CN106947409B - 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
CN106947409B
CN106947409B CN201610849680.3A CN201610849680A CN106947409B CN 106947409 B CN106947409 B CN 106947409B CN 201610849680 A CN201610849680 A CN 201610849680A CN 106947409 B CN106947409 B CN 106947409B
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conductive adhesive
resin
adhesive composition
type epoxy
base plate
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CN106947409A (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
    • 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
    • C08K3/00—Use of inorganic 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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    • 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
    • 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
    • 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
    • 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
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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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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)
  • Structure Of Printed Boards (AREA)
  • Conductive Materials (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Combinations Of Printed Boards (AREA)

Abstract

There is provided that a kind of crosslink density is high, the physical property of adhesive-layer after hardening is high and the superior conductive adhesive composition of processing performance and the conductive adhesive film for having used the conductive adhesive composition.A kind of conductive adhesive composition, it is characterized by: the conductive adhesive composition contains: each molecule containing be under more than two epoxy groups and room temperature the bisphenol-type epoxy resin (A) of solid, each molecule containing be the phenolic resin varnish type epoxy resin (B) of solid under more than two epoxy groups and room temperature, containing containing carboxy resin (C) and electroconductive stuffing (D), wherein, (C) containing carboxy resin is made of at least one of following substance: polyurethane resin containing carboxyl (C-1) and 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 At object, 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 plates.
Background technique
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, the requirement to the physical property of above-mentioned conducting resinl is also higher and higher. Specifically, increasingly such as the requirement to a variety of physical properties heat resistance, physical strength, water resistance, moisture-proof, electrical property It is high.
Patent document 1 ~ 3 discloses one kind and contains polyurethane polyureas carbamide resin (polyurethane polyurea resin) And hardenability polyurethane-polyurea (polyurethane polyurea) adhesive composition of epoxy (epoxy, similarly hereinafter) base.? It needs to further increase above-mentioned physical property in this adhesive composition, while needing sufficiently control processing characteristics.
Good heat resistance, physical strength, water resistance, moisture-proof and resistive performance in order to obtain, the method that can be used If any: the crosslink density of the film after improving hardening.In order to obtain the resin of high crosslink density, need to increase reactive site, from this One viewpoint considers, needs to measure more epoxides using functional group (functional group, similarly hereinafter).But function base unit weight is more Molecular weight of epoxy resin it is generally all lower, if being used as conductive adhesive film, be easy overflow (bleed out), exist and be difficult to The problem of processing.That is, needing to be binded as illustrated in fig. 2 at this time, 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 the above problem if any while using two or more epoxy resin, make one of point Son amount is higher, and another molecular weight is lower.But the mixture of this epoxy resin is difficult integrally to occur with epoxy resin uniform Reaction, can not improve whole crosslink density.In addition, if having used containing the low molecular weight epoxy compound compared with polyepoxy If, the epoxy reaction that the epoxide of the low molecular weight most starts is most fast, since second, third, reaction speed Degree is gradually slack-off, so being easy the unreacted epoxy group of remaining, the raising degree of crosslink density can not reach theoretical value.Cause This, it is low that remaining functional group will lead to physical property instead.
Documents 1 have used two kinds of epoxy resin simultaneously.But selection resin is not for same as above-mentioned viewpoint herein The considerations of, but for resin high using softening point low resin and softening point simultaneously, bending is generated with this.Therefore, right Than document 1, there is no studied, the purpose of the documents 1 to improve the crosslink density of hardening thing as in the present invention Not solve the above subject.
In addition, there are also ways as described in Patent Document 4, that is, 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 an example of this circuit base plate.When being used for such purposes, to above-mentioned various physical properties, processing characteristics Requirement it is higher.
Existing technical literature
Patent document
Patent document 1: special open (Japanese Patent Publication) 2010-143981 Patent Document 2: International Publication No. 2007/032463 Patent Document 3: special open (Japanese Patent Publication) 2007-189091 Patent Document 4: Special open (Japanese Patent Publication) 2005-317946 bulletin.
Brief summary of the invention
Subject to be solved by the invention
The present invention is in view of the above subject, and its purpose is to provide a kind of objects of the adhesive-layer after crosslink density height, hardening Rationality matter height and the superior conductive adhesive composition of processing performance 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 bis-phenol (bisphenol) type asphalt mixtures modified by epoxy resin under more than two epoxy groups and room temperature for solid Rouge (A),
Each molecule has novolaks (Novolac) type ring oxygen under more than two epoxy groups and room temperature for solid Resin (B),
Containing carboxyl (carboxyl group) resin (C) and
Electroconductive stuffing (D),
Wherein, (carboxyl group) resin Han carboxyl (C) contains selected from least one of following group substance: by containing Carboxyl (carboxyl group) polyurethane resin (C-1) and contain carboxyl (carboxyl group) polyacrylic acid (polyacrylic) group that resin (C-2) is constituted.
Above-mentioned bis-phenol (bisphenol) type epoxy resin (A) and above-mentioned novolaks (Novolac) type epoxy resin (B) Ratio it is best are as follows: weight ratio 85:15~99:1.
Epoxide equivalent (epoxy equivalent) is preferably 800 in above-mentioned bis-phenol (bisphenol) type epoxy resin (A) ~10000.
Epoxide equivalent (epoxy equivalent) is preferably in above-mentioned novolaks (Novolac) type epoxy resin (B) 90~300.
Above-mentioned electroconductive stuffing (D) is preferably selected from least one of following group: by silver powder, silver-coated copper powder, copper powder structure At group.
The average grain diameter of electroconductive stuffing (D) is preferably 3 ~ 50 μm.
In addition, conductive adhesive composition of the invention is characterized in that: not containing bis-phenol (bisphenol) type epoxy resin (A), the hardening other than novolaks (Novolac) type epoxy resin (B) and (carboxyl group) resin Han carboxyl (C) Agent.
Moreover, it relates to a kind of conductive adhesive film, which is the conduction using above-mentioned conductive adhesive composition Made of glue-line and protective layer lamination.
At this point, the thickness of above-mentioned conductive adhesive composition is preferably 15 ~ 100 μm.
Conductive adhesive film of the invention is characterized in that: first being binded it tentatively with press machine (press machine), is crossed 1 Zhou Houzai carries out hot pressing bonding, and peel strength at this time is in 10N/cm or more.
The present invention relates to a kind of adhesive method, this method is made of following steps:
Step (1): above-mentioned conductive adhesive film is first binded as by the electric conductivity stiffening plate or soft base of bonding substrate (X) On plate,
Step (2): it is sticked in being used as by superposition on bonding substrate (X) with conductive adhesive film obtained by step (1) The flexible base plate or electric conductivity stiffening plate for closing substrate (Y) carry out hot pressing.
The invention further relates to a kind of circuit base plates, it is characterised in that: at least part of the circuit base plate has by soft Position made of substrate, conductive adhesive layer and electric conductivity stiffening plate are laminated according to this statement sequence, wherein conductive adhesive layer is by described What conductive adhesive film was formed.
Face of the flexible base plate surface in addition to stiffening plate is preferably coating with electromagnetic shielding film in above-mentioned circuit base plate.
Invention effect
Conductive adhesive composition of the invention has good heat resistance, physical strength, water resistance, moisture-proof, electrical property, and After pressing step, the ingredient in film is not in overflow problem.It should in addition, being used in the stickup of the substrate with difference of height When invention, it is able to carry out good bonding.In addition, in the case where preservation for a long time after preliminary bonding, it also can be glutinous in hot pressing It closes in step and keeps good cement properties.
Detailed description of the invention
Fig. 1 is the schematic diagram of the peel strength measuring method in embodiment.
Fig. 2 is an example of the interconnection resistance measurement sample in embodiment.
Fig. 3 is the schematic diagram of the resin mobility status in embodiment.
Fig. 4 is an example 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 characterized in that: the conductive adhesive composition contains: there are two each molecule tools Be bis-phenol (bisphenol) the type epoxy resin (A) of solid under above epoxy group and room temperature, each molecule tool there are two with On epoxy group and room temperature under be solid novolaks (Novolac) type epoxy resin (B), (carboxyl containing carboxyl Group) resin (C) and electroconductive stuffing (D), wherein (carboxyl group) resin Han carboxyl (C) contain selected from At least one of lower group substance: by containing carboxyl (carboxyl group) polyurethane resin (C-1) and (carboxyl containing carboxyl Group) the group that polyacrylic acid (polyacrylic) resin (C-2) is constituted.It is formed by this conductive adhesive composition of the invention Crosslink density after bonding coat hardening is uniform, and can obtain higher crosslink density.Therefore it is capable of forming moisture-proof, water-fast The all very superior bonding coat such as property, heat resistance, physical strength, electrical property.In addition, the problems such as being not in spilling when processing, and Good processing characteristics can be obtained.In addition, in the case where preservation 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))
It is solid that epoxy resin used in the present invention (A), which is that each molecule has under more than two epoxy groups and room temperature, Bis-phenol (bisphenol) type epoxy resin of body.Under room temperature for solid be meant that be at 25 °C and in the state of solvent-free Do not have the solid state of mobility now.If above-mentioned bonding coat is only made of novolaks (Novolac) type epoxy resin Words, can have that adhesion property and filming performance are bad, it is therefore necessary to have bis-phenol (bisphenol) type epoxy resin (A).In addition, to obtain good processing performance, it is necessary to use the substance under room temperature being solid.
Above-mentioned bis-phenol (bisphenol) type epoxy resin (A) is not particularly limited, such as can be bis-phenol (bisphenol) A type epoxy resin, bis-phenol (bisphenol) F type epoxy resin, bis-phenol (bisphenol) S type epoxy resin, Tetrabromobisphenol (tetrabromobisphenol) A type epoxy resin etc..Above-mentioned epoxy resin can be used alone, can also 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 ring oxygen Resin or bis-phenol (bisphenol) F type epoxy resin are advisable.
The type that epoxide equivalent is 800 ~ 10000 is preferred in above-mentioned bis-phenol (bisphenol) type epoxy resin (A).This Sample can further increase the cohesive force with stiffening plate, more be suitable for.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.
Can be used as above-mentioned bis-phenol (bisphenol) type epoxy resin (A) Commercial epoxy resins have EPICLON4050, 7050, HM-091, HM-101(trade name, Dainippon Ink Chemicals 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) etc..
Above-mentioned novolaks (novolac) type epoxy resin (B) be a kind of each molecule have more than two epoxy groups, And under room temperature be solid novolaks (novolac) type epoxy resin.The epoxy of novolaks (novolac) type epoxy resin Resin density is high, and good with the Combination of other epoxy resin, and the reaction sex differernce between epoxy group is smaller, so can make to apply The crosslink density of film entirety was not only uniform but also high.
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 Rouge etc..Wherein, from the viewpoint of high adhesion, heat resistance, with phenol novolacs (phenol novolac) type asphalt mixtures modified by epoxy resin Rouge or cresol novolak (cresol novolac) type epoxy resin are advisable.
The epoxide equivalent of above-mentioned novolaks (novolac) type epoxy resin (B) is advisable with 90 ~ 300.It can be improved in this way 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.
Can be used as the Commercial epoxy resins of above-mentioned novolaks (novolac) type epoxy resin (B) 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- 865, N-865-80M(trade name, Dainippon Ink Chemicals's production) jER152,154,157S70(trade name, Mitsubishi Chemical's strain formula Commercial firm's production) 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) etc..
Above-mentioned bis-phenol (bisphenol) the type epoxy resin contained in the conductive adhesive layer of conductive adhesive composition in the present invention (A) and the weight ratio of novolaks (novolac) type epoxy resin (B) is 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 being capable of Reflow Soldering (reflow) step in actual installation components It is middle to guarantee enough heat resistances.About aforementioned proportion, if the ratio of bis-phenol (bisphenol) type epoxy resin (A) is greater than 99: If 1, in actual installation components, possible unbearable Reflow Soldering (reflow), so being not suitable for using.And if phenolic aldehyde The ratio of varnish (novolac) type epoxy resin (B) be greater than 85:15, then be 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))
Conductive adhesive composition of the invention is preferably also containing selected from least one of following group substance: by containing carboxyl (carboxyl group) polyurethane resin (C-1) and contain carboxyl (carboxyl group) polyacrylic acid (polyacrylic) The group that resin (C-2) is constituted.
That is, being hardened by carboxyl (carboxyl group) and the reaction of epoxy group, so can be improved heat-resisting Property, it can be improved and be attached to the cohesive force between body.
In addition, carboxyl (carboxyl group) both can also act as side chain, but be with side chain in the end of chain Preferably.
(containing carboxyl (carboxyl group) polyurethane resin (C-1))
Just above-mentioned (carboxyl group) polyurethane resin Han carboxyl (C-1) is illustrated below.
(carboxyl group) polyurethane resin containing carboxyl (C-1) is that one kind contains carboxyl (carboxyl in the molecule Group resin), it can be by making (carboxyl group) containing carboxyl polyalcohol (polyol) compound (1), polyalcohol (polyol) (2), short-chain diol (diol)) compound (3) (as needed), polyamine (polyamine) compound (4) (according to Need), polyisocyanate (polyisocyanate) compound (5) reaction obtain.When so being reacted, polyalcohol (polyol) compound (1) can thus be obtained well containing carboxyl using the substance with carboxyl (carboxyl group) (carboxyl group) polyurethane resin (C-1).
" polyurethane " in this specification is the general name of polyurethane and polyurethane-urea (polyurethane-urea).It must When wanting, being somebody's turn to do " polyurethane " and can also be makes amine (amine) ingredient carry out reacting obtained substance as needed.In this specification " containing active hydrogen-based ", which refers to, to react with isocyanate group (isocyanate group), 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..
(carboxyl group) polyalcohol (polyol) compound containing carboxyl (1) is at least to contain a carboxyl The compound of (carboxyl group) and more than two hydroxyls (hydroxyl group).Specifically if any dihydromethyl propionic acid The dihydroxymethyls such as (dimethylol propanoic acid), dimethylolpropionic acid (dimethylol butanoic acid) Alkyl acid (dimethylol alkanoic acid)；The alkene of dihydroxymethyl alkyl acid (dimethylol alkanoic acid) Changing oxygen (alkylene oxide) low mol adduct (adduct), (terminal functional group quantifies institute's number average molecular weight and is less than 500)；The 6-caprolactone (ε-caprolactone) of dihydroxymethyl alkyl acid (dimethylol alkanoic acid) is low to rub That adduct (adduct) (terminal functional group quantifies institute's number average molecular weight less than 500)；Dihydroxymethyl alkyl acid Acid anhydrides (acid anhydride) and glycerine (glycerin) in (dimethylol alkanoic acid) is derivative Half ester (half ester) class that (derived from) goes out；Dihydroxymethyl alkyl acid (dimethylol alkanoic acid) Hydroxyl, the monomer (monomer, similarly hereinafter) with unsaturated bond, with carboxyl (carboxyl group) and unsaturated bond Monomer carries out obtained compound of radical reaction etc..Wherein, from the point of view of being easy to get, being easily adjusted acid value etc., Dihydromethyl propionic acid (dimethylol propanoic acid) and dimethylolpropionic acid (dimethylol butanoic ) etc. acid dihydroxymethyl alkyl acid (dimethylol alkanoic acid) is more suitable for.Set polyurethane resin (C- 1) when the content of polyalcohol (polyol) compound (1) in, it should guarantee obtained polyurethane resin (C-1) and epoxy Crosslinking can be improved heat resistance, durability, guarantee flexibility and adhesion again.Specifically, in setting reacted constituent When the content of polyalcohol (polyol) compound (1), preferably make the acid value 3 of obtained polyurethane resin (C-1) ~ 100mgKOH/g。
Above-mentioned polyalcohol (polyol) (2) is the ingredient with more than two hydroxyls, it is preferred to use number-average molecular weight is 500 ~ 3000 substance.Above-mentioned polyalcohol (polyol) (2) only refers to the object for being not belonging to above-mentioned polyalcohol (polyol) compound (1) Matter.
Above-mentioned polyalcohol (polyol) (2) is not particularly limited, and can be used in the past for synthesizing amino Ethyl formate (urethane) well known polyalcohol (polyol).The specific example of polyalcohol (polyol) (2) is if any polyester (polyester) polyalcohol (polyol), polyethers (polyether, similarly hereinafter) polyalcohol (polyol), polycarbonate (polycarbonate) polyalcohol (polyol) and other polyalcohols (polyol) etc..
Polyester (polyester) polyalcohol (polyol) for example has following substances to pass through the obtained substance of polycondensation reaction: Aliphatic dicarboxylic acid (dicarboxylic acid, similarly hereinafter) is (for example, succinic 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) etc.) 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), 1,4-butanediol (Isosorbide-5-Nitrae-butylene glycol), 1,6- hexylene glycol (1,6-hexamethylene Glycol), neopentyl glycol (neopentyl glycol), Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane (Isosorbide-5-Nitrae-Bis ( Hydroxymethyl) cyclohexane) etc.).
The specific example of above-mentioned polyester (polyester) polyalcohol (polyol) is 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 esterdiol (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) etc..
The specific example of polyether polyol (polyol) is if any polyethylene glycol (poly ethylene glycol), poly- third Glycol (poly propylene glycol), poly- tetramethylene glycol (poly tetramethylene glycol) and above-mentioned Random/block copolymer of substance etc..
The specific example of polycarbonate polyol (polyol) is 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), 1,4 cyclohexanedimethanoester ester glycol of poly- carbonic acid (poly Isosorbide-5-Nitrae-cyclohexane dimethylene carbonate diol) and random/block of above-mentioned substance are total Polymers etc..
The specific example of other polyalcohols (polyol) is 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 are 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) etc..
The number-average molecular weight (Mn, quantitatively being obtained by terminal functional group) of polyalcohol (polyol) (2) is not particularly limited, But it is advisable with 500 ~ 3,000.The number-average molecular weight (Mn) of polyalcohol (polyol) (2) is more than 3,000, urethanes The cohesiveness of key (urethane bond) is difficult to show, and 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, can also be used in combination of two or more.
In addition, for obtaining the reacted constituent of polyurethane resin (C-1) preferably based on needing using short-chain diol (diol) Ingredient (3) uses polyamine (polyamine) ingredient (4) as needed.Thus be easier to control polyurethane resin hardness, Viscosity etc..The specific example of short-chain diol (diol) ingredient (3) is if any ethylene glycol (ethylene glycol), 1,2- the third two Alcohol (1,2-propylene glycol), 1,3-PD (1,3-propylene glycol), 1,4-butanediol (1, 4-butylene glycol), 1,6- hexylene glycol (1,6-hexamethylene glycol), neopentyl glycol (neopentyl ) etc. glycol aliphatic diol (glycol) and its low mol adduct (adduct) of alkylene oxide (alkylene oxide) (number-average molecular weight that terminal functional group quantitatively obtains is less than 500)；1,4-CHDM (Isosorbide-5-Nitrae-Bis Hydroxymethyl cyclohexane), 2- methyl-1,1- cyclohexanedimethanol (2-methyl-1,1- Cyclohexane dimethanol) etc. alicyclic diols (glycol) and its low mole of alkylene oxide (alkylene oxide) plus Close object (adduct) (number-average molecular weight less than 500, ibid)；The aromatic diols such as benzene dimethanol (xylylene glycol) (glycol) and its low mol adduct (adduct) of alkylene oxide (alkylene oxide) (number-average molecular weight less than 500, it is same On)；Bis-phenol (bisphenol) A, bisphenol sulfide (thiobisphenol), sulfonated bis phenol (sulfone bisphenol) etc. are double (number-average molecular weight is less than for phenol (bisphenol) and its low mol adduct (adduct) of alkylene oxide (alkylene oxide) 500, ibid)；Alkyl dialkanol amine (the alkyl such as the alkyldiethanolamine (alkyl diethanolamine) of C1 ~ C18 Dialkanolamine) etc..
The specific example of polyamine (polyamine) compound (4) is as follows: short chain has: methylene diamine (methylenediamine), ethylenediamine (ethylenediamine), propane diamine (trimethylene diamine), oneself two The aliphatic diamines (diamine) such as amine (hexamethylenediamine), octamethylenediamine (octamethylene diamine) are changed Close object；Phenylenediamine (phenylene diamine), 3,3 '-two chloro- 4,4 '-diaminodiphenylmethane (3,3 '-dichloro - 4,4 '-diaminodiphenyl methane), 4,4 '-two (aminobenzene) methane (4,4 '-methylenebis (phenylamine)), 4,4 '-diaminodiphenyl ethers (4,4 '-diaminodiphenyl ether), 4,4 '-diamino hexichol Aromatic diamines (diamine) compounds such as sulfone (4,4 '-diaminodiphenylsulfone)；Cyclopenta diamines (cyclopentyl diamine), cyclohexyl diamine (cyclohexyl diamine), 4,4 '-diamino-dicyclohexyl methanes (4,4 '-Diaminodicyclohexyl methane), Isosorbide-5-Nitrae-diaminocyclohexane (Isosorbide-5-Nitrae-diamino Cyclohexane), isophorone diamine (isophorone diamine) etc. alicyclic diamines (diamine) compound etc..This It outside, can also be by hydrazine (hydrazine), carbazide (carbodihydrazide), adipic dihydrazide (Adipic Acid dihydrazide), sebacic dihydrazide (Sebacic acid dihydrazide), phthalic acid (phthalic Acid) hydrazines (hydrazine) class such as two hydrazides (dihydrazide) 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), silicone-modified (siloxane modified) polyamine (polyamine) class etc.. Above-mentioned polyamine (polyamine) compound (4) both can be used alone, and can also be used in combination of two or more.
Previous manufacture polyurethane can be used in polyisocyanate (polyisocyanate) compound (5) (polyurethane) the well known polyisocyanate (polyisocyanate) used when.Polyisocyanate (polyisocyanate) specific example of (5) is if any Toluene-2,4-diisocyanate, 4- diisocyanate (toluene-2,4- Diisocyanate), 4- methoxyl group -1,3- phenylene diisocyanate (4-Methoxy-1,3-phenylene Diisocyanate), 4- isopropyl -1,3- phenylene vulcabond (4-Isopropyl-1,3-phenylene Diisocyanate), chloro- 1,3- phenylene vulcabond (4-chlor-1, the 3-phenylene of 4- Diisocyanate), 4- butoxy -1,3- phenylene vulcabond (4-butoxy-1,3-phenylene Diisocyanate), 2,4- diisocyanate diphenyl ether (2,4-diisocyanate diphenyl ether), 4,4 '-Asias Methyl-diphenylene isocyanide ester (4,4 '-methylene bis(phenylene isocyanate)) (MDI), tetramethyl For benzene to support diisocyanate (Durylene diisocyanate), tolidine diisocyanate (tolidine Diisocyanate), benzene dimethylene diisocyanate (Xylylene diisocyanate) (XDI), 1,5- naphthalene diisocyanate It is ester (1,5-naphthalenediisocyanate), benzidine diisocyanate (benzidine diisocyanate), o- Nitrobenzidine diisocyanate (o-nitrobenzidinediisocyanate), 4,4 '-dibenzyl diisocyanates (4, 4 '-diisocyanatedibenzyl) etc. aromatic diisocyanates (diisocyanate)；Methylene diisocyanate (methylenediisocyanate), Isosorbide-5-Nitrae-tetramethylene diisocyanate (Isosorbide-5-Nitrae-tetramethylene Diisocyanate), 1,6- hexa-methylene diisocyanate (1,6-hexamethylene diisocyanate), 1,10- ten The aliphatic diisocyanate of methylene diisocyanate (1,10-Decamethylene diisocyanate) etc. (diisocyanate)；Isosorbide-5-Nitrae-cyclohexyl diisocyanate (Isosorbide-5-Nitrae-cyclohexylene diisocyanate), 4,4- methylene Base two (cyclohexyl isocyanate) (4,4-methylenebis(cyclohexyl isocyanate)), 1,5- naphthane two it is different Cyanate (1,5-tetrahydro naphthalenediisocyanate), isophorone diisocyanate (isophorone Diisocyanate), the alicyclic diisocyanates such as (hydrogenation) MDI, hydrogenation (hydrogenation) XDI are hydrogenated (diisocyanate)；The polyalcohol (polyol) or polyamine of above-mentioned diisocyanate (diisocyanate) and low molecular weight (polyamine) carrying out reaction makes end become obtained polyurethane after isocyanates (isocyanate) (polyurethane) prepolymer etc..If obtaining having the polymer composition of preferable weatherability, it is preferred to use Aliphatic diisocyanate (diisocyanate) and alicyclic diisocyanate (diisocyanate).
The isocyanate group (isocyanate group) of polyisocyanate (polyisocyanate) compound (5) with it is upper State (carboxyl group) containing carboxyl polyalcohol (polyol) compound (1), polyalcohol (polyol) (2), short-chain diol (diol) the active hydrogen-based of compound (3) (as needed), polyamine (polyamine) compound (4) (as needed) etc. is not (but Carboxyl (carboxyl group) including (1)) equivalent proportion be preferably 0.5~1.5.It is available heat-resisting within the above range Property, all very high urethanes (urethan) of mechanical strength, with this more be suitable for.
There can also be the structure of closing base using end section.That is, can also be using the structure obtained as follows: in isocyanic acid It is reacted under conditions of ester group (isocyanate group) is superfluous, so as to form the end isocyanates (isocyanate), It reacts its isocyanates end (isocyanate) with monofunctional compound, the structure of endcapped is obtained with this.
(manufacturing method of polyurethane (polyurethane) resin (C-1))
Polyurethane (polyurethane) resin (C-1) can be manufactured with known polyurethane (polyurethane) Method manufactures.Specifically, firstly, making under conditions of being free of the organic solvent of reactive hydrogen presence or absence of intramolecular By (carboxyl group) containing carboxyl polyalcohol (polyol) compound (1), polyalcohol (polyol) (2), as needed work For short-chain diol (diol) compound (3) of chain extender selection, polyamine (polyamine) compound (4) (as needed), gather The reacted constituent of isocyanates (polyisocyanate) (5) composition is reacted, and is obtained reactant (such as prepolymer).About The composition of reacted constituent, in general, as long as being capable of forming with terminal isocyanate group (isocyanate group) Prepolymer.In addition, using a Completion Techniques (one shot method) or multistep processes when reaction, usually temperature is set It is 20~150 °C, is set as 60~110 °C more preferably, reaction is to reaching theoretical isocyanate (isocyanate) %.
About obtained reactant (prepolymer), when needing, polyamine (polyamine) compound (4) can also be made to join With react, make chain growth, with the molecular weight needed.Again, it is preferred to be reacted under the following conditions: polyisocyanate (polyisocyanate) isocyanate group (isocyanate group) (2) of compound (5) and (carboxyl containing carboxyl Group) polyalcohol (polyol) compound (1), polyalcohol (polyol) (2), short-chain diol (diol) compound (3) and poly- Amine (polyamine) compound (4) total active hydrogen-based (except the carboxyl (carboxyl group) of compound (1)) works as Amount is than being 0.5 ~ 1.5.
As above the weight average molecular weight (Mw) of polyurethane (polyurethane) resin (C-1) obtained is preferably 1,000 ~ 1, 000,000, because of the characteristics meeting such as the flexibility of polyurethane (polyurethane), adhesion, heat resistance and coating performance at this time More effectively play.In addition, " weight average molecular weight (Mw) " and " number-average molecular weight (Mn) " in this specification is not being said especially Refer to the value of polystyrene (polystyrene) conversion measured with gel permeation chromatography (GPC) in the case where bright.
In the present invention, it can according to need when synthesizing amino Ethyl formate (urethane) using catalyst.Such as have Dibutyl tin laurate (DIBUTYLTIN LAURATE), dioctyltin laurate (dioctyltin laurate), octanoic acid are sub- The metals such as tin (stannous octoate), zinc octoate, tetra-n-butyl titanate (Tetra n-butyl titanate) and have The organic amines, 1,8- diaza two such as machine acid, the salt of inorganic acid and Organometallic derivatives, triethylamine (Triethylamine) Ring [5.4.0] 11 carbon -7- alkene (Diazabicycloundecene) class catalyst etc..
Polyurethane (polyurethane) resin (C-1) can not both be synthesized by solvent or be closed by organic solvent At.The organic solvent inert for isocyanate group (isocyanate group) can be used in organic solvent, or makes With the organic solvent for compared with reacted constituent for isocyanate group (isocyanate group) being in low activity.Organic solvent Specific example is if any acetone (acetone), methyl ethyl ketone (methyl ethyl ketone), methyl iso-butyl ketone (MIBK) (methyl isobutyl ketone), cyclohexanone (cyclohexanone) etc. ketone (ketone) class solvent；Toluene (toluene), dimethylbenzene (xylene), Swasol(trade name, cosmo petroleum Co., Ltd. production), Solvesso(commodity Name, EXXON Chemical Co., Ltd. production) etc. aromatics hydro carbons (hydrocarbons) solvent；N-hexane (n-hexane) Equal aliphatic categories hydro carbons (hydrocarbons) solvent；Methanol (methanol), ethyl alcohol (ethanol), isopropanol (Isopropylalcohol) alcohol (alcohol) the class solvent such as；Dioxanes (dioxane), tetrahydrofuran (tetrahydrofuran) ethers (ether) the class solvent such as；Ethyl acetate (ethyl acetate), butyl acetate (Butyl Acetate), isobutyl acetate (isobutyl acetate) etc. esters (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), The glycol ether-ether such as ethyl -3- ethoxy-c acid esters (ethyl-3-ethoxy propionate) (glycolether ester) Class solvent；The amides such as dimethylformamide (dimethylformamide), dimethyl acetamide (Dimethylacetamide) (Amide) class solvent；N-methyl-2-pyrrolidone (N-methyl-2-Pyrrolidone) etc. lactams (lactam) class Solvent etc..
At synthesizing amino Ethyl formate (urethane), if isocyanate group (isocyanate group) remains in Polymer ends, preferably progress isocyanate group (isocyanate group) end capping reaction (Termination).Isocyanates The end capping reaction (Termination) of base (isocyanate group) can by with isocyanate group (isocyanate Group) there is reactive compound to carry out.This compound can be enumerated: monohydric alcohol (monoalcohol), monoamine (monoamine) monofunctional compounds such as；With the two kind functional groups different to isocyanates (isocyanate) reactivity Compound.The specific example of this compound is if any: methanol (methyl alcohol), ethyl alcohol (ethyl alcohol), just Propyl alcohol (n-propyl alcohol), isopropanol (Isopropylalcohol), n-butanol (n-butyl alcohol), The monohydric alcohols (monoalcohol) such as isobutanol (isobutyl alcohol), the tert-butyl alcohol (tert-butyl alcohol)；One second Amine (monoethylamine), n-propylamine (n-propylamine), diethylamine (Diethylamine), di-n-propylamine (di- N-propylamine), the monoamines such as di-n-butylamine (di-n-Butylamine) (monoamine)；Monoethanolamine (monoethanolamine), alkanolamines such as diethanol amine (diethanolamine) (alkanolamine) etc..Wherein, alkanol The reaction controlling of amine (alkanolamine) is relatively simple, therefore is suitable for using.
(acrylic resin (acrylic resin) (C-2))
The acrylic resin (acrylic resin) (C-2) that can be used in the present invention is that intramolecular contains carboxyl The resin of (carboxyl group) is crosslinked with epoxy (epoxy) resin and is reacted.The acrylic resin (acrylic Resin) (C-2) is obtained as follows: being made by the typical polymerizations method such as radical polymerization, cationic polymerization and anionic polymerisation containing carboxyl (carboxyl group) polymerizable monomer (6) polymerize with other polymerizable monomers (7).
Acrylic acid (acrylic acid), methyl can be used in (carboxyl group) polymerizable monomer containing carboxyl (6) Acrylic acid (methacrylic acid), containing carboxyl (carboxyl group) acrylate (acrylic acid ester), Such as 2- acrylyl oxy-ethyl-succinic 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) contains carboxyl (carboxyl group) methyl Acrylate (methacrylic acid ester), such as 2- methylacryoyloxyethyl-succinic acid (2- Methacryloyloxyethyl Succinic acid), 2- methylacryoyloxyethyl hexahydro-phthalic acid ester (2- Methacryloyloxyethylhexahydrophthalate), 2- methylacryoyloxyethyl phthalic acid (2- Methacryloyloxyethyl-phthalic acid) etc., wherein consider from reactivity and the being easy factors such as start with, with third Olefin(e) acid (acrylic acid) and methacrylic acid (methacrylic acid) are advisable (below sometimes by " acryloyl group (acryl) " and " methylacryloyl (methacryl) " is written as " (methyl) acryloyl group ((meth) acryl) " together).
Many kinds of substance can be used in other polymerizable monomers (7), wherein with (methyl) acrylic acid ((meth) acrylic Acid) class monomer is advisable.The specific example of above-mentioned (methyl) acrylic acid ((meth) acrylic acid) class monomer is 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) nonyl acrylate (nonyl(meth) Acrylate), the different nonyl ester of (methyl) acrylic acid (Isononyl (meth) acrylate), (methyl) isodecyl acrylate (isodecyl(meth) acrylate), (methyl) dodecyl acrylate (Dodecyl(meth) acrylate), (methyl) propylene Acid 13 esters (tridecyl(meth) acrylate), positive ten diester of (methyl) acrylic acid (n-lauryl (meth) Acrylate), (methyl) n-stearyla crylate (n-Stearyl (meth) acrylate), (methyl) acrylic acid different 18 Ester (isostearyl(meth) acrylate), (methyl) dicyclopentanyl acrylate (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) etc..In addition, other polymerizable monomers (7) can be used Styrene (styrene) class monomer or acrylonitrile (acrylonitrile) class monomer.Above-mentioned monomer both can be used alone It can also be applied in combination two or more.
The acid value of acrylic resin (acrylic resin) (C-2) is higher, and crosslinking points are more, and heat resistance is higher.But with acid The excessively high acrylic resin of valence (acrylic resin) (C-2) be ingredient obtain conductive adhesive composition there are it is really up to the mark cause it is soft Soft reduction or carboxyl (carboxyl group) cannot react completely with epoxy resin (epoxy) etc., durability decline Problem.Therefore, the acid value of acrylic resin (acrylic resin) (C-2) is advisable with 3 ~ 100mgKOH/g.
If made with the ester (ester) of (methyl) acrylic acid ((meth) acrylic acid) and long-chain alcohol (alcohol) For polymerizable monomer, the glass transition point (Tg) of obtained acrylic resin (acrylic resin) (C-2) can drop It is low.Using the low acrylic resin of this glass transition point (Tg) (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 If nitrile (acrylonitrile) is used as polymerizable monomer, obtained acrylic resin (acrylic resin) (C-2) Glass transition point (Tg) can increase.Use the high acrylic resin of this glass transition point (Tg) (acrylic resin) (C-2), all good conductive adhesive composition of heat resistance and durability can be obtained.That is, the type of selective polymerization ingredient, ratio When, making the glass transition point (Tg) of acrylic resin (acrylic resin) (C-2) is appropriate numerical value, can thus be obtained Flexibility, adhesion, heat resistance, durability.Specifically, most handy two or more (methyl) acrylic acid ((meth) Acrylic acid) class monomer is as ingredient containing double bonds.In addition, the glass of acrylic resin (acrylic resin) (C-2) Glass transition point (Tg) is preferably -20 ~ 30 °C.The glass transition point of acrylic resin (acrylic resin) (C-2) (Tg) more than 30 °C, flexibility and adhesion can be reduced.And if acrylic resin (acrylic resin) (C-2) If glass transition point (Tg) is less than -20 °C, heat resistance and durability can decline.
(manufacturing method of acrylic resin (acrylic resin) (C-2))
For example, being made with known polymerizations such as emulsion polymerization, suspension polymerisation, polymerisation in solution or blocky polymerizations containing carboxylic Base (carboxyl group) polymerizable monomer (6) and other polymerizable monomers (7) are polymerize, and can obtain acrylic acid with this Resin (acrylic resin) (C-2).For example, in polymerisation in solution, it is only necessary to suitable under conditions of there are polymerization initiator When solvent in polymerize polymeric composition.
The solvent type used in polymerisation in solution is not particularly limited, as long as adverse effect will not be caused to polymerization reaction ?.The specific example of solvent is if any water；Methanol (methanol), ethyl alcohol (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), propylene glycol (propylene Glycol), diethylene glycol (DEG) (diethylene glycol) etc. alcohol (alcohol) class solvent；Petroleum ether (petroleum ether), Hexane (hexane), heptane (heptane) etc. aliphatic hydrocarbons (hydrocarbons) class solvent；Benzene (benzene), toluene (toluene), dimethylbenzene (xylene) etc. aromatic hydrocarbons (hydrocarbons) class solvent；Diethyl ether (diethyl ether), The ethers such as butyl oxide (dibutyl ether), tetrahydrofuran (tetrahydrofuran) (THF), dioxanes (dioxane) (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) Equal ketone (ketone) class solvent；Ethyl acetate (ethyl acetate), propyl acetate (propyl acetate), butyl acetate (Butyl acetate) etc. esters (ester) class solvent；N,N-dimethylformamide (N, N-dimethylformamide) (DMF), DMAC N,N' dimethyl acetamide (N, N-Dimethylacetamide), N-Methyl pyrrolidone (N- Methylpyrrolidone) the amides such as (NMP) (Amide) class solvent.
The usage amount of solvent is suitably set according to the condition of polymerization reaction.Usually, exist with the mass ratio of polymeric composition 0.1 ~ 100 times or so is more suitable for, and 0.2 ~ 20 times or so more preferably.Above-mentioned solvent both can be used alone, can also be by two Kind combination of the above uses.
Known type can be used in polymerization initiator.The specific example of polymerization initiator is if any benzoyl peroxide first Acyl (benzoyl peroxide), dibutyl peroxide (Dibutyl Peroxide), cumyl hydroperoxide (cumene The peroxides such as hydroPeroxide)；Bis- (the 2,4- bis- of azodiisobutyronitrile (azobisisobutyronitrile), azo Methyl valeronitrile) (azobis(2,4-dimethylvaleronitrile)) etc. azos (azo) Type of Collective initiator.Above-mentioned polymerization Initiator can be used alone, and can also be used in combination of two or more.The usage amount of polymerization initiator does not limit especially It is fixed, it is 0.1 ~ 10 mass % or so for the quality of polymeric composition usually.
The temperature of polymerization reaction is suitably set according to reaction condition.Usually, as long as temperature room temperature (25 °C) ~ Below the boiling point of used solvent.In addition, in order to adjust obtained acrylic resin (acrylic resin) (C-2) The degree of polymerization, chain-transferring agents or the hydroquinones such as mercaptan (mercaptan) class can also be added in polymerization reaction substance (hydroquinone) polymerization inhibitors such as.
In order to meet the various property such as adhesion, heat resistance, durability, intermiscibility (compatibility), coating performance Can, the weight average molecular weight (Mw) of the acrylic resin (acrylic resin) (C-2) as above obtained is 1,000 ~ 1,500,000 It is relatively appropriate, it is more preferable between 5,000 ~ 1,000,000.
(epoxy (epoxy) resin and the mixing ratio for containing carboxyl (carboxyl group) resin)
In the present invention, bis-phenol (bisphenol) type ring oxygen (epoxy) resin (A) and novolaks (Novolac) type ring The mixture and polyurethane (polyurethane) resin (C-1) and acrylic resin (acrylic of oxygen (epoxy) resin (B) Resin) mixing ratio of (C-2) is preferably 70:30 ~ 30:70.It is disposed within above range, good film-forming property, and heat resistance It is easy to adjust, therefore is more suitable for.
(other compositions)
About the conductive adhesive composition in the present invention, other than above-mentioned (A), (B), (C), it is hard that participation had better not be added Change the ingredient of reaction.I.e., it is generally the case that the epoxy being used together with epoxy (epoxy) compound had better not be contained (epoxy) curing agent.
Conductive adhesive composition of the invention is particularly suitable for binding substrate and electric conductivity supporting material in soft circuit base plate. When being used for the purposes, it is preferred to use do not contain the type of above-mentioned epoxy (epoxy) curing agent.
About purposes, will hereafter be discussed in greater detail.After having carried out preliminary bonding, need to be binded by hot pressing, but Due to manufacturing step, is taken care of for a long time (one week or more) after preliminary bonding sometimes, then carry out hot pressing again. Start to carry out at this point, heating stepses when may tentatively bind will lead to sclerous reaction, sclerous reaction progress is fast during keeping Thus speed causes to be unable to get enough bonding strengths in hot pressing bonding step.
Under the circumstances, above-mentioned epoxy (epoxy) curing agent is not used, is thus not in the above problem, i.e., Make to take care of a very long time after preliminary bonding carries out hot pressing bonding again, and the peel strength after binding step also can be in 10N/cm More than, good cement properties are able to maintain, therefore be more suitable for.
The curing agent that should not be used in the present invention refers to for promoting polyurethane (polyurethane) resin and epoxy (epoxy) substance of the reaction between the reaction or promotion epoxy (epoxy) resin of resin.This curing agent is if any isocyanic acid Ester (isocyanate) compound, compound, the carbodiimides for containing hydroxyl (hydroxyl group) (carbodiimide) compound, oxazoline (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, having of the invention Feature, as long as the peel strength being able to satisfy after above-mentioned hot pressing bonding step can also add above-mentioned if 10N/cm or more Curing agent.Such as usage amount at this time relative to (A) ~ (C) ingredient total amount below 0.1 weight %.
(electroconductive stuffing (D))
Conductive adhesive composition of the invention contains electroconductive stuffing (D).Above-mentioned electroconductive stuffing (D) is not particularly limited, Metal packing, coating metal resin extender, carbon (carbon) filler and its mixture can be used for example.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 by electrolysis method, Atomization (atomization method), reduction method obtain.
In addition, the average grain diameter of electroconductive stuffing is preferably 3 ~ 50 μm in order to make to be easier between filler to contact.In addition, The shape of electroconductive stuffing is if any spherical, sheet, dendroid, threadiness etc..
From the viewpoints such as interconnection resistance, cost consider, above-mentioned electroconductive stuffing (D) be preferably selected from by silver powder, silver-coated copper powder, At least one of the group of copper powder composition.
It is 40 ~ 90 weights preferably for the total amount of conductive adhesive composition about the content of above-mentioned electroconductive stuffing (D) Measure %.
In addition, silane coupling agent (silane coupling agent), anti-oxidant can also be added in conductive adhesive composition Agent, pigment, dyestuff, tackifier resins (tackifier resin), plasticizer, ultraviolet absorbing agent, defomaing agent, leveling agent (leveling agent), filler, fire retardant etc., as long as being controlled in the model for not making reflux-resisting welded (reflow) property deterioration In enclosing.
(conductive adhesive composition)
It is applied after so that above-mentioned each ingredient is reacted and is obtained conductive adhesive composition about conductive adhesive composition of the invention It is distributed on substrate and forms film, conducting resinl can serve as with this and use.Conductive adhesive composition is coated on to be formed on substrate and is applied When film, can use following production methods: then dissolution or dispersed electro-conductive glue constituent in a solvent are coated on substrate On, it is dried as needed, forms film.
(conductive adhesive film)
Conductive adhesive film of the invention can be made up of coating (coating) conducting resinl on release film.Coating (coating) method is not particularly limited, and can be used with die coating (die-coating), die lip coating (lip Coating), scraper type coating (comma coating) is machine well known to coating (coating) machine of representative etc..This Outside, after by conducting resinl coating (coating) to release film, it can according to need and be dried.Drying condition at this time can To set most suitable condition from the viewpoint of productivity.
The film obtained as follows can be used in release film: in polyethylene terephthalate (polyethyleneterephthalate), the basement membranes such as polyethylene naphthalate (polyethylenenaphthalate) On, silicon (silicon) class or non-silicon (silicon) class release agent are coated on to the surface for being formed with conductive adhesive layer side.It is release The thickness of film is not set especially, can suitably be set from the viewpoint of easy to use.
The thickness of the conductive adhesive layer formed on release film is preferably 15 ~ 100 μm.Not if it is less than embeddability at 15 μm It is good, and more than 100 μm, then cost can be increased, and not be able to satisfy the requirement of filming.Above range is set by its thickness, when When there are bumps on substrate, recess portion can be filled out by flowing appropriate, so deformed, can closely be binded, Therefore more it is suitable for.
(adhesive method)
Illustrate the application method of conductive adhesive film of the invention below.The purposes of the conductive adhesive film is not particularly limited, such as It can be used for binding stiffening plate on circuit base plate.Especially when stiffening plate is electric conductivity stiffening plate, in addition to bonding should Other than made of metal stiffening plate, it can be also used for making being powered between the ground electrode in circuit base plate main body and the made of metal stiffening plate.
The material of circuit base plate main body is not particularly limited, as long as having insulating properties and being capable of forming the material of insulating layer Material, representative example is if any polyimides (polyimide) resin etc..
Metal plate is preferred in the stiffening plate of electric conductivity, and stainless steel plate, iron plate, copper sheet or aluminium sheet can be used in metal plate Deng.Wherein it is advisable with stainless steel plate.If using stainless steel plate, also there are enough strength support electronics zero in when thinner thickness of plate Component.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 in the range when, can be simply built in small machines, and with enough strength support actual installations Electronic component.
Electronic component described herein is if any chips components such as connector, IC, resistor, capacitor etc..
Adhesive method of the invention is made of following steps: above-mentioned conductive adhesive film is tentatively binded and is being binded by step (1) Substrate (X) --- on stiffening plate or flexible base plate；Step (2), step (1) it is obtained with conductive adhesive film by bonding base Superposition carries out hot pressing as by the flexible base plate or stiffening plate of bonding substrate (Y) on material (X).
Above-mentioned conductive adhesive film in soft circuit base plate especially suitable for binding flexible base plate and stiffening plate.That is, as compared Described in file 4, uses metal 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, sclerous reaction can be very slow, therefore is formally being sticked by hot pressing when taking care of certain time after preliminary bonding The case where being not in cement properties decline when conjunction.
In adhesive method of the invention, conductive adhesive film is tentatively binded on by bonding substrate (X) first.By bonding base Material (X) is either stiffening plate is also possible to flexible base plate, but stiffening plate is preferred.Condition when preliminary bonding is not special It limits, as long as conductive adhesive film can be fixed on by bonding substrate, is binded in the case where not shifting, but Preferably with face bonding mode, non-dots is binded.That is, preferably tentatively binding entire bond area.
It can tentatively be binded by press machine, bonding condition for example can be set to: temperature: 120 °C, time: 5 seconds, Pressure: 0.5MPa.
Can being carried out immediately step (2) by bonding substrate (X) for conductive adhesive film has tentatively been binded in step (1), it can also First to take care of one week or more time before carrying out step (2).The big advantage of the one of conductive adhesive composition of the invention be even if It will not decline in partially hardened postadhesion performance.
Step (2) is being removed on conductive adhesive film on bonding substrate (X) from step (1) acquisition, with conductive adhesive film Release film, be then superimposed by bonding substrate (Y) --- flexible base plate or stiffening plate, carry out hot pressing.By bonding substrate (X) and quilt Bind the relationship of substrate (Y) are as follows: a side is stiffening plate, and another party is flexible base plate.
Hot pressing can carry out under normal conditions, such as can carry out under the following conditions: 1 ~ 5MPa, 140 ~ 190 °C, 15 ~ 90 points.
(circuit base plate)
At least part of circuit base plate of the invention has by flexible base plate, conductive adhesive composition and electric conductivity stiffening plate Position made of being laminated according to this statement sequence.This circuit base plate can both be binded by above-mentioned adhesive method, can also To be obtained by 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 this The conductive adhesive composition of invention is binded, and can be powered.
In above-mentioned circuit base plate, electric conductivity stiffening plate is preferably existed only in a part of circuit base plate.That is, preferably setting The part for being calculated as electronic component has the structure of stiffening plate.
In circuit base plate of the invention, preferably make at least part in the face other than above-mentioned stiffening plate by electromagnetic wave shielding Film is coating.That is, electromagnetic shielding film both can only be coated a part in the face other than stiffening plate, can also be coated stiffening plate with The entire surface in outer face.At this point, electromagnetic shielding film can also be overlapped at least part of stiffening plate.It thus can be entire Good electromagnetic wave shielding function is obtained in circuit base plate, therefore is more suitable for.Electromagnetic shielding film is not particularly limited, with tool There are the structure of the tropisms conductive adhesive layer such as insulating layer or the structure with insulating layer metal layer 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 the following embodiments.Do not saying especially In the case where bright, " part " and " % " in embodiment and comparative example refers to quality criteria.
(1) the synthesis > of < polyurethane (polyurethane) resin (C-1)
[synthesis example c1: (carboxyl group) containing carboxyl polyurethane (polyurethane) ammoniacum (urethaneurea)]
Prepare blender, reflux condensing tube, thermometer, nitrogen and is blown into pipe and the reaction vessel with wellhole (manhole).With Nitrogen replaces the gas of reaction vessel interior, is then placed in dihydromethyl propionic acid (dimethylol propionic acid) (DMPA) 6.0g, poly- carbonic acid hexylene glycol esterdiol (poly hexamethylene carbonate diol) (trade name " a kind of name of product of PLACCEL CD(, Japanese are " プ ラ Network セ Le CD ") 220 ", the production of daicel Co., Ltd., end The number-average molecular weight that functional group quantitatively obtains is 2000) 100g and dimethylformamide (dimethylformamide) (DMF) 59.0g.Then hexamethylene diisocyanate (hexamethylene diisocyanate) (HDI) 31.9g is added (for OH base, NCO base is 2 times of equivalents), is reacted at 90 °C, until the NCO base of resin reaches the 4. of theoretical value 0%, obtain urethanes (urethane) pre-polymer solution.In obtained urethanes (urethane) pre-polymerization DMF298.5g is added in object solution, is cooled to 40 °C, isophorone diamine of dripping (isophorone diamine) (IPDA) 16.1g is reacted with the NCO base of urethanes (urethane) prepolymer.It is stirred, until infrared absorption spectrum Analysis measures, free isocyanate groups (isocyanate group) disappear to the absorption of 2,270cm-1, and obtaining acid value is 16.4mgKOH/g, the polyurethane that number-average molecular weight (Mn) is 50,000, weight average molecular weight (Mw) is 105,000 (polyurethane) DMF solution (solid concentration 30%) of resin (c1).
[synthesis example c2: (no urea bond (urea containing carboxyl (carboxyl group) polyurethane (polyurethane) Bond))]
Prepare blender, reflux condensing tube, thermometer, nitrogen and is blown into pipe and the reaction appearance with wellhole (manhole) Device.With the gas of nitrogen displacement reaction vessel interior, it is then placed in DMPA6.0g, 1,4-butanediol (Isosorbide-5-Nitrae-butane diol) A kind of name of product of 6.0g, PLACCEL CD(, Japanese are " プ ラ Network セ Le CD ") 220 100g and DMF139.1g.So HDI27.1g(is added afterwards for OH base, NCO base is equivalent), it is stirred at 90 °C, until infrared absorption spectrum point Analysis measurement obtains, free isocyanate groups (isocyanate group) disappear to the absorption of 2,270cm-1, then add DMF185.5g, obtains that acid value is 18.1mgKOH/g, number-average molecular weight (Mn) is that 52,000, weight average molecular weight (Mw) is 112, The DMF solution (solid concentration 30%) of 000 polyurethane (polyurethane) resin (c2).It is true by infrared absorption spectrum Polyurethane (polyurethane) resin (c2) is recognized without urea bond (urea bond).
[synthesis example c3: (carboxyl group) polyurethane Han carboxyl (polyurethane) (has urea bond (urea Bond))]
Prepare blender, reflux condensing tube, thermometer, nitrogen and is blown into pipe and the reaction appearance with wellhole (manhole) Device.With the gas of nitrogen displacement reaction vessel interior, it is then placed in a kind of name of product of DMPA6.0g, PLACCEL CD(, Japanese For 220 100g, DMF70.8g of " プ ラ Network セ Le CD ").Then isophorone diisocyanate (isophorone is added Diisocyanate) for (IPDI) 42.1g(for OH base, NCO base is 2 times of equivalents), it is reacted at 90 °C, until tree The NCO base of rouge reaches the 3.6% of theoretical value, obtains urethanes (urethane) pre-polymer solution.To obtained amino DMF312.3g is added in Ethyl formate (urethane) pre-polymer solution, is cooled to 40 °C, then drip IPDA16.1g, makes it It is reacted with the NCO base of urethanes (urethane) prepolymer.It is stirred, until infrared absorption spectrum analysis is measured , free isocyanate groups (isocyanate group) disappear to the absorption of 2,270cm-1, obtaining acid value is 15. The polyurethane (polyurethane) that 3mgKOH/g, number-average molecular weight (Mn) are 50,000, weight average molecular weight (Mw) is 102,000 The DMF solution (solid concentration 30%) of resin (c3).
[comparing synthesis example c4: without carboxyl (carboxyl group)]
Prepare blender, reflux condensing tube, thermometer, nitrogen and is blown into pipe and the reaction appearance with wellhole (manhole) Device.With nitrogen displacement reaction vessel interior gas, be then placed in 1,4-butanediol (Isosorbide-5-Nitrae-butane diol) 4.0g, CD220 100g and DMF58.2g.Then HDI31.7g(is added for OH base, NCO base is 2 times of equivalents), at 90 ° C is reacted, until the NCO base of resin reaches the 4.1% of theoretical value, it is molten to obtain urethanes (urethane) prepolymer Liquid.DMF295.8g is added into urethanes (urethane) pre-polymer solution of acquisition, 40 °C is cooled to, drips IPDA16.0g reacts it with the NCO base of urethanes (urethane) prepolymer.It is stirred, until infrared Absorption spectroanalysis measurement, free isocyanate groups (isocyanate group) are to the absorption disappearance of 2,270cm-1 Only, obtaining without carboxyl (carboxyl group), number-average molecular weight (Mn) is that 52,000, weight average molecular weight (Mw) is 109, The DMF solution (solid concentration 30%) of 000 polyurethane (polyurethane) resin (c4).
(2) the synthesis > of < acrylic resin (acrylic resin) (C-2)
[synthesis example c5: containing carboxyl (carboxyl group) acrylic resin (acrylic resin)]
Prepare blender, reflux condensing tube, thermometer, nitrogen and is blown into pipe and the reaction appearance with wellhole (manhole) Device.With the gas of nitrogen displacement reaction vessel interior, it is then placed in methyl ethyl ketone (methyl ethyl ketone) (MEK) 100g is heated to 80 °C in a nitrogen environment.Prepare methyl methacrylate (methyl methacrylate) 5g, methyl-prop Olefin(e) acid 2- ethylhexyl (2-Ethylhexyl methacrylate) 65g, the positive ten diester (n-Lauryl of methacrylic acid Methacrylate) 25g, methacrylic acid (methacrylic acid) (2,4- dimethyl-penten of 5g and 2,2 '-azo two Nitrile) (2,2 '-azobis(2,4-dimethylvaleronitrile)) 2g mixture.The 1/3 of mixture is added to anti- It answers in container, remaining part was instilled in reaction vessel by dropping funel with 1 hour time.After dripping, shape at that time is kept State reacts 6 hours, obtains that acid value is 32.5mgKOH/g, weight average molecular weight (Mw) is that 29,000, number-average molecular weight (Mn) is 10, 000, the solution (solid concentration 50%) for the acrylic resin (acrylic resin) (c5) that the calculated value of Tg is -18.5 °C.
[comparing synthesis example c6: without carboxyl (carboxyl group)]
Prepare blender, reflux condensing tube, thermometer, nitrogen and is blown into pipe and the reaction appearance with wellhole (manhole) Device.After gas with nitrogen displacement reaction vessel interior, it is added methyl ethyl ketone (methyl ethyl ketone) (MEK) 100g is heated to 80 °C in a nitrogen environment.Prepare methyl methacrylate (methyl methacrylate) 10g, methyl-prop Olefin(e) acid 2- ethylhexyl (2-Ethylhexyl methacrylate) 65g, the positive ten diester (n-Lauryl of methacrylic acid Methacrylate) 25g, 2, and 2 '-azos two (2,4- methyl pentane nitrile) (2,2 '-azobis(2,4- Dimethylvaleronitrile the)) mixture of 2g.The 1/3 of mixture is added in reaction vessel, remainder passes through Dropping funel was dripped in reaction vessel with 1 hour time.After dripping, state of remaining stationary simultaneously is reacted 6 hours, obtains Weight-average molecular The acrylic resin that the amount calculated value that (Mw) is 35,000, number-average molecular weight (Mn) is 14,000, Tg is -19.1 °C The solution (solid concentration 50%) of (acrylic resin) (c6).
(manufacturing method of embodiment membrane sample)
Illustrate the manufacturing method of the conductive adhesive film of each embodiment, each reference example and each comparative example below.Combine a variety of materials, Certain paste is made.It is coated with (hand coat) method by hand by scraper blade (doctor blade) (flat spatula) It is coated on polyethylene terephthalate (polyethylene terephthalate) film for having carried out release processing, It is 100 °C × 3 points dry, conductive adhesive film is made.About scraper blade (doctor blade), according to the thickness for the conductive adhesive film to be made Degree is different, can suitably select the product of 1mil ~ 5mil.Here, 1mil=1/1000 inches=25.4 μm.In each implementation Example, reference example, when making each conductive adhesive film in comparative example, conductive adhesive film with a thickness of certain thickness.Here, conductive adhesive film Thickness is measured by mircrometer gauge.
[table 1]
Here, listed each ingredient uses the ingredient in following table 2 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. produces)
Electroconductive stuffing D-2: silver-coated copper powder (average grain diameter is 20 μm, Fukuda Metal Foil & POwder Co., Ltd. produces)
Electroconductive stuffing D-3: silver-coated copper powder (average grain diameter is 25 μm, Fukuda Metal Foil & POwder Co., Ltd. produces)
(adhesive method)
Pass through hot pressing for stiffening plate and conductive adhesive film using hot press (temperature: 120 °C, time: 5 seconds, pressure: 0.5MPa) It tentatively sticks together, then peels the stripping film on conductive adhesive film off, it is preliminary by above-mentioned preliminary adhesive method and flexible base plate It sticks together, then reusable heat press (temperature: 170 °C, time: 30 points, pressure: 3MPa) carries out hot pressing.
(evaluation method)
For the case where hot pressing is carried out within 1 hour after above-mentioned preliminary bonding and first takes care of one after preliminary bonding The case where carrying out hot pressing again in week, is evaluated respectively, evaluate its peel strength, interconnection resistance value, reflux-resisting welded (reflow) property, Resin flows (resin flow), reliability test.Herein, it is envisioned that the case where will appear long-term preservation, conditioning extremely 23 °C, indoor preservation one week of 60%RH.
(peel strength)
Pass through the adhesion force between 90 ° of disbonded test measurements and stiffening plate.Specifically, as shown in Figure 1, passing through stainless steel Gather in plate (width 10mm, length 100mm), the copper-clad laminated board with polyimides (polyimide) layer and film-form layers of copper The surface side of acid imide (polyimide) layer and the conductive adhesive film in the present embodiment, according to conductive in above embodiment The explanation of the application method of glue film, is pressed, and then pulls removing copper-clad laminated board to vertical direction.If 10N/cm with On then explanation there is no problem, can be used.
(interconnection resistance value)
Electrical characteristic evaluation has been carried out to the manufactured circuit base plate with metal reinforcement plate in aforementioned manners.It is connected in simulation Component aperture (opening size) is that the position indentation on the ground wire soft printing substrate of diameter 1.0mm between stiffening plate is led Electric glue film measures the interconnection resistance of the circuit base plate at this time with metal reinforcement plate (between the electrode of Fig. 2).If numerical value is in 1 Ω It is to ensure that shielding properties below.
(reflux-resisting welded (reflow) property)
Carry out the evaluation after Reflow Soldering (reflow).Temperature condition about Reflow Soldering (reflow), it is assumed that use nothing Kupper solder sets a kind of maximum temperature as 265 °C of temperature curve (temperature profile).It will be between stiffening plate Position indentation conductive adhesive film, circuit base plate test film with metal reinforcement plate pass through IR Reflow Soldering (reflow) 5 times, observation Whether there is or not expansions.
(resin flows (resin flow))
For the circuit base plate with metal reinforcement plate made of in aforementioned manners, measurement resin flowing (resin flow) away from From.When the circuit base plate with metal reinforcement plate produced from stiffening plate unilateral observation, measures and led from what stiffening plate lower section was overflowed Electric glue one end is at a distance from stiffening plate one end.If the distance at 300 μm hereinafter, if explanation there is no problem, can be used.
(reliability test)
By the disbonded test test film made in aforementioned manners and interconnection resistance measurement test film in high-temperature high-humidity (85 °C, 85%) are placed 1000 hours under environment, then measure respective peel strength and interconnection resistance 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. In addition, also can guarantee good cement properties even if having carried out saving for a long time after preliminary bonding.In addition, being binded When on the substrate with difference of height, good cement properties, electric conductivity can be also obtained.
A possibility that industry utilizes
Conductive adhesive composition of the invention is especially suitable for stiffening plate and flexible base plate made of bonding metal.
Label declaration
1. metal reinforcement plate (Ni-SUS is made)
2. electrode (Ni-Au electroless treatment)
3. resin flows (resin flow)
4.GND(Ni-Au electroless treatment)
5. conducting resinl
6. covering layer film
7. copper foil layer
8. copper-clad laminated board
9. at interconnection resistance measurement

Claims (12)

1. a kind of conductive adhesive composition, it is characterised in that:
The conductive adhesive composition contains:
Each molecule containing under more than two epoxy groups and room temperature be solid bisphenol-type epoxy resin (A),
Each molecule containing under more than two epoxy groups and room temperature be solid phenolic resin varnish type epoxy resin (B),
Containing carboxy resin (C) and
Electroconductive stuffing (D),
Wherein,
Contain polyurethane resin containing carboxyl (C-1) containing carboxy resin (C),
The ratio of bisphenol-type epoxy resin (A) and phenolic resin varnish type epoxy resin (B) are as follows: weight ratio 85:15~99:1.
2. conductive adhesive composition according to claim 1, it is characterised in that:
Epoxide equivalent is 800~10000 in above-mentioned bisphenol-type epoxy resin (A).
3. conductive adhesive composition according to claim 1, it is characterised in that:
Epoxide equivalent is 90~300 in above-mentioned phenolic resin varnish type epoxy resin (B).
4. conductive adhesive composition according to claim 1, it is characterised in that:
Electroconductive stuffing (D) is selected from least one of following group: the group being made of silver powder, silver-coated copper powder, copper powder.
5. conductive adhesive composition according to claim 1, it is characterised in that: the average grain diameter of electroconductive stuffing (D) be 3 ~ 50μm。
6. conductive adhesive composition according to claim 1, it is characterised in that:
Without containing bisphenol-type epoxy resin (A), phenolic resin varnish type epoxy resin (B) and containing the hardening other than carboxy resin (C) Agent.
7. a kind of conductive adhesive film, which formed using conducting resinl described in any one of the claims 1 ~ 6 The conductive adhesive layer and protective layer of object are laminated and are formed.
8. conductive adhesive film according to claim 7, it is characterised in that:
Conductive adhesive layer with a thickness of 15 ~ 100 μm.
9. conductive adhesive film according to claim 7 or 8, it is characterised in that:
Peel strength when hot pressing bonding is carried out after binding it tentatively 1 week with press machine in 10N/cm or more.
10. a kind of adhesive method, this method are made of following steps:
Step (1): conductive adhesive film described in any one of the claims 7 ~ 9 is tentatively binded as by bonding substrate (X) on electric conductivity stiffening plate or flexible base plate,
Step (2): in being used as by bonding base by superposition on bonding substrate (X) with conductive adhesive film obtained by step (1) The flexible base plate or electric conductivity stiffening plate of material (Y), and carry out hot pressing.
11. a kind of circuit base plate, it is characterised in that:
At least part of the circuit base plate has by flexible base plate, conductive adhesive layer and electric conductivity stiffening plate according to this statement sequence The position being laminated, wherein conductive adhesive layer is that the conductive adhesive film as described in any one of claim 7 ~ 9 is formed.
12. circuit base plate according to claim 11, it is characterised in that:
Face of the flexible base plate surface in addition to stiffening plate is coating with electromagnetic shielding film.
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