also be flexible base plate, but stiffening plate is preferred.Condition during preliminary bonding is without special Limit, as long as conductive adhesive film can be fixed on by bonding base material, binded in the case where not shifting, but Preferably with face bonding mode, non-dots is binded.That is, whole bond area is preferably tentatively binded.
Can tentatively it be binded by forcing press, bonding condition can be for example set to：Temperature：120 °C, time：5 seconds, Pressure：0.5MPa.
In step（1）In it is preliminary binded conductive adhesive film by bonding base material（X）Step can be carried out immediately（2）, also may be used To carry out step（2）Time of more than one week is first taken care of before.Even if a big advantage of the conductive adhesive composition of the present invention is It will not also decline in partially hardened postadhesion performance.
Step（2）It is from step（1）Obtain, with conductive adhesive film by bonding base material（X）On upper stripping conductive adhesive film Mould release membrance, be then superimposed by bonding base material（Y）--- flexible base plate or stiffening plate, carry out hot pressing.By bonding base material（X）With quilt Bind base material（Y）Relation be：One side is stiffening plate, and the opposing party is flexible base plate.
Hot pressing can be carried out under normal conditions, for example, can carry out under the following conditions：1~5MPa、140~190°C、15 ~ 90 points.
（Circuit base plate）
The present invention circuit base plate at least a portion have by flexible base plate, conductive adhesive composition and electric conductivity stiffening plate according to The position of this statement order lamination.This circuit base plate can both be binded by above-mentioned adhesive method, can also be led to Cross the acquisition of other adhesive methods.The schematic diagram of the circuit base plate is shown in Fig. 4.In Fig. 4, circuit base plate and stiffening plate pass through the present invention Conductive adhesive composition binded, can be powered.
In above-mentioned circuit base plate, electric conductivity stiffening plate is preferably existed only in a part for circuit base plate.That is, preferably set Being calculated as the part of electronic component has the structure of stiffening plate.
In the circuit base plate of the present invention, preferably make at least a portion in face beyond above-mentioned stiffening plate by electromagnetic wave shielding Film is coated to.That is, electromagnetic shielding film both can only be coated to the part in the face beyond stiffening plate, can also be coated to stiffening plate with The entire surface in outer face.Now, electromagnetic shielding film can also be overlapped with least a portion of stiffening plate.Thus can be whole Good electromagnetic wave shielding function is obtained in circuit base plate, thus it is more suitable.Electromagnetic shielding film is not particularly limited, to have There are the structure of the tropism conductive adhesive layer such as insulating barrier or the structure with insulating barrier metal level anisotropy conductiving glue layer to be advisable.
Embodiment
The present invention is illustrated by the following examples, but the present invention is not limited to following embodiments.Do not saying especially In the case of bright, " part " and " % " in embodiment and comparative example refers to quality criteria.
（1）＜ polyurethane（polyurethane）Resin（C-1）Synthesis ＞
[synthesis example c1：Containing carboxyl（carboxyl group）Polyurethane（polyurethane）Ammoniacum（urethaneurea）]
Prepare mixer, reflux condensing tube, thermometer, nitrogen and be blown into pipe and with wellhole（manhole）Reaction vessel.Use nitrogen The gas of reaction vessel interior is replaced, dihydromethyl propionic acid is then placed in（dimethylol propionic acid）（DMPA） 6.0g, poly- carbonic acid hexylene glycol esterdiol（poly hexamethylene carbonate diol）（Trade name " PLACCEL CD （A kind of name of product, Japanese is " プ ラ Network セ Le CD "）220 ", daicel Co., Ltd. produces, and terminal functional group quantifies The number-average molecular weight arrived is 2000）100g and dimethylformamide（dimethylformamide）(DMF) 59.0g.Then Add hexamethylene diisocyanate（hexamethylene diisocyanate）（HDI）31.9g（For OH bases, NCO bases are 2 times of equivalents）, reacted at 90 °C, until the NCO bases of resin reach the 4.0% of theoretical value, obtain urethane Ester（urethane）Pre-polymer solution.In resulting urethanes（urethane）Added in pre-polymer solution DMF298.5g, is cooled to 40 °C, and drip IPD（isophorone diamine）（IPDA）16.1g, with amino first Acetoacetic ester（urethane）The NCO bases of prepolymer are reacted.It is stirred, until infrared absorption spectrum analysis is determined, trip Free isocyanate groups（isocyanate group）Absorption to 2,270cm-1 disappears, and obtains acid value for 16.4mgKOH/g, number Average molecular weight（Mn）For 50,000, weight average molecular weight（Mw）For 105,000 polyurethane（polyurethane）Resin（c1）'s DMF solution（Solid concentration 30%）.
[synthesis example c2：Containing carboxyl（carboxyl group）Polyurethane（polyurethane）（Without urea bond（urea bond））]
Prepare mixer, reflux condensing tube, thermometer, nitrogen and be blown into pipe and with wellhole（manhole）Reaction vessel.With The gas of nitrogen displacement reaction vessel interior, is then placed in DMPA6.0g, BDO（Isosorbide-5-Nitrae-butane diol）6.0g, PLACCEL CD（A kind of name of product, Japanese is " プ ラ Network セ Le CD "）220 100g and DMF139.1g.Then plus Enter HDI27.1g（For OH bases, NCO bases are equivalent）, it is stirred at 90 °C, until infrared absorption spectrum analysis is surveyed Surely obtain, free isocyanate groups（isocyanate group）Absorption to 2,270cm-1 disappears, and then adds DMF185.5g, obtains acid value for 18.1mgKOH/g, number-average molecular weight（Mn）For 52,000, weight average molecular weight（Mw）For 112, 000 polyurethane（polyurethane）Resin（c2）DMF solution（Solid concentration 30%）.It is true by infrared absorption spectroscopy Recognize polyurethane（polyurethane）Resin（c2）There is no urea bond（urea bond）.
[synthesis example c3：Containing carboxyl（carboxyl group）Polyurethane（polyurethane）（There is urea bond（urea bond））]
Prepare mixer, reflux condensing tube, thermometer, nitrogen and be blown into pipe and with wellhole（manhole）Reaction vessel.With The gas of nitrogen displacement reaction vessel interior, is then placed in DMPA6.0g, PLACCEL CD（A kind of name of product, Japanese is " プ ラ Network セ Le CD "）220 100g, DMF70.8g.Then IPDI is added（isophorone diisocyanate）（IPDI）42.1g（For OH bases, NCO bases are 2 times of equivalents）, reacted at 90 °C, until tree The NCO bases of fat reach the 3.6% of theoretical value, obtain urethanes（urethane）Pre-polymer solution.To resulting amino Ethyl formate（urethane）DMF312.3g is added in pre-polymer solution, 40 °C are cooled to, then drip IPDA16.1g, makes it With urethanes（urethane）The NCO bases reaction of prepolymer.It is stirred, until infrared absorption spectrum analysis is determined , free isocyanate groups（isocyanate group）Absorption to 2,270cm-1 disappears, and it is 15. to obtain acid value 3mgKOH/g, number-average molecular weight（Mn）For 50,000, weight average molecular weight（Mw）For 102,000 polyurethane（polyurethane） Resin（c3）DMF solution（Solid concentration 30%）.
[compare synthesis example c4：There is no carboxyl（carboxyl group）]
Prepare mixer, reflux condensing tube, thermometer, nitrogen and be blown into pipe and with wellhole（manhole）Reaction vessel.With The gas of nitrogen displacement reaction vessel interior, is then placed in BDO（Isosorbide-5-Nitrae-butane diol）4.0g, CD220 100g and DMF58.2g.Then HDI31.7g is added（For OH bases, NCO bases are 2 times of equivalents）, in 90 °C of progress Reaction, until the NCO bases of resin reach the 4.1% of theoretical value, obtains urethanes（urethane）Pre-polymer solution.To The urethanes of acquisition（urethane）DMF295.8g is added in pre-polymer solution, 40 °C are cooled to, drip IPDA16. 0g, makes itself and urethanes（urethane）The NCO bases of prepolymer are reacted.It is stirred, until infrared absorption light Analysis of spectrum is determined, free isocyanate groups（isocyanate group）Untill being disappeared to 2,270cm-1 absorption, obtain Without carboxyl（carboxyl group）, number-average molecular weight（Mn）For 52,000, weight average molecular weight（Mw）For 109,000 it is poly- Urethane（polyurethane）Resin（c4）DMF solution（Solid concentration 30%）.
（2）＜ acrylic resins（acrylic resin）（C-2）Synthesis ＞
[synthesis example c5：Containing carboxyl（carboxyl group）Acrylic resin（acrylic resin）]
Prepare mixer, reflux condensing tube, thermometer, nitrogen and be blown into pipe and with wellhole（manhole）Reaction vessel.With The gas of nitrogen displacement reaction vessel interior, is then placed in methyl ethyl ketone（methyl ethyl ketone）（MEK）100g, 80 °C are heated in a nitrogen environment.Prepare methyl methacrylate（methyl methacrylate）5g, methacrylic acid 2- Octyl Nitrite（2-Ethylhexyl methacrylate）Positive ten diester of 65g, methacrylic acid（N-Lauryl methacrylate）25g, methacrylic acid（methacrylic acid）5g and 2,2 '-azo two（2,4- dimethyl-pentens Nitrile）（2,2 '-azobis（2,4-dimethylvaleronitrile））2g mixture.By the 1/3 of mixture added to instead Answer in container, remaining part is instilled in reaction vessel by dropping funel with 1 hours.After dripping, shape at that time is kept State, reacts 6 hours, obtains acid value for 32.5mgKOH/g, weight average molecular weight（Mw）For 29,000, number-average molecular weight（Mn）For 10, 000th, Tg calculated value is -18.5 °C of acrylic resin（acrylic resin）（c5）Solution（Solid concentration 50%）.
[compare synthesis example c6：There is no carboxyl（carboxyl group）]
Prepare mixer, reflux condensing tube, thermometer, nitrogen and be blown into pipe and with wellhole（manhole）Reaction vessel.With After the gas of nitrogen displacement reaction vessel interior, methyl ethyl ketone is added（methyl ethyl ketone）（MEK）100g, 80 °C are heated under nitrogen environment.Prepare methyl methacrylate（methyl methacrylate）10g, methacrylic acid 2- Octyl Nitrite（2-Ethylhexyl methacrylate ）Positive ten diester of 65g, methacrylic acid（N-Lauryl methacrylate）25g, 2,2 '-azo two（2,4- methyl pentane nitriles）（2,2 '-azobis（2,4- dimethylvaleronitrile））2g mixture.The 1/3 of mixture is added in reaction vessel, remainder passes through Dropping funel was dripped in reaction vessel with the time of 1 hour.After dripping, state of remaining stationary simultaneously is reacted 6 hours, obtains Weight-average molecular Amount（Mw）For 35,000, number-average molecular weight（Mn）For 14,000, the acrylic resin that Tg calculated value is -19.1 °C （acrylic resin）（c6）Solution（Solid concentration 50%）.
（The manufacture method of embodiment membrane sample）
Illustrate the manufacture method of the conductive adhesive film of each embodiment, each reference example and each comparative example below.Various materials are combined, are made Certain paste.Pass through wing（doctor blade）（Flat spatula）It is coated with by hand（hand coat）Method by its It is coated on the PET for having carried out release processing（polyethylene terephthalate）On film, dry 100 °C × 3 points, conductive adhesive film is made.On wing（doctor blade）, according to the thickness for the conductive adhesive film to be made not Together, 1mil ~ 5mil product can suitably be selected.Here, 1mil=1/1000 inches=25.4 μm.In each embodiment, ginseng Examine when each conductive adhesive film is made in example, comparative example, the thickness of conductive adhesive film is certain thickness.Here, the thickness of conductive adhesive film Measured by mircrometer gauge.
[table 1]
Here, listed each composition uses the composition in table 2 below in table 1.
Curing agent uses tertiary amine（tertiary amine）Compound（Mitsubishi Chemical's production, trade name jER3010）.
[table 2]
Electroconductive stuffing in table 1 uses following substances.
Electroconductive stuffing D-1：Silver powder（Average grain diameter is 12 μm, Fukuda Metal Foil ＆ POwder Co., Ltd.'s production）
Electroconductive stuffing D-2：Silver-coated copper powder（Average grain diameter is 20 μm, Fukuda Metal Foil ＆ POwder Co., Ltd.'s production）
Electroconductive stuffing D-3：Silver-coated copper powder（Average grain diameter is 25 μm, Fukuda Metal Foil ＆ POwder Co., Ltd.'s production）
（Adhesive method）
Utilize hot press（Temperature：120 °C, time：5 seconds, pressure：0.5MPa）It is by hot pressing that stiffening plate and conductive adhesive film is preliminary Stick together, then peel the stripping film on conductive adhesive film off, tentatively binded with flexible base plate by above-mentioned preliminary adhesive method Together, then reusable heat press（Temperature：170 °C, time：30 points, pressure：3MPa）Carry out hot pressing.
（Evaluation method）
One week is first taken care of when carrying out hot pressing within 1 hour after above-mentioned preliminary bonding and after preliminary bonding again The situation for carrying out hot pressing is evaluated respectively, evaluates its peel strength, interconnection resistance value, reflux-resisting welded (reflow）Property, resin Flowing（resin flow）, reliability test.Herein, it is envisioned that situation about preserving for a long time occurs, conditioning to 23 °C, 60%RH indoor preservation one week.
（Peel strength）
Pass through the adhesion force between 90 ° of disbonded test measure and stiffening plate.Specifically, as shown in figure 1, passing through stainless steel plate （Width 10mm, length 100mm）, with polyimides（polyimide）Polyamides in layer and the copper-clad laminated board of film-form layers of copper Imines（polyimide）Conductive adhesive film in the surface side of layer and the present embodiment, according to conducting resinl in above-mentioned embodiment The explanation of the application method of film, is pressed, and then pulls stripping copper-clad laminated board to vertical direction.If in more than 10N/cm Then explanation has no problem, and can use.
（Interconnection resistance value）
Electrical characteristic evaluation has been carried out to the circuit base plate with metal reinforcement plate being made in aforementioned manners.In simulation connection member Aperture（opening size）Conducting resinl is pressed into for the position on diameter 1.0mm ground wire soft printing substrate between stiffening plate Film, determines the interconnection resistance of the circuit base plate now with metal reinforcement plate（Between Fig. 2 electrode）.If numerical value is in 1 below Ω It is to ensure that shielding properties.
（Reflux-resisting welded (reflow）Property)
Carry out Reflow Soldering (reflow）Evaluation afterwards.On Reflow Soldering (reflow）Temperature conditionss, it is assumed that use Pb-free coating Material, sets a kind of maximum temperature as 265 °C of temperature curve（temperature profile）.By the position between stiffening plate Put press-in conductive adhesive film, the circuit base plate test film with metal reinforcement plate pass through IR Reflow Solderings (reflow）5 times, observation whether there is Expansion.
（Resin flows（resin flow））
For the circuit base plate with metal reinforcement plate being made in aforementioned manners, resin flowing is determined（resin flow）Distance. From the circuit base plate with metal reinforcement plate that stiffening plate unilateral observation is produced when, determine the conducting resinl overflowed below the stiffening plate The distance of one end and stiffening plate one end.If the distance is below 300 μm, illustrate to have no problem, can use.
（Reliability test）
By the disbonded test test film made in aforementioned manners and interconnection resistance measure test film in high-temperature high-humidity environment Under（85°C、85%）Place 1000 hours, respective peel strength and interconnection resistance are then determined respectively.
Evaluation result is as shown in table 3 below.
[table 3]
From the results shown in Table 3, conductive adhesive composition of the invention has good physical property and electrical properties.This Outside, carried out preserving for a long time after preliminary bonding, also can guarantee that good cement properties.In addition, being binded in tool When having on the base material of difference of height, good cement properties, electric conductivity are also resulted in.
The possibility that industry is utilized
The conductive adhesive composition of the present invention is particularly suitable for use in binding stiffening plate and flexible base plate that metal is made.
Label declaration
1. metal reinforcement plate（Ni-SUS is made）
2. electrode（Ni-Au electroless treatments）
3. resin flows（resin flow）
4.GND（Ni-Au electroless treatments）
5. conducting resinl
6. covering layer film
7. copper foil layer
8. copper-clad laminated board
9. at interconnection resistance measure

Claims (13)

1. a kind of conductive adhesive composition, it is characterised in that：
The conductive adhesive composition contains：
It is the bisphenol-type epoxy resin of solid under each molecule epoxy radicals containing two or more and normal temperature（A）、
It is the phenolic resin varnish type epoxy resin of solid under each molecule epoxy radicals containing two or more and normal temperature（B）、
Containing carboxy resin（C）And
Electroconductive stuffing（D）,
Wherein contain carboxy resin（C）Contain polyurethane resin containing carboxyl（C-1）.
2. conductive adhesive composition according to claim 1, it is characterised in that：
Bisphenol-type epoxy resin（A）And phenolic resin varnish type epoxy resin（B）Ratio be：Weight compares 85：15~99：1.
3. conductive adhesive composition according to claim 1 or 2, it is characterised in that：
Above-mentioned bisphenol-type epoxy resin（A）Middle epoxide equivalent is 800~10000.
4. conductive adhesive composition according to claim 1 or 2, it is characterised in that：
Above-mentioned phenolic resin varnish type epoxy resin（B）Middle epoxide equivalent is 90~300.
5. conductive adhesive composition according to claim 1 or 2, it is characterised in that：
Electroconductive stuffing（D）It is at least one in following group：The group being made up of silver powder, silver-coated copper powder, copper powder.
6. conductive adhesive composition according to claim 1 or 2, it is characterised in that：Electroconductive stuffing（D）Average grain diameter be 3~50μm。
7. conductive adhesive composition according to claim 1 or 2, it is characterised in that：
Bisphenol-type epoxy resin is not contained（A）, phenolic resin varnish type epoxy resin（B）And containing carboxy resin（C）Hardening in addition Agent.
8. a kind of conductive adhesive film, the conductive adhesive film is to use the conducting resinl in the claims 1 ~ 7 described in any one to constitute Formed by conductive adhesive layer and the protective layer lamination of thing.
9. conductive adhesive film according to claim 8, it is characterised in that：
The thickness of conductive adhesive layer is 15 ~ 100 μm.
10. conductive adhesive film according to claim 8 or claim 9, it is characterised in that：
It is set tentatively to bind peel strength when carrying out hot pressing bonding after 1 week in more than 10N/cm with forcing press.
11. a kind of adhesive method, this method is made up of following steps：
Step（1）：Conductive adhesive film described in any one in the claims 8 ~ 10 is tentatively binded as by bonding base material （X）Electric conductivity stiffening plate or flexible base plate on,
Step（2）：Passing through step（1）Obtain have conductive adhesive film by bonding base material（X）Upper superposition is as by bonding base Material（Y）Flexible base plate or electric conductivity stiffening plate, and carry out hot pressing.
12. a kind of circuit base plate, it is characterised in that：
At least a portion of the circuit base plate have by flexible base plate, conductive adhesive layer and electric conductivity stiffening plate according to this statement sequentially The position being laminated, wherein, conductive adhesive layer is formed as the conductive adhesive film described in any one in claim 8 ~ 10.
13. circuit base plate according to claim 12, it is characterised in that：
Face of the flexible base plate surface in addition to stiffening plate is coated with electromagnetic shielding film.
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Cited By (3)

* Cited by examiner, † Cited by third party
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CN109943252A (en) * 2019-02-28 2019-06-28 苏州金枪新材料股份有限公司 A kind of wicker copper conducting resinl and preparation method thereof
CN111512398A (en) * 2018-04-12 2020-08-07 东洋纺株式会社 Conductive paste

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104487534B (en) * 2012-07-11 2016-11-09 大自达电线股份有限公司 Hardening conductive adhesive composition, electromagnetic shielding film, conductive adhesive film, adhesive method and circuit base plate
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WO2016076096A1 (en) * 2014-11-12 2016-05-19 デクセリアルズ株式会社 Heat-curable adhesive composition
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101120627A (en) * 2005-02-18 2008-02-06 东洋油墨制造株式会社 Electromagnetic-wave-shielding adhesive film, process for producing the same, and method of shielding adherend from electromagnetic wave
CN101133096A (en) * 2005-03-04 2008-02-27 昭和电工株式会社 Carboxyl group-containing polyurethane and thermosetting resin composition using the same
CN101268163A (en) * 2005-09-16 2008-09-17 东洋油墨制造株式会社 Bonding agent composition, bonding agent tablet using same and its uses

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09263683A (en) * 1996-03-29 1997-10-07 Sumitomo Kinzoku Electro Device:Kk Electroconductive epoxy resin composition
JP4275221B2 (en) * 1998-07-06 2009-06-10 リンテック株式会社 Adhesive composition and adhesive sheet
JP2000086981A (en) * 1998-09-17 2000-03-28 Nitto Denko Corp Sheetlike adhesive composition and its production
JP2000129216A (en) * 1998-10-26 2000-05-09 Nitto Denko Corp Sheet-like adhesive composition, electronic component device prepared by using same, and method of repairing the device
JP2000129217A (en) * 1998-10-26 2000-05-09 Nitto Denko Corp Sheet-like adhesive composition, electronic component device prepared by using same, and method of repairing the device
JP3904798B2 (en) * 1999-04-01 2007-04-11 三井化学株式会社 Anisotropic conductive paste
JP2001115127A (en) 1999-10-19 2001-04-24 Hitachi Chem Co Ltd Electrically conductive adhesive and wiring board using the same
JP2001332124A (en) * 2000-05-22 2001-11-30 Toshiba Chem Corp Conductive paste and optical semiconductor device
JP2005184022A (en) * 2000-12-14 2005-07-07 Hitachi Chem Co Ltd Heat for connection/electrical conductive film, and application thereof
JP2003082318A (en) * 2001-09-13 2003-03-19 Three M Innovative Properties Co Cationically polymerizable adhesive composition and anisotropically electroconductive adhesive composition
JP2005264095A (en) * 2004-03-22 2005-09-29 Kyoto Elex Kk Conductive resin composition and conductive paste
JP4843979B2 (en) 2004-03-30 2011-12-21 住友ベークライト株式会社 Circuit board
JP4828151B2 (en) * 2005-04-15 2011-11-30 タツタ電線株式会社 Conductive adhesive sheet and circuit board
KR20080109895A (en) * 2006-04-27 2008-12-17 스미토모 베이클리트 컴퍼니 리미티드 Adhesive tape, semiconductor package, and electronic device
JP4933217B2 (en) * 2006-10-26 2012-05-16 タツタ電線株式会社 Conductive adhesive
KR100787727B1 (en) * 2006-10-31 2007-12-24 제일모직주식회사 Anisotropic conductive film composition using styrene-acrylonitrile copolymer for high reliability
JP5348867B2 (en) * 2007-09-28 2013-11-20 株式会社きもと Adhesive and adhesive sheet
JP5487419B2 (en) * 2008-02-12 2014-05-07 タツタ電線株式会社 Conductive adhesive sheet, wiring board including the same, and method for producing conductive adhesive sheet
JP2009290195A (en) * 2008-04-30 2009-12-10 Toyo Ink Mfg Co Ltd Curable electromagnetic shielding adhesive film, and method for manufacturing the same
JP2010143981A (en) 2008-12-17 2010-07-01 Toyo Ink Mfg Co Ltd Curable electroconductive polyurethane polyurea adhesive composition, curable electromagnetic wave shielding adhesive film, and method for producing the same
JP5257125B2 (en) * 2009-02-20 2013-08-07 東洋インキＳｃホールディングス株式会社 Curable flame retardant electromagnetic shielding film
JP2010229282A (en) * 2009-03-27 2010-10-14 Toyo Ink Mfg Co Ltd Polyurethane polyurea resin composition, curable adhesive film with electromagnetic wave-shielding property and method of manufacturing the same
JP5742112B2 (en) * 2010-01-18 2015-07-01 東洋インキＳｃホールディングス株式会社 Curable electromagnetic wave shielding adhesive film and method for producing the same
JP5528857B2 (en) * 2010-03-11 2014-06-25 タツタ電線株式会社 Electromagnetic wave shielding film, flexible substrate using the same, and method for producing the same
WO2012011265A1 (en) * 2010-07-23 2012-01-26 タツタ電線株式会社 Adhesive agent composition and adhesive film
JP5840131B2 (en) * 2010-09-13 2016-01-06 株式会社カネカ Reinforcing plate integrated flexible printed circuit board, and reinforcing plate integrated flexible printed circuit board
CN102443370A (en) * 2010-10-15 2012-05-09 深圳市道尔科技有限公司 Low-halogen high-conductivity single-ingredient conductive gum
JP5662104B2 (en) * 2010-10-26 2015-01-28 京セラケミカル株式会社 Conductive resin composition and semiconductor device using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101120627A (en) * 2005-02-18 2008-02-06 东洋油墨制造株式会社 Electromagnetic-wave-shielding adhesive film, process for producing the same, and method of shielding adherend from electromagnetic wave
CN101133096A (en) * 2005-03-04 2008-02-27 昭和电工株式会社 Carboxyl group-containing polyurethane and thermosetting resin composition using the same
CN101268163A (en) * 2005-09-16 2008-09-17 东洋油墨制造株式会社 Bonding agent composition, bonding agent tablet using same and its uses

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111512398A (en) * 2018-04-12 2020-08-07 东洋纺株式会社 Conductive paste
CN111512398B (en) * 2018-04-12 2022-09-30 东洋纺株式会社 Conductive paste
CN109943252A (en) * 2019-02-28 2019-06-28 苏州金枪新材料股份有限公司 A kind of wicker copper conducting resinl and preparation method thereof
CN109897567A (en) * 2019-03-13 2019-06-18 松裕印刷包装有限公司 A kind of PETG heat shrink films suitable for high speed hand middle-envelope bag-made machine are puted the palms together before one glue

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