CN105907355B - Adhesive composite - Google Patents

Adhesive composite Download PDF

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Publication number
CN105907355B
CN105907355B CN201610243761.9A CN201610243761A CN105907355B CN 105907355 B CN105907355 B CN 105907355B CN 201610243761 A CN201610243761 A CN 201610243761A CN 105907355 B CN105907355 B CN 105907355B
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China
Prior art keywords
adhesive composite
mass
ingredient
substrate
electroconductive particle
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CN201610243761.9A
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CN105907355A (en
Inventor
伊泽弘行
有福征宏
横田弘
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Lishennoco Co ltd
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Hitachi Chemical 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09J171/12—Polyphenylene oxides
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S30/00—Structural details of PV modules other than those related to light conversion
    • H02S30/10—Frame structures
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
    • 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
    • C09J2471/00—Presence of polyether
    • 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
    • C09J2475/00—Presence of polyurethane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
    • H01L2224/83101—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus as prepeg comprising a layer connector, e.g. provided in an insulating plate member
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
    • H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Wire Bonding (AREA)

Abstract

The present invention relates to adhesive composites, it contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) radical polymerization initiator and (d) salt of boracic, wherein, the salt of (d) boracic is the following general formula (A) compound represented, in formula (A), R1、R2、R3And R4Each independently represent the alkyl or aryl of hydrogen atom, carbon atom number 1~18, X+Indicate the cation comprising quaternary phosphonium atom, for the salt packet of (d) boracic containing phosphonium compounds as the cation comprising quaternary phosphonium atom, stated phosphonium compounds are at least one selected from the group being made of three alkane base Phosphonium, two alkane Ji Fangji Phosphonium, the fragrant base Phosphonium of alkyl two, three fragrant base Phosphonium, four alkane base Phosphonium, trialkyl virtue base Phosphonium, the fragrant base Phosphonium of dialkyl group two and three virtue base Phosphonium of alkyl.

Description

Adhesive composite
It is on December 17th, 2012 that the application, which is the applying date, application No. is 201210548890.0, entitled " bonding Agent composition, film-like adhesive, adhesive sheet and connection structural bodies " Chinese patent application divisional application.
Technical field
The present invention relates to adhesive composite, film-like adhesive, adhesive sheet, connection structural bodies, the systems of connection structural bodies Make the application of method and adhesive composite.
Background technique
In semiconductor element and liquid crystal display element, for the purpose that the various parts made in element combine, always with Come using various bonding agents.For the requirement of bonding agent, it is related under cementability and heat resistance, humid tropical condition The many aspects such as reliability.Above-mentioned bonding agent is for the connection of liquid crystal display element and TCP (COF), the company of FPC and TCP (COF) It connects, connection, FPC and the connection of printed wiring board of TCP (COF) and printed wiring board etc..In addition, above-mentioned bonding agent be also used to by Semiconductor element mounting is in the substrate the case where.
As the adherend for bonding, printed wiring board or polyimides, polyethylene terephthalate are used (PET), the organic substrates such as polycarbonate (PC), polyethylene naphthalate (PEN), cyclic olefin polymer (COP), and The metals such as copper, aluminium or ITO (composite oxides of indium and tin), IZO (compound of indium oxide and zinc oxide), AZO (zinc-aluminium Oxide), SiN (silicon nitride), SiO2(silica) etc. has the substrate of various surface state.Therefore, it is necessary to suitable Together in the MOLECULE DESIGN of the adhesive composite of each adherend.
Recently, along with highly integrated, liquid crystal display element the High precision of semiconductor element, interelement spacing and Wiring closet spacing is just narrowing.In addition, gradually using the low organic substrate of the heat resistances such as PET, PC, PEN Semiconductor element, liquid crystal display element or touch tablet.If the adhesive composite solidification for such semiconductor element etc. When heating temperature it is high and curing rate is slow, then not only desired interconnecting piece has even peripheral parts can be also heated excessively The tendency of the main reason for as peripheral parts damage etc., therefore, for adhesive composite, it is desirable that under low-temperature setting Bonding.
All the time, as above-mentioned semiconductor element or bonding agent used for liquid crystal display element, always using table The thermosetting resin of existing high adhesiveness and the epoxy resin of high reliability (for example, referring to following patent documents 1).As resin Constituent is generally had the curing agent such as reactive phenolic resin using epoxy resin, with epoxy resin, promotes epoxy resin With the hot potentiality catalyst of curing agent reacted.Hot potentiality catalyst be do not react under the storage temperatures such as room temperature but The substance for showing high response when heated, becomes an important factor for determining solidification temperature and curing rate, from bonding agent in room The various compounds of use from the perspective of curing rate when the lower storage stability and heating of temperature.In actual process, By 170~250 DEG C at a temperature of solidify 1~3 hour condition of cure, obtained desired bonding.But to make on Bonding agent low-temperature setting is stated, needs the hot potentiality catalyst low using activation energy, but so that it is had both storage stability is very Difficult.
In recent years, and with free-radical polymerised compounds such as acrylate derivative or methacrylate derivatives and make Radical-curable bonding agent for the peroxide of radical polymerization initiator attracts attention.For radically curing, Since the free radical as chain carrier is imbued with reactivity, short time solidification can be realized (for example, referring to following special Sharp document 2).For such radical-curable bonding agent, proposed and with benzoyl peroxide (BPO), amine compound, The method (for example, referring to following patent documents 3) as radical polymerization initiator such as organoboron compound.
Existing technical literature
Patent document 1: Japanese Unexamined Patent Publication 1-113480 bulletin
Patent document 2: International Publication No. 98/44067
Patent document 3: Japanese Unexamined Patent Publication 2000-290121 bulletin
Summary of the invention
Problems to be solved by the invention
In order to make above-mentioned radical-curable bonding agent low-temperature setting, need using radical polymerization initiator, but for For existing radical-curable bonding agent, has both curability at low temperatures and storage stability is very difficult.For example, when making Use above-mentioned benzoyl peroxide (BPO), amine compound, organoboron compound etc. as acrylate derivative or metering system When the radical polymerization initiator of the free-radical polymerised compounds such as acid ester derivant, even if at room temperature (25 DEG C, same as below) Under also will do it curing reaction, therefore have the case where storage stability reduction.
The adhesive composite excellent the object of the present invention is to provide curability at low temperatures and storage stability as a result,.In addition, The object of the present invention is to provide the film-like adhesive, the adhesive sheets, connection structural bodies, connection that use such adhesive composite The manufacturing method of structural body and the application of adhesive composite.
The technical solution solved the problems, such as
The present inventor conducts in-depth research to solve above-mentioned technical problem, as a result, it has been found that, by using specific boron Constituent of the compound as adhesive composite, available excellent curability at low temperatures and storage stability, thus complete At the present invention.
That is, adhesive composite of the invention contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) certainly By base polymerization initiator and (d) salt of boracic, wherein the salt of (d) boracic is the following general formula (A) compound represented.
[changing 1]
In formula (A), R1、R2、R3And R4Each independently represent the alkyl or aryl of hydrogen atom, carbon atom number 1~18, X+ Indicate the cation comprising quaternary phosphonium atom and/or quaternary nitrogen atoms.
In the present invention, by making adhesive composite contain the salt of (d) boracic, low temperature (such as 80~120 can be promoted DEG C) under (c) radical polymerization initiator decomposition, therefore the curability at low temperatures of adhesive composite is excellent.In addition, in this hair In bright, since the salt of above-mentioned (d) boracic is general formula (A) compound represented, storage stability (such as the room of adhesive composite Storage stability under warm nearby (such as -20~25 DEG C)) it is excellent, even if in the case where long-term preservation adhesive composite, Excellent adhesive strength and connection resistance can be obtained (for example, in the connection structural bodies or solar battery mould of circuit block Adhesive strength and connection resistance in block).As described above, the curability at low temperatures and stable storing of adhesive composite of the invention Property is excellent.
In turn, in the present invention, whether long-term preservation adhesive composite, can obtain excellent adhesive strength and Connect resistance.In addition, in the present invention, whether long-term preservation adhesive composite, even if being tried in prolonged reliability It tests after (high temperature and humidity test) and is also able to maintain that stable performance (adhesive strength and connection resistance).
It, can be containing shown in the following general formula (A1) as the salt of (d) boracic for adhesive composite of the invention Compound curability at low temperatures and storage stability can be made to further increase in this case.
[changing 2]
In formula (A1), R1、R2、R3、R4、R5a、R6a、R7aAnd R8aEach independently represent hydrogen atom, carbon atom number 1~18 Alkyl or aryl.
R in above-mentioned general formula (A)5a、R6a、R7aAnd R8aIn preferably any one and only one be hydrogen atom.Such case Under, curability at low temperatures can be made to further increase.
It, can be containing shown in the following general formula (A2) as the salt of (d) boracic for adhesive composite of the invention Compound curability at low temperatures and storage stability can be made to further increase in this case.
[changing 3]
In formula (A2), R1、R2、R3And R4The alkyl or aryl of hydrogen atom, carbon atom number 1~18 are each independently represented, R5b、R6b、R7b、R8bAnd R9bEach independently represent hydrogen atom, halogen atom, alkyl, aryl or alkoxy, R8bAnd R9bIt can be mutual It combines and forms ring.
In addition, (b) free-radical polymerised compound can contain with phosphate in adhesive composite of the invention Free-radical polymerised compound other than vinyl compound and the vinyl compound.In this case, under low-temperature setting Bonding becomes easy, meanwhile, it is capable to make to further increase with the adhesive strength of the substrate with connection terminal.
In addition, (d) fusing point of the salt of boracic can be 60 DEG C or more 300 DEG C or less.In this case, stability (for example, The stability of near room temperature) it further increases, storage stability further increases.
In addition, (a) thermoplastic resin can be containing from by phenoxy resin, polyurethane resin, polyester urethane resin, contracting Butyral resin, acrylic resin, polyimide resin and polyamide and with vinylacetate as structural unit At least one selected in the group of copolymer composition.In this case, heat resistance and cementability further increase, even if when long Between reliability test (high temperature and humidity test) after also can easily maintain these excellent characteristic.
In addition, adhesive composite of the invention can further contain (e) electroconductive particle.In this case, can Adhesive composite is assigned with good electric conductivity or anisotropic conductive, therefore can be more appropriately used for connecting pin The mutual bonding purposes of circuit block or solar cell module of son etc..In addition, being electrically connected via above-mentioned adhesive composite The connection resistance of obtained connection structural bodies further can be reduced fully.
In addition, the inventors discovered that, above-mentioned adhesive composite is effectively used for the company with the component of connection terminal It connects.Adhesive composite of the invention can be used for by the interarea for being configured at first substrate the first connection terminal be configured at Second connection end on the interarea of the second substrate is electrically connected, and can be used for have on the interarea for being configured at substrate The connection terminal and the distribution component of the solar battery cell of connection terminal are electrically connected.
Film-like adhesive of the present invention includes above-mentioned adhesive composite.Adhesive sheet of the present invention has base Material and above-mentioned film-like adhesive, film-like adhesive are configured on substrate.
The connection structural bodies that one aspect of the present invention is related to has: having first substrate and is configured at the first substrate First circuit block of the first connection terminal on interarea, with the second substrate and be configured on the interarea of the second substrate The second circuit component of two connection terminals and the connecting component being configured between the first circuit block and second circuit component, Connecting component contains the solidfied material of above-mentioned adhesive composite, and the first connection terminal and second connection end are electrically connected. In the connection structural bodies being related in one aspect of the invention, connecting component contains the solidfied material of above-mentioned adhesive composite, by This, can improve the connection resistance and adhesive strength of connection structural bodies.
In the connection structural bodies being related in one aspect of the invention, at least one party in first substrate and the second substrate can By being constituted comprising the substrate that glass transition temperature is 200 DEG C of thermoplastic resins below.In this case, using bonding agent The adhesive strength of the connection structural bodies of composition can be further improved.
In the connection structural bodies being related in one aspect of the invention, at least one party in first substrate and the second substrate can By comprising from by polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cyclic olefin polymer group At group in at least one substrate selected constitute.In this case, even with by above-mentioned specific material structure At substrate the first circuit block or second circuit component the case where, the bonding agent being related to by using aforementioned present invention is combined Low-temperature setting also may be implemented in object, therefore, can reduce the thermal damage for the first circuit block or second circuit component.This Outside, the wetability of the substrate and adhesive composite that are made of above-mentioned specific material improves, viscous thus, it is possible to further increase Connect intensity.As a result, when using the substrate being made of above-mentioned specific material, excellent connection reliability can be obtained.
The connection structural bodies that one aspect of the present invention is related to can be such as under type: first substrate is by comprising from by poly- pair Ethylene terephthalate, polycarbonate, polyethylene naphthalate and cyclic olefin polymer composition group in select to Few a kind of substrate is constituted, and the second substrate is by comprising from the group being made of polyimide resin and polyethylene terephthalate In at least one substrate selected constitute.In this case, even with the base being made of above-mentioned specific material The case where the first circuit block or second circuit component of plate, the adhesive composite being related to by using aforementioned present invention, Low-temperature setting may be implemented, therefore, can reduce the thermal damage for the first circuit block or second circuit component.In addition, by The wetability of substrate and adhesive composite that above-mentioned specific material is constituted improves and can further increase adhesive strength.By This can obtain excellent connection reliability when using the substrate being made of above-mentioned specific material.
The connection structural bodies that other aspects of the present invention are related to has: with substrate and the company being configured on the interarea of the substrate Solar battery cell, distribution component and the connection being configured between solar battery cell and distribution component of connecting terminal Component, connecting component contain the solidfied material of above-mentioned adhesive composite, and are electrically connected connection terminal and distribution component.At this It invents in the connection structural bodies that other aspects are related to, connecting component contains the solidfied material of above-mentioned adhesive composite, thereby, it is possible to Improve the connection resistance and adhesive strength of connection structural bodies.
The present invention provides the manufacturing method of connection structural bodies, and this method is by making above-mentioned adhesive composite between having the First circuit block of one substrate and the first connection terminal being configured on the interarea of the first substrate, with have the second substrate and It is configured between the second circuit component of second connection end on the interarea of the second substrate, makes this viscous in such a state The solidification of agent composition is connect, is thus bonded the first circuit portion in the state of making the first connection terminal and second connection end is electrically connected Part and second circuit component.In addition, the present invention provides the manufacturing method of connection structural bodies, this method is by making above-mentioned bonding agent group Close object between with substrate and the connection terminal being configured on the interarea of the substrate solar battery cell and distribution component it Between, in such a state solidify the adhesive composite, thus in the state for being electrically connected connection terminal and distribution component Lower bonding solar battery cell and distribution component.
The present invention provides the application of above-mentioned adhesive composite, is used to make to be configured at first on the interarea of first substrate Connection terminal is electrically connected with second connection end on the interarea for being configured at the second substrate.The present invention provides above-mentioned bonding agent The application of composition is used to manufacture connecting component, which is used to make to be configured at first on the interarea of first substrate Connection terminal is electrically connected with second connection end on the interarea for being configured at the second substrate.
The present invention provides the application of above-mentioned adhesive composite, is used to make the connection with being configured on the interarea of substrate The connection terminal and the distribution component of the solar battery cell of terminal are electrically connected.The present invention provides above-mentioned bonding agent combination The application of object is used to manufacture connecting component, which is used to make the connection terminal with being configured on the interarea of substrate The connection terminal of solar battery cell be electrically connected with distribution component.
The present invention provides above-mentioned adhesive composite, becomes the connecting component in connection structural bodies, the connection structural bodies Have: there is the first circuit block of first substrate and the first connection terminal being configured on the interarea of the first substrate, have The second circuit component of the second substrate and the second connection end being configured on the interarea of the second substrate and it is configured at first Connecting component between circuit block and second circuit component, the first connection terminal and second connection end are electrically connected. The present invention provides above-mentioned adhesive composite, becomes the connecting component in connection structural bodies, which has: having The solar battery cell of substrate and the connection terminal being configured on the interarea of the substrate, distribution component and it is configured at the sun Connecting component between energy battery unit and distribution component, connection terminal and distribution component are electrically connected.
Beneficial effect
In accordance with the invention it is possible to provide curability at low temperatures and the excellent adhesive composite of storage stability.It is such viscous Agent composition is connect, compared with the case where being recorded in above patent document 3 using alkyl boron compound, can be improved stable storing Property.In addition, the curability at low temperatures of adhesive composite of the present invention and the balance of storage stability are excellent.Due to this hair The storage stability of the bright adhesive composite being related to is excellent, therefore, even if in the case where long-term preservation adhesive composite, Also excellent adhesive strength and connection resistance can be obtained.In turn, for adhesive composite of the present invention, no matter Whether long-term preservation adhesive composite, excellent adhesive strength and connection resistance can be accessed.In addition, being related to for the present invention And adhesive composite for, whether long-term preservation adhesive composite, even if (high in prolonged reliability test Warm high humidity test) after, also it is able to maintain that stable performance (adhesive strength and connection resistance).The present invention is capable of providing using in this way The film-like adhesive of adhesive composite, adhesive sheet, connection structural bodies, the manufacturing method of connection structural bodies and bonding The application of agent composition.
Detailed description of the invention
Fig. 1 be indicate the first embodiment of the present invention is related to connection structural bodies schematic sectional view.
Fig. 2 is the schematic sectional view for indicating the manufacturing method of connection structural bodies shown in FIG. 1.
Fig. 3 is the schematic sectional view for the connection structural bodies for indicating that second embodiment of the present invention is related to.
Fig. 4 is the schematic sectional view for indicating the manufacturing method of connection structural bodies shown in Fig. 3.
Fig. 5 is the schematic sectional view for the connection structural bodies for indicating that third embodiment of the present invention is related to.
Description of symbols
10 be circuit block (the first circuit block)；12 be circuit substrate (first substrate)；12a is interarea；14 be connection Terminal (the first connection terminal)；20 be circuit block (second circuit component)；22 be circuit substrate (the second substrate)；22a is main Face；24 be connection terminal (second connection end)；30,40 be connecting component；30a, 40a are adhesive composites；44 be conductive Property particle；100,200 be circuit block connection structural bodies；300 be solar cell module (connection structural bodies)；310a, 310b is solar battery cell；312 be substrate；312a is surface (interarea)；312b is the back side (interarea)；314 be surface electricity Pole；316 be rear electrode；320 be distribution component；330 be connecting component.
Specific embodiment
Hereinafter, being described in detail to the preferred embodiments of the present invention.Here, in the present specification, " (methyl) Acrylic acid " means acrylic acid and corresponding methacrylic acid, and " (methyl) acrylate " means acrylate And corresponding methacrylate, " (methyl) acryloyl group " mean acryloyl group and methylacryloyl, " (first Base) acryloxy " mean acryloxy and corresponding methacryloxy.
In addition, in the present specification, the temperature for meaning that the method recorded according to the K0064 of JIS standard and obtaining of " fusing point " Degree, alternatively, the weighing 5.0mg sample in non-hermetic type sample disc, with differential scanning calorimeter, (DSC7 PERKIN ELMER is public Department's system) under a nitrogen with the temperature of the endotherm peak of the determination of heating rate of 10 DEG C/min.
In addition, in the present specification, " weight average molecular weight ", which refers to, passes through gel permeation chromatography according to condition as follows Method (GPC) is used by the value of the calibrating curve determining of standard polystyren.
(determination condition)
Device: TOSOH Co., Ltd GPC-8020
Detector: TOSOH Co., Ltd RI-8020
Chromatographic column: Hitachi Chemical Co., Ltd. Gelpack GL-A-160-S+GL-A150
Sample solution concentration: 120mg/3ml
Solvent: tetrahydrofuran
Injection rate: 60 μ l
Pressure: 30kgf/cm2
Flow: 1.00ml/min
The adhesive composite of present embodiment contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) certainly By base polymerization initiator and (d) salt of boracic.
((a) thermoplastic resin)
(a) thermoplastic resin refers to the resin (macromolecule) with following property: heated to become high liquid of viscosity State and with external force Free Transform, cooling and while removing external force, keeps its shape and is hardened, which can be repeated.In addition, (a) thermoplastic resin is also possible to the resin (macromolecule) for having the reactive functional groups of above-mentioned property.(a) thermoplastic resin The glass transition temperature (Tg) of rouge is for example preferably -30 DEG C or more, more preferably -25 DEG C or more, further preferably -20 DEG C More than.(a) glass transition temperature (Tg) of thermoplastic resin for example be preferably 190 DEG C hereinafter, more preferably 170 DEG C hereinafter, Further preferably 150 DEG C or less.
(a) thermoplastic resin may include for example from by phenoxy resin, polyurethane resin, polyester urethane resin, contracting Butyral resin (such as polyvinyl butyral resin), acrylic resin, polyimide resin and polyamide and have Copolymer (the vinyl acetate co-polymer, such as ethylene-vinyl acetate copolymer) group of vinylacetate as structural unit At group in at least one selected.These can the individually a kind of or two or more uses of mixing.In turn, these (a) thermoplasticity It can also include siloxanes key or fluoro substituents in resin.For them, preferably mixed resin mixes completely each other State or the state of microphase-separated and gonorrhoea occurs.
Adhesive composite in application, the weight average molecular weight of (a) thermoplastic resin is bigger, is more easy to get good with membranaceous Film formative, furthermore, it is possible to which the viscosity that dissolves that will affect the mobility of film-like adhesive composition is set in a wide range It is fixed.(a) weight average molecular weight of thermoplastic resin is for example preferably 5000 or more, more preferably 7000 or more, further preferably 10000 or more.If (a) weight average molecular weight of thermoplastic resin is 5000 or more, has and be easy to get good film formative Tendency.(a) weight average molecular weight of thermoplastic resin for example be preferably 150000 hereinafter, more preferably 100000 hereinafter, further Preferably 80000 or less.If (a) weight average molecular weight of thermoplastic resin be 150000 hereinafter, be easy to get with other at The tendency of the good intermiscibility divided.
The use level of (a) thermoplastic resin in adhesive composite, (is eliminated with bonding agent ingredient in adhesive composite The ingredient of electroconductive particle) all-mass on the basis of, such as preferably 5 mass % or more, more preferably 15 mass % or more. If (a) use level of thermoplastic resin be 5 mass % or more, especially adhesive composite with membranaceous in application, there is appearance It is easy to get to the tendency of good film formative.(a) thermoplastic resin use level (is arranged with bonding agent ingredient in adhesive composite In addition to the ingredient of electroconductive particle) all-mass on the basis of, such as preferably 80 mass % are hereinafter, more preferably 70 mass % Below.If (a) use level of thermoplastic resin is 80 mass % hereinafter, there is the stream for being easy to get good adhesive composite The tendency of dynamic property.
((b) free-radical polymerised compound)
(b) free-radical polymerised compound refers to the change that free radical polymerization occurs under the action of radical polymerization initiator Object is closed but it is also possible to be by assigning the activation energy such as the light or heat compound that its own is generated free radicals.As (b) free radical Polymerizable compound can properly use for example with vinyl, (methyl) acryloyl group, allyl, dimaleoyl imino Deng the compound for the functional group being polymerize by living radical.
As (b) free-radical polymerised compound, it can specifically enumerate epoxy (methyl) acrylate oligomer, gather Urethane (methyl) acrylate oligomer, polyethers (methyl) acrylate oligomer, polyester (methyl) acrylate oligomer etc. Oligomer, trimethylolpropane tris (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polyalkylene glycol two (methyl) acrylate, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) acrylic acid dicyclopentenyl oxygen ethyl ester, neopentyl glycol Modified two functions (methyl) acrylate of two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, isocyanuric acid, Isocyanuric acid is modified trifunctional (methyl) acrylate, two phenoxetol fluorenes acrylate, is added to (methyl) acrylic acid Epoxy group obtained from the glycidyl of bisphenol fluorene diglycidyl ether (methyl) acrylate, by ethylene glycol or propylene glycol It is added in compound obtained from the glycidyl of bisphenol fluorene diglycidyl ether and imports (methyl) acryloxy and obtain Compound, the following general formula (B) or general formula (C) compound represented for arriving etc..
[changing 4]
In formula (B), R9And R10Each independently represent hydrogen atom or methyl, a and b each independently represent 1~8 it is whole Number.
[changing 5]
In formula (C), R11And R12Each independently represent hydrogen atom or methyl, c and d each independently represent 0~8 it is whole Number.
In addition, as (b) free-radical polymerised compound, even individually showing as wax-like (ワ ッ Network in 30 DEG C of standings ス shape), wax oil shape (ろ う shape), crystalloid, the not no solid state of mobility such as glassy, powdery substance, can also not have Have and especially uses to limitation.As such (b) free-radical polymerised compound, specifically, N can be enumerated, N '-methylene Diacrylamine, diacetone acrylamide, N hydroxymethyl acrylamide, N- phenyl methacrylamide, 2- acrylamide -2- first Base propane sulfonic acid, three (2- acrylyl oxy-ethyl) isocyanuric acid esters, N-phenylmaleimide, N- (o-methyl-phenyl) maleimide Amine, N- (aminomethyl phenyl) maleimide, N- (p-methylphenyl) maleimide, N- (o-methoxyphenyl) maleimide Amine, N- (m-methoxyphenyl) maleimide, N- (p-methoxyphenyl) maleimide, N- methylmaleimido, N- Ethyl maleimide, N- octyl maleimide, 4,4 '-diphenyl-methane dimaleimides, two maleimide of metaphenylene Amine, 3,3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl-methane dimaleimide, 4- methyl-1, two Malaysia of 3- phenylene Acid imide, N- methacryloxy maleimide, N- acryloxy maleimide, 1,6- dimaleimide-(2, 2,4- trimethyl) hexane, N- methacryloxysuccinimide, N- acryloxy succinimide, 2- naphthyl methyl Acrylate, 2- naphthalene acrylate, pentaerythritol tetraacrylate, divinyl ethylidene-urea, divinyl propylidene urea, The polystyrene-based ethylmethyl acrylate of 2-, N- phenyl-N '-(3- methacryloxy -2- hydroxypropyl)-are to phenylene two Amine, N- phenyl-N '-(3- acryloxy -2- hydroxypropyl)-P- pHENYLENE dI AMINE, tetramethyl piperidine methyl acrylate, four Methyl piperidine base acrylate, pentamethvl methyl acrylate, pentamethvl base acrylate, octadecyl propylene Shown in acid esters, N tert butyl acrylamide, diacetone acrylamide, N- (methylol) acrylamide, the following general formula (D)~(M) Compound etc..
[changing 6]
In formula (D), e indicates 1~10 integer.
[changing 7]
[changing 8]
In formula (F), R13And R14Hydrogen atom or methyl are each independently represented, f indicates 15~30 integer.
[changing 9]
In formula (G), R15And R16Hydrogen atom or methyl are each independently represented, g indicates 15~30 integer.
[changing 10]
In formula (H), R17Indicate hydrogen atom or methyl.
[changing 11]
In formula (I), R18Indicate that hydrogen atom or methyl, h indicate 1~10 integer.
[changing 12]
In formula (J), R19Indicate organic group shown in hydrogen atom or the following general formula (i) or (ii), i indicate 1~10 it is whole Number.
[changing 13]
[changing 14]
[changing 15]
In formula (K), R20Indicate that organic group shown in hydrogen atom or the following general formula (iii) or (iv), j indicate 1~10 Integer.
[changing 16]
[changing 17]
[changing 18]
In formula (L), R21Indicate hydrogen atom or methyl.
[changing 19]
In formula (M), R22Indicate hydrogen atom or methyl.
In addition, urethane acrylate can be used as (b) free-radical polymerised compound.Urethane acrylate It can be used alone, can also be used in combination with (b) free-radical polymerised compound other than urethane acrylate.By individually making It is used in combination with urethane acrylate or with (b) free-radical polymerised compound other than urethane acrylate, flexibility is able to It improves, can be further improved adhesive strength.
It as urethane acrylate, is not particularly limited, but preferably polyurethane propylene shown in the following general formula (N) Acid esters.Herein, urethane acrylate shown in the following general formula (N), can pass through fatty family diisocyanate or ester ring type Be diisocyanate, with from by two pure and mild ester ring type ester system's glycol of aliphatic ester system and the pure and mild alicyclic ring of aliphatic acid ester carbonate system two At least one condensation reaction for selecting in the group of formula carbonic ester system's glycol composition and obtain.
[changing 20]
In formula (N), R23And R24Each independently represent hydrogen atom or methyl, R25Indicate ethylidene or propylidene, R26It indicates Representative examples of saturated aliphatic base or saturated fat cyclic group, R27It indicates the representative examples of saturated aliphatic base containing ester group or saturated fat cyclic group or contains There are the representative examples of saturated aliphatic base or saturated fat cyclic group of carbonate group, k indicates 1~40 integer.Here, in formula (N), R25Each other, R26It each other can be respectively identical or different.
The fatty family diisocyanate of above-mentioned urethane acrylate is constituted, tetramethylene diisocyanate can be selected from Ester, hexamethylene diisocyanate, lysine diisocyanate, 2- methylpentane -1,5- diisocyanate, 3- methylpentane - 1,5- diisocyanate, 2,2,4- tri-methyl hexamethylene -1,6- diisocyanate, 2,4,4- tri-methyl hexamethylene -1,6- Diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated xylene diisocyanate, hydrogenation hexichol Dicyclohexylmethane diisocyanate, hydrogenation trimethyl xylene diisocyanate etc..
In addition, constitute the aliphatic ester system glycol of above-mentioned urethane acrylate, can selected from ethylene glycol, propylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, neopentyl glycol, 1,2- pentanediol, 1,4- pentanediol, 1, 5- pentanediol, 2,4-PD, 2- methyl -2,4-PD, 2,4- dimethyl -2,4-PD, 2,2,4- trimethyl -1,3- Pentanediol, 1,2- hexylene glycol, 1,5- hexylene glycol, 1,6-HD, 2,5-HD, 2- ethyl -1,3- hexylene glycol, 2,5- diformazan Base -2,5-HD, 1,2- ethohexadiol, 1,8- ethohexadiol, 1,7- heptandiol, 1,9- nonanediol, Decane-1,2-diol, the 1,10- last of the ten Heavenly stems Glycol, 1,12- dodecanediol, dodecanediol, pinacol, 1,4- butynediols, triethylene glycol, diethylene glycol (DEG), dipropylene glycol, ring The low-molecular-weight diol class of the saturations such as hexane dimethanol, 1,4-CHDM, adipic acid, 3- methyl adipic acid, 2,2,5,5- Tetramethyl adipic acid, maleic acid, fumaric acid, succinic acid, 2,2- dimethyl succinate, 2- Ethyl-2-Methyl succinic acid, 2,3- first Base succinic acid, oxalic acid, malonic acid, methylmalonic acid, ethyl malonic acid, butylmalonic acid, dimethyl malonic acid, glutaric acid, 2- Methylglutaric acid, 3- methylglutaric acid, 2,2- dimethylated pentanedioic acid, 3,3- dimethylated pentanedioic acid, 2,4- dimethylated pentanedioic acid, heptan Polyester-diol obtained by the binary acid such as diacid, suberic acid, azelaic acid, decanedioic acid or acid anhydrides dehydrating condensation corresponding to them Class, polyester-diol class obtained by the cyclic ester compounds ring-opening polymerisation such as 6-caprolactone.Above-mentioned aliphatic ester system glycol can be independent A kind of or two or more uses of mixing.
In addition, constituting the aliphatic acid ester carbonate system glycol of above-mentioned urethane acrylate, it can be selected from and pass through at least one Kind or more above-mentioned glycols and phosgene reaction obtained by polycarbonate glycol class.It is obtained by above-mentioned glycols and phosgene reaction Polycarbonate-based glycol, can the individually a kind of or two or more uses of mixing.
The weight average molecular weight of above-mentioned urethane acrylate is for example preferably 5000 or more, more preferably 8000 or more, into One step is preferably 10000 or more.The weight average molecular weight of above-mentioned urethane acrylate, such as preferably less than 30000, more preferably For less than 25000, further preferably less than 20000.In addition, above-mentioned urethane acrylate, strong from bonding is further increased From the viewpoint of degree, freely weight average molecular weight can be adjusted in the range of 5000 less than 30000 and properly used. If the weight average molecular weight of above-mentioned urethane acrylate is within the above range, it can fully obtain flexibility and cohesive force is double Side further increases with the adhesive strength of the organic substrates such as PET, PC, PEN, can obtain superior connection reliability.This Outside, from the viewpoint of more fully obtaining such effect, the weight average molecular weight of above-mentioned urethane acrylate is for example preferred For 8000 less than 25000, more preferably 10000 less than 20000.In addition, from such effect is more fully obtained From the viewpoint of, the weight average molecular weight of above-mentioned urethane acrylate is preferably 10000 less than 25000.Here, if weight Average molecular weight is 5000 or more, has the tendency that being easy to get adequately flexibility, if weight average molecular weight, less than 30000, having can The tendency for inhibiting the mobility of adhesive composite to reduce.
In addition, the use level of above-mentioned urethane acrylate, (eliminates conduction with bonding agent ingredient in adhesive composite The ingredient of property particle) all-mass on the basis of, such as preferably 5 mass % or more, more preferably 10 mass % or more, into one Step is preferably 15 mass % or more.If above-mentioned use level is 5 mass % or more, it is easy to get sufficient heat resistance after solidification Tendency.In addition, the use level of above-mentioned urethane acrylate, (eliminates conduction with bonding agent ingredient in adhesive composite The ingredient of property particle) all-mass on the basis of, such as preferably 95 mass % hereinafter, more preferably 80 mass % hereinafter, into One step is preferably 70 mass % or less.If above-mentioned use level is 95 mass % hereinafter, using adhesive composite as membranaceous Bonding agent is in use, have the tendency that being easy to get good film formative.
(b) free-radical polymerised compound may include the vinyl compound (second with phosphate containing phosphate Alkenyl compound) and should free-radical polymerised compound other than vinyl compound containing phosphate respectively more than one. (b) free-radical polymerised compound can also be comprising from by N- vinyl compound and N, N- dialkyl group vinyl compound composition Group in free-radical polymerised compound other than the N- vinyl compound and the N- vinyl compound selected it is each From more than one.By and with the vinyl compound containing phosphate, adhesive composite can be further increased for tool There is the cementability of the substrate of connection terminal.In addition, passing through and using N- vinyl compound, adhesive composite can be improved Crosslinking rate.
As the vinyl compound containing phosphate, without spy as long as the compound with phosphate and vinyl Other limitation, it is preferred that being the following general formula (O)~(Q) compound represented.
[changing 21]
In formula (O), R28Indicate (methyl) acryloxy, R29Indicate that hydrogen atom or methyl, l and m each independently represent 1~8 integer.Here, in formula (O), R28Each other, R29Each other, l is each other and m is respectively identical or different each other.
[changing 22]
In formula (P), R30Indicate (methyl) acryloxy, n, o and p each independently represent 1~8 integer.Here, formula (P) in, R30Each other, n each other, o each other and p each other respectively it is identical or different.
[changing 23]
In formula (Q), R31Indicate (methyl) acryloxy, R32Indicate that hydrogen atom or methyl, q and r each independently represent 1~8 integer.
As the vinyl compound containing phosphate, specifically, acid phosphate base ethyl-methyl propylene can be enumerated Acid esters (acid phosphooxy ethyl methacrylate), acid phosphate base ethyl propylene acid esters, acid phosphate base third Methyl acrylate, acid phosphate base polyoxyethylene glycol monomethacrylates, acid phosphate base polyoxypropylene glycol monomethyl Acrylate, 2,2 '-two (methyl) acryloxy diethylphosphates, EO modified phosphate dimethylacrylate, phosphoric acid change Property epoxy acrylate, 2- (methyl) acryloyl-oxyethyl phosphate, phosphoric acid vinyl acetate etc..
As N- vinyl compound, specifically, N- vinyl imidazole, N- vinylpyridine, N- second can be enumerated Vinyl pyrrolidone, N- vinyl formamide, N- caprolactam, 4,4 '-ethenylidenes two (N, accelerine), N- vinyl acetamide, N, N- dimethylacrylamide, N, N- acrylamide etc..
About the above-mentioned vinyl compound containing phosphate and the respective use level of N- vinyl compound, and contain The use level of the vinyl compound of phosphate and the free-radical polymerised compound other than N- vinyl compound independently, On the basis of the all-mass of bonding agent ingredient (eliminating the ingredient of electroconductive particle in adhesive composite), such as it is preferably 0.2 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more.If above-mentioned use level For 0.2 mass % or more, have the tendency that being easy to get high adhesive strength.Above-mentioned vinyl compound and N- containing phosphate The respective use level of vinyl compound, with bonding agent ingredient (eliminating the ingredient of electroconductive particle in adhesive composite) All-mass on the basis of, such as preferably 15 mass % hereinafter, more preferably 10 mass % hereinafter, further preferably 5 matter Measure % or less.If above-mentioned use level is 15 mass % hereinafter, the physical property after having adhesive composite to solidify is difficult to decrease, is easy Ensure the tendency of reliability.
In addition, about the chemical combination in addition to meeting the above-mentioned vinyl compound containing phosphate or N- vinyl compound The use level of (b) free-radical polymerised compound other than object (eliminates electric conductivity with bonding agent ingredient in adhesive composite The ingredient of particle) all-mass on the basis of, such as preferably 5 mass % or more, more preferably 10 mass % or more, further Preferably 15 mass % or more.If above-mentioned use level is 5 mass % or more, have be easy to get solidify after sufficient heat resistance Tendency.The use level of (b) free-radical polymerised compound other than meeting the compound of above-mentioned vinyl compound, with On the basis of the all-mass of bonding agent ingredient (eliminating the ingredient of electroconductive particle in adhesive composite), such as preferably 95 Quality % hereinafter, more preferably 80 mass % hereinafter, further preferably 70 mass % or less.If above-mentioned use level is 95 matter % is measured hereinafter, using adhesive composite as film-like adhesive in use, having the tendency that being easy to get good film formative.
((c) radical polymerization initiator)
As (c) radical polymerization initiator, existing known organic peroxide and azo-compound etc. can be used The compound generated free radicals by assigning external energy.As (c) radical polymerization initiator, from stability, reactivity, phase From the viewpoint of dissolubility, preferably 1 minute half life temperature is 90~175 DEG C and weight average molecular weight is 180~1000 organic mistake Oxide.In the range by 1 minute half life temperature, storage stability is more excellent, free-radical polymerised also sufficiently high, energy Solidification in enough short time.
As (c) radical polymerization initiator, specifically, 1,1,3, the 3- tetramethyl butyl peroxidating new last of the ten Heavenly stems can be enumerated Acid esters, two (4- tert-butylcyclohexyl) peroxy dicarbonates, two (2- ethylhexyl) peroxy dicarbonates, cumenyl peroxide Change neodecanoic acid ester, 1,1,3,3- tetramethyl butyl new decanoate ester peroxide, dilauroyl peroxide, 1- cyclohexyl -1- methyl Ethyl new decanoate ester peroxide, tert-hexyl peroxide neodecanoic acid ester, tert-butyl hydroperoxide neodecanoic acid ester, tert-butyl hydroperoxide new penta Acid esters, 1,1,3,3- tetramethyl butyl peroxidating -2 ethyl hexanoic acid ester, two (2- ethyihexanoylperoxy of 2,5- dimethyl -2,5- Change) hexane, tert-hexyl peroxide -2 ethyl hexanoic acid ester, tert-butyl hydroperoxide -2 ethyl hexanoic acid ester, tert-butyl hydroperoxide new heptan Acid esters, t-amyl peroxy -2 ethyl hexanoic acid ester, di-tert-butyl peroxide hexahydro terephthalic acid ester, t-amyl peroxy -3, 5,5- tri-methyl hexanoic acid ester, 3- hydroxyl -1,1- dimethylbutyl new decanoate ester peroxide, 1,1,3,3- tetramethyl butyl peroxide Change -2 ethyl hexanoic acid ester, t-amyl peroxy neodecanoic acid ester, t-amyl peroxy -2 ethyl hexanoic acid ester, two (3- methylbenzene first Acyl) peroxide, dibenzoyl peroxide, two (4- toluyl) peroxide, tert-hexyl peroxide isopropyl single carbon Acid esters, tert-butyl hydroperoxide maleic acid, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, tert-butyl hydroperoxide laurate, 2,5- dimethyl -2,5- two (peroxidating of 3- toluyl) hexane, tert-butyl hydroperoxide -2- ethylhexyl monocarbonate, uncle Hexyl peroxide benzoate, 2,5- dimethyl -2,5- two (benzoyl peroxide) hexane, tert butyl peroxy benzoate, Dibutyl peroxidating trimethyladipic acid ester, t-amyl peroxy caprylic acid ester, t-amyl peroxy isononoate, tertiary pentyl mistake Aoxidize the organic peroxides such as benzoic ether, 2,2 '-azos two -2,4- methyl pentane nitrile, 1,1 '-azo, two (1- acetoxyl group - 1- diphenylphosphino ethane), 2,2 '-azodiisobutyronitriles, 2,2 '-azos two (2- methylbutyronitrile), two isobutyl of dimethyl -2,2 '-azo Azo-compounds such as nitrile, 4,4 '-azos two (4- cyanopentanoic acid), 1,1 '-azos two (1- cyclohexanenitrile) etc..These compounds can be with The individually a kind of or two or more uses of mixing.
In addition, can be used and generated free radicals by the light irradiation of 150~750nm as (c) radical polymerization initiator Compound.As such compound, to the high sensitivity of light irradiation, therefore it can be cited for example that, Photoinitiation,Photopolymerization,and Photocuring,J.-P.Fouassier,Hanser The alpha-aminoacetophenone derivative and phosphine oxide derivative recorded in Publishers (nineteen ninety-five, p17~p35).These are changed Close object, can individually a kind of use, in addition it can be used in mixed way with above-mentioned organic peroxide or azo-compound.
The use level of above-mentioned (c) radical polymerization initiator (eliminates conduction with bonding agent ingredient in adhesive composite The ingredient of property particle) all-mass on the basis of, such as preferably 0.5 mass % or more, more preferably 1 mass % or more, into One step is preferably 2 mass % or more.If above-mentioned use level is 0.5 mass % or more, there is adhesive composite to be easy sufficiently solid The tendency of change.The use level of above-mentioned (c) radical polymerization initiator (is eliminated in adhesive composite and is led with bonding agent ingredient The ingredient of conductive particles) all-mass on the basis of, such as preferably 40 mass % hereinafter, more preferably 30 mass % hereinafter, Further preferably 20 mass % or less.If above-mentioned use level is 40 mass % hereinafter, there is storage stability to be difficult to decrease Tendency.
(d) salt of boracic
(d) salt (hereinafter referred to as " (d) ingredient ") of boracic is the following general formula (A) compound represented.(d) ingredient contains boron The counter cation X of phosphate compounds and borate compound+。
[changing 24]
In formula (A), R1、R2、R3And R4Each independently represent the alkyl or aryl of hydrogen atom, carbon atom number 1~18, X+ Indicate the cation comprising quaternary phosphonium atom and/or quaternary nitrogen atoms.
As borate compound included in (d) ingredient, can enumerate tetraalkyl borate, four aromatic yl acid salts, Trialkyl aromatic yl acid salt, dialkyl group diarylborinic acid salt, alkyl triaryl borate.Borate compound includes preferably virtue The borate of base, more preferably four aromatic yl acid salts.As borate compound, intramolecular can be with these multiple chemical combination The compound of object or polymer main chain and/or side chain have above compound compound.
As the alkyl for being incorporated into boron atom in borate compound, straight chain, branch or cricoid alkyl can be used. The concrete example of alkyl as carbon atom number 1~18 can enumerate methyl, trifluoromethyl, ethyl, butyl, hexyl, octyl, 2- Ethylhexyl, decyl, dodecyl, octadecyl, propyl, isopropyl, isobutyl group, sec-butyl, tert-butyl, amyl, 1- ethyl Amyl, cyclopenta, cyclohexyl, isopentyl, heptyl, nonyl, undecyl, t-octyl etc..The carbon atom number of alkyl can be 1~ 12。
In addition, the concrete example as the aryl for being incorporated into boron atom in borate compound, can enumerate phenyl, to first Phenyl, tolyl,Base, xylyl, to tert-butyl-phenyl, p-methoxyphenyl, xenyl, naphthalene, p-fluorophenyl, five Fluorophenyl, rubigan, Chloro-O-Phenyl, 3,5- bis- (trifluoromethyl) phenyl etc..In these aryl, preferably phenyl.
In addition, be incorporated into borate compound boron atom alkyl and aryl it is respectively same to each other or different.
As the cation comprising quaternary phosphonium atom, Ke Yi Ju Chu phosphonium ion etc..It, can as the cation comprising quaternary nitrogen atoms To enumerate ammonium ion, imidazol ion, imidazoline ion etc..
For the adhesive composite involved in the present embodiment, as (d) ingredient, the following general formula is preferably comprised (A1) compound represented and/or the following general formula (A2) compound represented.General formula (A1) compound represented Han You Phosphonium chemical combination Counter cation of the object as borate compound.General formula (A2) compound represented contains imidazolium compounds as borate The counter cation of compound.
[changing 25]
In formula (A1), R1、R2、R3And R4Each independently represent the alkyl or aryl of hydrogen atom, carbon atom number 1~18. In addition, R5a、R6a、R7aAnd R8aEach independently represent the alkyl or aryl of hydrogen atom, carbon atom number 1~18.Here, aryl can With substituent group.
[changing 26]
In formula (A2), R1、R2、R3And R4The alkyl or aryl of hydrogen atom, carbon atom number 1~18 are each independently represented, R5b、R6b、R7b、R8bAnd R9bEach independently represent hydrogen atom, halogen atom, alkyl, aryl or alkoxy, R8bAnd R9bIt can be mutual It combines and forms ring.Aryl can have substituent group.
As counter cation phosphonium compounds are used as in (d) ingredient, San Wan Ji Phosphonium, di alkylaryl can be enumerated Phosphonium, alkyl Er Fang Ji Phosphonium, San Fang Ji Phosphonium, Si Wan Ji Phosphonium, Si Fang Ji Phosphonium, trialkyl Fang Ji Phosphonium, dialkyl group Er Fang Ji Phosphonium, alkyl three Fang Ji Phosphonium.Zuo Wei phosphonium compounds can be compound of the intramolecular with these multiple compounds or the main chain in polymer And/or side chain has the compound of above compound.
Especially, stated in phosphonium compounds upper, from curability at low temperatures and storage stability it is more excellent from the viewpoint of, preferably It is taken using at least one three selected from the group being made of three alkane base Phosphonium, two alkane Ji Fangji Phosphonium and the fragrant base Phosphonium of alkyl two for Phosphonium. That is, it is preferred that R5、R6、R7And R8Any of and only one be hydrogen atom.By using San Qu Dai Phosphonium, can make and borated The reactivity for closing object improves, and can be further improved curability at low temperatures.
Furthermore , phosphonium compounds are preferably Wan Ji Phosphonium, the San Wan Ji Phosphonium in more preferably above-mentioned San Qu Dai Phosphonium.
Straight chain, branch or cricoid alkyl can be used in the alkyl of substituent group as Yong Zuo phosphonium compounds.As carbon original The concrete example of the alkyl of subnumber 1~18, can enumerate methyl, trifluoromethyl, ethyl, butyl, hexyl, octyl, 2- ethylhexyl, Decyl, dodecyl, octadecyl, propyl, isopropyl, isobutyl group, sec-butyl, tert-butyl, amyl, 1- ethylpentyl, ring penta Base, cyclohexyl, isopentyl, heptyl, nonyl, undecyl, t-octyl etc..The carbon atom number of alkyl can be 1~12.At these In alkyl, preferably tert-butyl.
The concrete example of the aryl of substituent group as Yong Zuo phosphonium compounds can enumerate phenyl, p-methylphenyl, toluene Base,Base, xylyl, to tert-butyl-phenyl, p-methoxyphenyl, xenyl, naphthalene, p-fluorophenyl, pentafluorophenyl group, to chlorine Phenyl, Chloro-O-Phenyl etc..
Furthermore, the alkyl of the substituent group of Zuo Wei phosphonium compounds and aryl are respectively same to each other or different.
As the imidazolium compounds for being used as counter cation in (d) ingredient, imidazoles can be enumerated and imidazoles spreads out Biology.As imdazole derivatives, for example, 2-methylimidazole, 2- phenylimidazole, 2-ethyl-4-methylimidazole , benzimidazole, 1- tolimidazole, 1- propyl -5- chloro benzimidazole, 1- ethyl -5,6- dichloro benzimidazole Deng.As imidazolium compounds, the compound with these multiple compounds in the molecule can be or in polymer Main chain and/or side chain have the compound of above compound.
In imidazolium compounds, for curability at low temperatures and the further excellent viewpoint of storage stability, preferably Imidazolium compounds with the alkyl or phenyl for being incorporated into imidazole ring, more preferably 2-methylimidazole, 2- phenylimidazole , 2-ethyl-4-methylimidazole.
As the halogen atom for the substituent group for being used as imidazolium compounds, bromine, chlorine, fluorine etc. can be enumerated.It, can as alkyl To enumerate methyl, trifluoromethyl, ethyl, butyl, hexyl, octyl, 2- ethylhexyl, decyl, dodecyl, octadecyl, third Base, isopropyl, isobutyl group, sec-butyl, tert-butyl, amyl, 1- ethylpentyl, cyclopenta, cyclohexyl, isopentyl, heptyl, nonyl Base, undecyl, t-octyl etc..As aryl, can enumerate phenyl, p-methylphenyl, tolyl,It is base, xylyl, right Tert-butyl-phenyl, p-methoxyphenyl, xenyl, naphthalene, p-fluorophenyl, pentafluorophenyl group, rubigan, Chloro-O-Phenyl, 3,5- Two (trifluoromethyl) phenyl etc..As alkoxy, methoxyl group, ethyoxyl, butoxy etc. can be enumerated.R8bAnd R9bIt can be mutual In conjunction with and form aromatic rings, heterocycle, alicyclic ring etc..The substituent group of imidazolium compounds is respectively mutually identical or difference.
As (d) ingredient, the preferably combination of borate and Wan Ji Phosphonium comprising aryl and the borate comprising aryl With the combination of imidazolium compounds.By making (d) ingredient be the salt being made of the borate comprising aryl and Wan Ji Phosphonium or being The salt being made of the borate comprising aryl and imidazolium compounds can more balancedly obtain the low-temperature solid of adhesive composite The raising for the property changed and the raising of storage stability.
Specifically, (d) salt obtained by existing synthetic method can be used in ingredient.For example, in alkali metal or alkaline earth In the mixture of metal and alkyl halide or aryl halide, after instilling the etherate solution of boron trifluoride, hydrogen is instilled Sodium oxide molybdena and generate tetraalkyl boric acid sodium salt or four aryl boric acid sodium salts, then leading to the displacement with Phosphonium and reacting can be obtained by boron - phosphonium salt of hydrochlorate.In addition, for example, by the way that the aqueous solution dissolved with aryl boric acid sodium or alkylboronic acids sodium is added to methylimidazole Hydrochloric acid 10mol (10mol) solution in carry out salt exchange, so that it may obtain borate-imidazole salts.
It can the individually a kind of or two or more uses of mixing by the salt that these compounds obtain.
(d) fusing point of ingredient, from the viewpoint of further increasing from storage stability, such as preferably 60 DEG C or more, more Preferably 70 DEG C or more, further preferably 80 DEG C or more.(d) fusing point of ingredient, the sight further increased from storage stability Point consider, such as preferably 300 DEG C hereinafter, more preferably 270 DEG C hereinafter, further preferably 250 DEG C or less.Bonding agent combination When object includes a variety of (d) ingredient, preferably at least a kind of fusing point of salt is met the above range, and the fusing point of more preferably whole salt all meets Above range.
(d) use level of ingredient, with bonding agent ingredient (eliminating the ingredient of electroconductive particle in adhesive composite) On the basis of all-mass, such as preferably 0.1 mass % or more, more preferably 0.5 mass % or more.If (d) ingredient is matched Resultant is 0.1 mass % or more, has the tendency that the reactive effect for being easy sufficiently to be promoted radical polymerization initiator. (d) use level of ingredient, with the all-mass of bonding agent ingredient (eliminating the ingredient of electroconductive particle in adhesive composite) On the basis of, for example, preferably 20 mass % hereinafter, more preferably 15 mass % hereinafter, further preferably 10 mass % or less. If (d) use level of ingredient is 20 mass % hereinafter, having the tendency that the storage stability of adhesive composite is difficult to decrease.
((e) electroconductive particle)
As long as (e) the electroconductive particle particle conductive in its entirety or surface, but connect for having When the connection of the component of connecting terminal, the preferred average grain diameter particle smaller than the distance between connection terminal.
As (e) electroconductive particle, can enumerate the metallic being made of metals such as Au, Ag, Ni, Cu, Pd or scolding tin, And the particle being made of carbon etc..In addition, (e) electroconductive particle is also possible to dielectric glass, ceramics or plastics etc. As core, the particle of above-mentioned metal, metallic or carbon is coated on the core.As (e) electroconductive particle, in the core of plastics On be coated with the particle of above-mentioned metal, metallic or carbon and thermosol melts metallic, due to having by heating pressurization Morphotropism, therefore increase and reliability raising when connection with the contact area of electrode, therefore preferably.(e) electroconductive particle is for example It can be the particle that silver is coated on the metallic being made of copper.In addition, as (e) electroconductive particle, can be used as The gold for the shape being connected documented by Japanese Unexamined Patent Publication 2005-116291 bulletin, with many minute metal particles with chain Belong to powder.
In addition, by using the surface of these (e) electroconductive particle by macromolecule resin etc. further coating particle, Or it is provided with via the methods of hydridization (hybridization) on the surface of (e) electroconductive particle and is made of insulating properties substance Insulating layer particle, can inhibit electroconductive particle use level increase when be in contact with each other due to particle caused by short circuit so that Insulating properties between telegraph circuit improves, therefore it can individually or with (e) electroconductive particle be used in mixed way.
About the average grain diameter of (e) electroconductive particle, from the aspect of dispersibility and electric conductivity, such as preferably 1~ 18μm.When containing such (e) electroconductive particle, adhesive composite can be suitably used as to anisotropic conductive bonding Agent.(e) laser diffraction formula particle size distribution device can be used (for example, Co., Ltd. island in the average grain diameter of electroconductive particle The manufactured laser diffraction formula SALD-2100 of saliva production) it is measured.
(e) use level of electroconductive particle is not particularly limited, but (is excluded in adhesive composite with bonding agent ingredient The ingredient of electroconductive particle) whole volumes on the basis of, such as preferably 0.1 volume % or more, more preferably 0.2 volume % More than.If above-mentioned use level is 0.1 volume % or more, have the tendency that electric conductivity being inhibited to be lower.(e) electroconductive particle Use level, on the basis of whole volumes of bonding agent ingredient (eliminating the ingredient of electroconductive particle in adhesive composite), example It is such as preferably 30 volume % hereinafter, more preferably 10 volume % or less.If above-mentioned use level is 30 volume % hereinafter, being difficult to The tendency of generation circuit short circuit.Here, " volume % " is determined based on the volume of 23 DEG C of each ingredient before curing, each ingredient Volume can use specific gravity volume be converted by weight.Further, it is also possible to be added in graduated cylinder etc. not make the ingredient dissolve or The solvent appropriate (water, alcohol etc.) for being swollen and soaking the ingredient sufficiently puts into the ingredient wherein and makees increased volume It is found out for the volume of the ingredient.
(other compositions)
For adhesive composite of the present embodiment, for control curing rate and to make storage stability It further increases, stabilizer can be added.As such stabilizer, well known chemical combination can be used without particular limitation The quinone derivatives such as object, preferably benzoquinones and hydroquinone；The phenol derivatives such as 4- metoxyphenol and 4- tert-butyl catechol；2, The aminooxy groups (aminoxyl) such as 2,6,6- tetramethyl piperidine -1- oxygroup and 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygroup spread out Biology；Hindered amine derivatives such as tetramethyl piperidine methacrylate etc..Stabilizer can be individually a kind of or be mixed two or more It uses.
About the use level of stabilizer, with bonding agent ingredient (eliminating the ingredient of electroconductive particle in adhesive composite) All-mass on the basis of, such as preferably 0.005 mass % or more, more preferably 0.01 mass % or more, further preferably For 0.02 mass % or more.If above-mentioned use level is 0.005 mass % or more, it is easy to control curing rate and stores steady The tendency of qualitative easy raising.About the use level of stabilizer, electric conductivity (is eliminated with bonding agent ingredient in adhesive composite The ingredient of particle) all-mass on the basis of, such as preferably 10 mass % hereinafter, more preferably 8 mass % hereinafter, further Preferably 5 mass % or less.If above-mentioned use level is that 10 mass % are difficult to decrease hereinafter, having with the intermiscibility of other compositions Tendency.
In addition, can also be properly added derivative with alkoxy silane in adhesive composite of the present embodiment Object and silazane derivatives are the bonding additives such as coupling agent, closely sealed promotor and the levelling agent of representative.As coupling agent, specifically For, preferably the following general formula (R) compound represented.Coupling agent can the individually a kind of or two or more uses of mixing.
[changing 27]
In formula (R), R33、R34And R35Each independently represent hydrogen atom, the alkyl of carbon atom number 1~5, carbon atom number 1~ The alkoxy carbonyl or aryl of 5 alkoxy, carbon atom number 1~5, R36Indicate (methyl) acryloyl group, vinyl, isocyanates Base, imidazole radicals, sulfydryl, amino, methylamino, dimethylamino, benzyl amino, phenylamino, Cyclohexylamino, morpholino base, piperazinyl, urea Base or glycidyl, s indicate 1~10 integer.
Adhesive composite of the present embodiment can contain for the purpose that stress mitigation and cementability improve Rubber constituent.So-called rubber constituent refers to the ingredient of the status and appearance caoutchouc elasticity of itself (JIS K6200) or by anti- The ingredient of caoutchouc elasticity should be showed.Rubber constituent either solid-state is also possible to liquid, but is flowed in room temperature (25 DEG C) from improving From the viewpoint of dynamic property, preferably liquid.As rubber constituent, it is however preferred to have the compound of polybutadiene skeleton.Rubber at Dividing can have cyano, carboxyl, hydroxyl, (methyl) acryloyl group or morpholinyl.In addition, from the viewpoint of improving cementability, Preferably in the rubber constituent of side chain or end comprising cyano, carboxyl as highly polar group.Wherein, even if having polybutadiene Alkene skeleton is classified as (a) thermoplastic resin when showing thermoplasticity, (b) free radical polymerization is classified as when showing free-radical polymerised Property compound.
As rubber constituent, specifically, polyisoprene, polybutadiene, carboxyl terminal polybutadiene, hydroxyl can be enumerated Base end polybutadiene, 1,2- polybutadiene, carboxyl terminal 1,2- polybutadiene, C-terminal 1,2- polybutadiene, acrylic acid Rubber, SBR styrene butadiene rubbers, C-terminal SBR styrene butadiene rubbers, acrylonitrile-butadiene rubber, polymer end Acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl of the end containing carboxyl, hydroxyl, (methyl) acryloyl group or morpholinyl End poly- (propylene oxide), alkoxysilyl end poly- (propylene oxide), poly- (tetramethylene ether) glycol, polyolefin diols Deng.
In addition, as with above-mentioned highly polar group and in the rubber constituent that room temperature is liquid, specifically, can enumerate Liquid acrylonitrile-butadiene rubber, the liquid for containing carboxyl, hydroxyl, (methyl) acryloyl group or morpholinyl in polymer ends Acrylonitrile-butadiene rubber, liquid carboxylated nitrile rubber etc., the use level of the acrylonitrile as polar group is preferably 10~ 60 mass %.
These rubber constituents can the individually a kind of or two or more uses of mixing.
In addition, in adhesive composite of the present embodiment, mitigated for stress and purpose that cementability improves, Organic fine particles can also be added.The average grain diameter of organic fine particles is for example preferably 0.05~1.0 μm.Here, when organic fine particles by Above-mentioned rubber constituent constitute when, classification in rubber constituent rather than organic fine particles, when organic fine particles are by above-mentioned (a) thermoplastic resin When composition, classification in (a) thermoplastic resin rather than organic fine particles.
As organic fine particles, specifically, can enumerate by polyisoprene, polybutadiene, carboxyl terminal polybutadiene, C-terminal polybutadiene, 1,2- polybutadiene, carboxyl terminal 1,2- polybutadiene, acrylic rubber, styrene-butadiene rubber Glue, acrylonitrile-butadiene rubber, the propylene for containing in polymer ends carboxyl, hydroxyl, (methyl) acryloyl group or morpholinyl Poly- (the oxidation third in nitrile-butadiene rubber, carboxylated nitrile rubber, C-terminal poly- (propylene oxide), alkoxysilyl end Alkene), poly- (tetramethylene ether) glycol, polyolefin diols, (methyl) alkyl acrylate-butadiene-styrene copolymer, (first Base) having of constituting of alkyl acrylate-silicone copolymer or silicone-(methyl) acrylic copolymer or their compound Machine particle.
In addition, the adhesive composite that can be used for aftermentioned connection structural bodies can also be containing silicone particle, in above-mentioned company It connects in structural body, substrate is by containing from by polyethylene terephthalate, polycarbonate, polyethylene naphthalate and ring At least one substrate selected in the group of olefin polymer composition is constituted.
By making substrate by containing from by polyethylene terephthalate, polycarbonate, polyethylene naphthalate Bonding agent group used in the connection structural bodies constituted at least one substrate selected in the group of cyclic olefin polymer composition It closes object and contains silicone particle, thus, it is possible to sufficiently mitigate internal stress, therefore for polyethylene terephthalate, poly- carbonic acid The adhesive strength of ester, polyethylene naphthalate and cyclic olefin polymer further increases, and can be further improved for having The adhesive strength of the component of connection terminal.In addition, can remain further stable after prolonged reliability test Performance.
As above-mentioned silicone particle, it is known to the particle of the organic poly sesquisiloxane resin with caoutchouc elasticity, it can be with Use spherical or unsetting silicone particle.In addition, from the viewpoint of mitigating from dispersibility and internal stress, preferred silicone particle With 1,000,000 or more weight average molecular weight.Furthermore it is preferred that silicone particle has three-dimensional crosslinking structure.Such silicone particle pair High in the dispersibility of resin, the stress retentivity after solidification is more excellent.Silicone with 1,000,000 or more weight average molecular weight is micro- Grain and/or the silicone particle with three-dimensional crosslinking structure, all dissolubility for the polymer such as thermoplastic resin, monomer, solvent It is low, therefore said effect can be obtained more significantly.Herein, so-called " having three-dimensional crosslinking structure ", refers to that polymer chain has three Tie up reticular structure.In addition, the glass transition temperature of silicone particle is for example preferably -130 DEG C or more -20 DEG C hereinafter, more preferably It is -120 DEG C or more -40 DEG C or less.Such silicone particle can sufficiently mitigate the adhesive composite as circuit connection material Internal stress.
As the silicone particle having a structure in which, specifically, following silicone particle can be used: by making to have There is the organopolysiloxane of at least two vinyl, the poly- silicon oxygen of organic hydrogen of hydrogen atom that silicon atom is incorporated into at least two The silicone particle (for example, Japanese Unexamined Patent Application 62-257939 bulletin) that the reaction of alkane and platinum group catalyst obtains；Use tool The silicone particle for thering is the organopolysiloxane of alkenyl, the organopolysiloxane with silicon hydrogen-based and platinum group catalyst to obtain (for example, Japanese Unexamined Patent Application 63-77942 bulletin)；With two organosiloxanes, single organic sesqui siloxane, three organosiloxanes And the silicone particle (for example, Japanese Unexamined Patent Application 62-270660 bulletin) that platinum group catalyst obtains；By methyl-monosilane triol And/or water/alcoholic solution of its partial condensate is added dropwise in aqueous alkali, carry out polycondensation reaction obtain silicone particle (for example, No. 3970453 bulletins of Japanese Patent Publication No.) etc..In addition, addition can also be used to make dispersibility and improving with the adaptation of substrate Or it is copolymerized the silicone particle (for example, Japanese Unexamined Patent Publication 3-167228) of epoxide, added or be copolymerized acroleic acid esterification Close the silicone particle etc. of object.
In addition, in order to further increase dispersibility, it is preferable to use the silicone particle with coreshell type structure.As hud typed Structure has and is formed with the superficial layer with the glass transition temperature higher than the glass transition temperature on core material (stratum nucleare) surface The structure of (shell) and the outside of core material (stratum nucleare) have grafting layer (shell) structure, stratum nucleare and shell can be used Form different silicone particles.Specifically, can be used: in the aqueous dispersions of silicone rubber spheroidal particle, addition alkalinity Substance or alkaline aqueous solution and organotrialkoxysilane, and be hydrolyzed, the hud typed silicone particle (example that condensation reaction obtains Such as, Japanese Patent Publication No. 2832143), the hud typed silicone particle as documented by No. WO2009/051067.In addition it is possible to use Molecular end or intramolecular side chain contain the silicone particle of the functional groups such as hydroxyl, epoxy group, ketimide, carboxyl, sulfydryl.It is such Silicone particle is since the dispersibility for film forming component and free-radical polymerised substance improves, preferably.
The average grain diameter of above-mentioned silicone particle is for example preferably 0.05~25 μm, more preferably 0.1~20 μm.If average Partial size is 0.05 μm or more, has the tendency that inhibiting the reduction of adhesive composite mobility since surface area increases.In addition, if Average grain diameter is 25 μm hereinafter, having the tendency that being easy to give full play to the alleviation effects of internal stress.
About the use level of above-mentioned silicone particle, electroconductive particle (is eliminated with bonding agent ingredient in adhesive composite Ingredient) all-mass on the basis of, such as preferably 3 mass % or more, more preferably 5 mass % or more.If silicone is micro- The use level of grain is 3 mass % or more, has the tendency that internal stress is easy sufficiently to mitigate.About the use level of silicone particle, with On the basis of the all-mass of bonding agent ingredient (eliminating the ingredient of electroconductive particle in adhesive composite), such as preferably 40 Quality % is hereinafter, more preferably 30 mass % or less.If the use level of silicone particle is 40 mass % hereinafter, having can inhibit The flexibility (elasticity modulus, elongation) of adhesive composite reduces, and the tendency that adhesive strength is difficult to decrease.
These silicone particles can be individually a kind of or mix two or more uses.
For adhesive composite of the present embodiment, the adhesive composite is when room temperature is liquid, energy It is enough to be used with paste.Adhesive composite is used by heating when room temperature is solid, solvent additionally can be used and pasted Change.As the solvent that can be used, preferably with adhesive composite and additive without reactivity and performance adequately dissolution Property solvent, the solvent that boiling point preferably under normal pressure is 50~150 DEG C.If boiling point is 50 DEG C or more, it is being placed at room temperature for When the case where volatilizing reduction, have the tendency that the use in open system becomes easy.In addition, if boiling point be 150 DEG C hereinafter, It is easy that solvent is made to volatilize, the reliability after having the tendency that bonding is difficult to decrease.
In addition, adhesive composite of the present embodiment can also be configured to membranaceous and be used as film-like adhesive.This The film-like adhesive that embodiment is related to contains above-mentioned adhesive composite.It will be added in adhesive composite as needed molten Solution obtained by agent etc., after being coated on the fissilities substrate such as fluororesin film, polyethylene terephthalate film, processing release paper, Or above-mentioned solution is impregnated on the substrates such as non-woven fabrics after being placed on fissility substrate, removing solvent etc. can make as film With.If used with the shape of film, it is more convenient to consider from operability etc..It is capable of providing and has according to the present embodiment The adhesive sheet of substrate and film-like adhesive.Film-like adhesive is configured on substrate in adhesive sheet, such as forms bonding Oxidant layer.
Adhesive composite of the present embodiment, which can be used together, to be heated and pressurizeed to be bonded.Heating temperature is preferably 100~200 DEG C of temperature.Pressure is preferably that the range of damage will not be caused to adherend, it is however generally that, preferably 0.1~ 10MPa.These, which are heated and pressurizeed, preferably carries out in the range of 0.5~120 second, can also be in 120~190 DEG C, 3MPa, 10 seconds Heating under be bonded.
Adhesive composite of the present embodiment can be used in making to be configured at the first company on the interarea of first substrate Connecting terminal is electrically connected with second connection end on the interarea for being configured at the second substrate.According to the present embodiment, use is provided Second connection end on the first connection terminal on the interarea for making to be configured at first substrate and the interarea for being configured at the second substrate The application of adhesive composite, film-like adhesive or adhesive sheet that son is electrically connected.According to the present embodiment, it provides and is used for The first connection terminal that preparing makes to be configured on the interarea of first substrate is connect with second on the interarea for being configured at the second substrate The application of the adhesive composite, film-like adhesive or adhesive sheet of the connecting component that terminal is electrically connected.
In addition, adhesive composite of the present embodiment may be used to the company being configured on the interarea of substrate The connection terminal and the distribution component of the solar battery cell of connecting terminal are electrically connected.It provides and is used for according to the present embodiment The connection terminal and distribution component for making the solar battery cell with the connection terminal being configured on the interarea of substrate carry out The application of the adhesive composite, film-like adhesive or adhesive sheet of electrical connection.There is provided according to the present embodiment makes for manufacturing Connection terminal and distribution component of solar battery cell with the connection terminal on the interarea for being configured at substrate carry out electricity The application of the adhesive composite, film-like adhesive or adhesive sheet of the connecting component of connection.
Adhesive composite of the present embodiment, may be used as the bonding agent of homogeneity adherend, and may be used as The bonding agent of the different heterogeneous adherend of thermal expansion coefficient.Specifically, adhesive composite of the present embodiment can be with It is circuit connection material, the CSP elastomer, the bottom CSP of representative as anisotropic conductive adhesive, silver paste, silverskin etc. Layer filler material, LOC band etc. are the semiconductor element adhesives of representative.
For example, by the first connection terminal with the first circuit substrate and configuration on the interarea of first circuit substrate First circuit block and with second circuit substrate and configure on the interarea of the second circuit substrate second connection end son Second circuit component, with the first connection terminal and mutual opposite and the first connection terminal of second connection end and second connection end The state of son electrical connection, is configured, thus, it is possible to constitute the connection of circuit block via the adhesive composite of present embodiment Structural body.In this case, adhesive composite of the present embodiment can effectively serve as adhesive for circuit connection.
(connection structural bodies)
Next, being illustrated to the connection structural bodies and its manufacturing method that use above-mentioned adhesive composite.According to this Embodiment provides the manufacturing method of connection structural bodies, and this method is by making adhesive composite between with first substrate and matching First circuit block of the first connection terminal being placed on the interarea of the first substrate, with there is the second substrate and be configured at this Between the second circuit component of second connection end on the interarea of two substrates, make the adhesive composite in such a state Thus solidification is bonded the first circuit block and the second electricity in the state of making the first connection terminal and second connection end is electrically connected Circuit unit.In addition, providing the manufacturing method of connection structural bodies according to the present embodiment, this method is by making adhesive composite be situated between Between solar battery cell and distribution component with the connection terminal on substrate and the interarea for being configured at the substrate, at this Solidify the adhesive composite in the state of sample, is thus bonded too in the state of making connection terminal and distribution component is electrically connected Positive energy battery unit and distribution component.
Fig. 1 is the schematic sectional view for the connection structural bodies for indicating that first embodiment is related to.Fig. 2 is to indicate shown in FIG. 1 The schematic sectional view of the manufacturing method of connection structural bodies.100 use of connection structural bodies of circuit block shown in FIG. 1 does not contain (e) adhesive composite of electroconductive particle obtains.
The connection structural bodies 100 of circuit block shown in FIG. 1 has circuit block (the first circuit block) 10, circuit block (second circuit component) 20 and connecting component 30.Circuit block 10 has circuit substrate (first substrate) 12 and is configured at circuit Connection terminal (the first connection terminal) 14 on the interarea 12a of substrate 12.Circuit block 20 has circuit substrate (the second substrate) 22 and the connection terminal (second connection end son) 24 that is configured on the interarea 22a of circuit substrate 22.
Connecting component 30 is configured between circuit block 10 and circuit block 20.Connecting component 30 is with interarea 12a and interarea 22a is generally parallel to each other opposite mode and connects circuit block 10 and circuit block 20.In connection structural bodies 100, connection terminal 14 and connection terminal 24 it is oppositely disposed, and be electrically connected and contacting with each other.Connecting component 30 is combined by aftermentioned bonding agent The solidfied material of object 30a is constituted.
Connection structural bodies 100 can for example proceed as follows manufacture.Firstly, as shown in Fig. 2, prepare circuit block 10, Circuit block 20 and the adhesive composite 30a being made of above-mentioned adhesive composite.Adhesive composite 30a for example by Above-mentioned adhesive composite is configured to membranaceous and obtains.Next, the formation in circuit block 20 has the interarea 22a of connection terminal 24 Upper placement adhesive composite 30a.Moreover, in adhesive composite in such a way that connection terminal 14 and connection terminal 24 are opposite Circuit block 10 is placed on 30a.Then, adhesive composite 30a is carried out across circuit block 10 and circuit block 20 on one side Heating on one side solidifies adhesive composite 30a, and pressurizes along the direction vertical with interarea 12a, 22a, circuit block 10, Connecting component 30 is formed between 20.Connection structural bodies 100 is obtained as a result,.
When above-mentioned adhesive composite includes electroconductive particle, by the way that such adhesive composite will be used to make Anisotropic conductive film heats pressurization between opposite connection terminal, and connection terminal is made via electroconductive particle each other Electrical connection, while circuit block being made to be bonded to each other, thus, it is possible to obtain the connection structural bodies of circuit block.Fig. 3 is to indicate that second is real The schematic sectional view for the connection structural bodies that the mode of applying is related to.Fig. 4 is to indicate that the manufacturing method of connection structural bodies shown in Fig. 3 is shown Meaning cross-sectional view.The connection structural bodies 200 of circuit block shown in Fig. 3 uses the adhesive composite for containing (e) electroconductive particle It obtains.
The connection structural bodies 200 of circuit block shown in Fig. 3 have circuit block 10 identical with connection structural bodies 100 and Circuit block 20 and connecting component 40.In connection structural bodies 200, connection terminal 14 is with connection terminal 24 to be mutually isolated State it is oppositely disposed.
Connecting component 40 configures between circuit block 10 and circuit block 20.Connecting component 40 is by aftermentioned bonding agent group The solidfied material for closing object 40a is constituted, with bonding agent ingredient 42 and the electroconductive particle 44 being scattered in bonding agent ingredient 42.It is viscous Agent ingredient 42 is connect to be made of the solidfied material of aftermentioned bonding agent ingredient 42a.In connection structural bodies 200, in opposite connecting pin Between son 14 and connection terminal 24, electroconductive particle 44 is contacted with connection terminal 14,24, and connection terminal 14,24 is via leading as a result, Conductive particles 44 are electrically connected to each other.
Connection structural bodies 200 can for example proceed as follows manufacture.Firstly, as shown in figure 4, prepare circuit block 10, Circuit block 20 and the adhesive composite 40a being made of above-mentioned adhesive composite.Adhesive composite 40a for example by Above-mentioned adhesive composite is configured to membranaceous and obtains.Adhesive composite 40a has bonding agent ingredient 42a and is scattered in viscous Connect the electroconductive particle 44 in agent ingredient 42a.Hereafter, pass through the side with the connection structural bodies 100 for obtaining above-mentioned circuit block The identical method of method, via adhesive composite 40a connection circuit block 10 and circuit block 20.Connection structure is obtained as a result, Body 200.
At least one party in the circuit substrate 12 and circuit substrate 22 of the connection structural bodies 100,200 of foregoing circuit component, It can be by being constituted containing the substrate that glass transition temperature is 200 DEG C of thermoplastic resins below.For example, circuit substrate 12 and electricity At least one party in base board 22, can be by comprising from by polyethylene terephthalate, polycarbonate, poly- naphthalenedicarboxylic acid second At least one organic substrate selected in the group of diol ester and cyclic olefin polymer composition is constituted.It is poly- to benzene in use as a result, When the organic substrates such as naphthalate, polycarbonate, polyethylene naphthalate and cyclic olefin polymer, circuit substrate It is improved with the wetability of adhesive composite, excellent adhesive strength can be obtained under the condition of cure of low temperature as a result,. Therefore, even if stable performance (adhesive strength and company can also be maintained after prolonged reliability test (high temperature and humidity test) Connecting resistance), excellent connection reliability can be obtained.
In addition, side's circuit substrate in circuit substrate 12 and circuit substrate 22 is by containing from by poly terephthalic acid second two At least one substrate selected in the group that alcohol ester, polycarbonate, polyethylene naphthalate and cyclic olefin polymer form When composition, another party's circuit substrate in circuit substrate 12 and circuit substrate 22 can be by containing from by polyimides and poly- to benzene At least one substrate selected in the group of naphthalate composition is constituted.Circuit substrate and adhesive composite as a result, Wetability and adhesive strength further increase, superior connection reliability can be obtained.
Here, circuit substrate 12,22 can be by containing the inanimate matters, poly terephthalic acid second such as semiconductor, glass or ceramics The organic matters such as diol ester, polyethylene naphthalate, cyclic olefin polymer, polyimides or polycarbonate, glass/epoxy etc. The substrate of these composite material is constituted.In addition, circuit substrate 12,22 can be flexible base board.
Fig. 5 is the schematic sectional view for the connection structural bodies for indicating that third embodiment is related to.Solar battery shown in fig. 5 Module 300 has solar battery cell 310a, 310b and distribution component 320 and connecting component 330.
Solar battery cell 310a, 310b have substrate 312, are configured on surface (interarea) 312a of substrate 312 Surface electrode (connection terminal) 314 and the rear electrode (connection terminal) being configured on the back side (interarea) 312b of substrate 312 316.Substrate 312 is made of such as composite materials such as the inanimate matters such as semiconductor, glass or ceramics, glass/epoxy.In addition, substrate 312 can be flexible base board.Surface 312a is light-receiving surface.
Distribution component 320 is the component for solar battery cell 310a to be electrically connected with other component, for example, by one A solar battery cell is electrically connected with other solar battery cells.In Fig. 5, by distribution component 320, make solar-electricity The surface electrode 314 of pool unit 310a is electrically connected with the rear electrode 316 of solar battery cell 310b.
Connecting component 330 is respectively arranged between solar battery cell 310a and distribution component 320 and solar-electricity Between pool unit 310b and distribution component 320, and connect solar battery cell 310a, 310b and distribution component 320.Connection Component 330 contains the solidfied material of above-mentioned adhesive composite, and contains insulating properties substance.Connecting component 330 can further contain Conductive particle can also not contain electroconductive particle.When connecting component 330 contains electroconductive particle, solar battery The surface electrode 314 of unit 310a can be electrically connected with distribution component 320 via electroconductive particle.In addition, solar battery The rear electrode 316 of unit 310b can also be electrically connected with distribution component 320 via electroconductive particle.When connecting component 330 When without containing electroconductive particle, for example, the surface electrode 314 and/or solar battery cell of solar battery cell 310a The rear electrode 316 of 310b can be contacted with distribution component 320.
For solar cell module 300, connecting component 330 is made of the solidfied material of above-mentioned adhesive composite.By This, the company between solar battery cell 310a and distribution component 320 and between solar battery cell 310b and distribution component 320 The adhesive strength of relay part 330 is sufficiently high, and the connection resistance between solar battery cell 310a and distribution component 320 is abundant It is small.In addition, even if also can sufficiently inhibit reduction and the connection electricity of adhesive strength when placing for a long time under hot and humid environment The increase of resistance.In turn, connecting component 330 can be formed by the heat treatment between low-temperature short-time.The sun shown in fig. 5 as a result, Energy battery module can not be such that solar battery cell 310a, 310b deteriorates and be manufactured in connection, can have than existing There is high reliability.
Solar cell module 300 can be replaced upper with solar battery cell 310a, 310b and distribution component 320 State the circuit block 10 and circuit block 20 in the manufacturing method of connection structural bodies 100,200, with above-mentioned connection structural bodies The identical method of manufacturing method is manufactured.
Here, above-mentioned viscous as connecting component in connection structural bodies 100,200 and solar cell module 300 It connects agent composition and does not need to be fully cured the solidification of attainable top (in the case where providing condition of cure), as long as on generating It states characteristic then and can be partially cured state.
Embodiment
Hereinafter, the present invention is specifically described according to embodiment, however, the present invention is not limited thereto.
< thermoplastic resin >
(preparation of polyester polyurethane)
By polyester urethane resin (Japan spin Co. Ltd. system, UR-4800 (trade name), weight average molecular weight: 32000, Glass transition temperature: 106 DEG C) it is dissolved in the 1:1 in the mixed solvent of methyl ethyl ketone and toluene, prepare 30 mass %'s of resin component Mixed solvent dissolves product.
(preparation of phenoxy resin)
By phenoxy resin (trade name: YP-50 (Toto Kasei KK's system), weight average molecular weight: 60000, vitrifying turn Temperature: 80 DEG C) 40 mass parts are dissolved in 60 mass parts of methyl ethyl ketone, prepare the solution of 40 mass % of solid component.
< free-radical polymerised compound >
(synthesis of urethane acrylate (UA1))
In the reaction for having blender, thermometer, the reflux condensing tube with calcium chloride tube and nitrogen ingress pipe In container, poly- (1,6- hexylene glycol the carbonic ester) (trade name: Duranol of number-average molecular weight 1000 was equably instilled with 3 hours T5652, Asahi Chemical Corp's system) 2500 mass parts (2.50mol) and isophorone diisocyanate (Sigma- Aldrich system) 666 mass parts (3.00mol), after fully importing nitrogen into reaction vessel, are heated at 70~75 DEG C It is reacted.In the reaction vessel, hydroquinone monomethyl ether (Sigma-Aldrich corporation) 0.53 mass parts and tin dilaurate are added After dibutyl tin (Sigma-Aldrich corporation) 5.53 mass parts, 2-Hydroxy ethyl acrylate (Sigma-Aldrich is added Corporation) 238 mass parts (2.05mol), it is reacted 6 hours under air environment at 70 DEG C, obtains urethane acrylate (UA1).The weight average molecular weight of urethane acrylate is 15000.
(preparation of the vinyl compound (P-2M) with phosphate)
As the vinyl compound with phosphate, prepare 2- (methyl) acryloyl-oxyethyl phosphate (trade name: Light Ester P-2M, Kyoeisha Chemical Co., Ltd.'s system).
The preparation > of < boron compound
As boron compound, prepare three tertiary Ding Ji Phosphonium tetraphenyl borate salts (referred to as: TBPTB, Tokyo chemical conversion industry strain formula meeting Society's system, fusing point: 261 DEG C), di-t-butyl Jia Ji Phosphonium tetraphenyl borate salts (referred to as: DBMPTB, Tokyo Chemical Industry Co., Ltd System, fusing point: 158 DEG C).
In addition, 2-ethyl-4-methylimidazole tetraphenyl borate salts (EMI-B) is synthesized as follows as boron compound.It is first First, agitating device, thermometer and return channel are assemblied in the four-hole boiling flask of 30ml.Next, by sodium tetraphenylborate (Aldrich system) 3.4g (10mmol) is dissolved in solution obtained from distilled water 100ml, is added to 2- ethyl -4- methyl In the solution of the 1mol/l hydrochloric acid 10mol (10mol) of imidazoles (Aldrich system) 1.1g (10mmol).It is small in 25 DEG C of stirrings 1 Shi Hou separates oily mater.After obtained oily mater is diluted with methyl ethyl ketone (MEK), washing, and then use rotary evaporator Concentration.Obtained solid is washed with hexane, it is (molten to obtain white solid 2-ethyl-4-methylimidazole tetraphenyl borate salts Point: 200 DEG C), yield 35%.
The preparation > of < amine compounds
As amine compounds, prepare n,N-Dimethylaniline (referred to as: DMA, Aldrich system).
< radical polymerization initiator >
As radical polymerization initiator, prepare dibenzoyl peroxide (trade name: NYPER BW, day oil strain formula meeting Society's system) and dilauroyl peroxide (trade name: PEROYL L, Japan Oil Co's system).
< electroconductive particle >
(production of electroconductive particle)
0.2 μm of thickness of nickel layer is being set using polystyrene as the surface of the particle of core, is then being set on the outside of the nickel layer Set 0.02 μm of thickness of layer gold, the electroconductive particle of 10 μm of average grain diameter of production, specific gravity 2.5.
[Examples 1 to 8 and comparative example 1~4]
(production of adhesive for circuit connection)
Draw by solid masses than cooperation thermoplastic resin, free-radical polymerised compound and free radical polymerization as shown in table 1 Hair agent and boron compound or amine compounds (eliminate electric conductivity with bonding agent ingredient in turn in adhesive for circuit connection The ingredient of particle) whole volumes on the basis of, cooperate 1.5 volume % of dispersed electro-conductive particle, obtain adhesive for circuit connection. Obtained adhesive for circuit connection is set with painting tooling on the fluororesin film for being coated on 80 μm of thickness, passes through 70 DEG C, 10 points The heated-air drying of clock obtain adhesive layer with a thickness of 20 μm of membranaceous adhesive for circuit connection.
Table 1
UR-4800 YP-50 UA1 P-2M TBPTB DBMPTB EMI-B DMA NYPER BW PEROYL L
Embodiment 1 50 - 50 3 5 - - - 8 -
Embodiment 2 50 - 50 3 - 5 - - 8 -
Embodiment 3 50 - 50 3 5 - - - - 8
Embodiment 4 50 - 50 3 - 5 - - - 8
Embodiment 5 - 50 50 3 3 - - - 8 -
Embodiment 6 - 50 50 3 - 3 - - - 8
Embodiment 7 50 - 50 3 - - 5 - 8 -
Embodiment 8 50 - 50 3 - - 5 - - 8
Comparative example 1 50 - 50 3 - - - 3 8 -
Comparative example 2 50 - 50 3 - - - 3 - 8
Comparative example 3 50 - 50 3 - - - - 8 -
Comparative example 4 50 - 50 3 - - - - - 8
(measurement of connection resistance, adhesive strength)
Make the adhesive for circuit connection of Examples 1 to 8 and comparative example 1~4 that there are 500 on polyimide film 25 μm of line width, 50 μm of spacing, the flexible circuit board (FPC) of the copper circuit of 8 μm of thickness, the thin layer with the ITO for being formed with 0.2 μm Between the glass (ITO, 20 Ω of sheet resistance/) of thickness 1.1mm.With thermo-compression bonding device (heating method: permanent heat type, the beautiful work in east Journey corporation), heating pressurization 10 seconds at 120 DEG C, 2MPa carry out the connection that width is 2mm, make connection structural bodies A.Even After connecing immediately and after being kept for 240 hours in 85 DEG C, the constant temperature and humidity cabinet of 85%RH (after high temperature and humidity test), with ten thousand The resistance value between the adjoining circuit of connection structural bodies A is measured with table.Resistance value is to abut being averaged for 37 resistance between circuit To indicate.
In addition, upon connection immediately and after high temperature and humidity test, according to JIS-Z0237 with 90 degree of stripping method measurement connection knots The adhesive strength of structure body A.Herein, as the measurement device of adhesive strength, Japan BALDWIN Co. Ltd. system TENSILON is used UTM-4 (peeling rate 50mm/min, 25 DEG C).
Make the adhesive for circuit connection of Examples 1 to 8 and comparative example 1~4 between polyimide film (350 DEG C of Tg) It is upper with 80 150 μm of line widths, 300 μm of spacing, 8 μm of thickness copper circuit flexible circuit board (FPC), be formed with 5 μ of thickness Between 0.1 μm of thickness of pet substrate (Ag) of the thin layer of the Ag paste of m.With thermo-compression bonding device (heating method: permanent heat type, the beautiful work in east Journey corporation), heating pressurization 20 seconds at 120 DEG C, 2MPa carry out the connection that width is 2mm, make connection structural bodies B.Even After connecing immediately and after being kept for 240 hours in 85 DEG C, the constant temperature and humidity cabinet of 85%RH (after high temperature and humidity test), with ten thousand The resistance between the adjoining circuit for the connection structural bodies B being made of the pet substrate of FPC and the thin layer for being formed with Ag paste is measured with table Value.Resistance value is indicated with abutting the average of 37 resistance between circuit.
In addition, upon connection immediately and after high temperature and humidity test, being surveyed under the same conditions with above-mentioned connection structural bodies A Fixed, evaluation connection structural bodies B adhesive strength.
As above the connection resistance of connection structural bodies A, B measured and the measurement result of adhesive strength are shown in the following table 2.
Table 2
(storage stability test)
The adhesive for circuit connection of Examples 1 to 2,7 and comparative example 1~2 is added in gas-barrier container (Asahi Chemical Industry PAX Co. Ltd. system, trade name: Polyflexbag (Port リ Off レ ッ Network ス バ ッ グ) flying dragon, model: N-9, material: nylon 60 μm of thickness of 15 μm/PE of thickness, size: 200mm × 300mm), after removing the air in gas-barrier container, with heat-sealing secret Envelope, is then placed 48 hours under 40 DEG C of environment.By being placed under above-mentioned environment, with 5 phases of the moons of placement under -10 DEG C of environment When.Hereafter, make the adhesive for circuit connection of Examples 1 to 2,7 and comparative example 1~2 respectively between FPC same as described above and It is formed between the glass of the thin layer of ITO and between FPC and the pet substrate of thin layer for being formed with Ag paste.With with above-mentioned connection Identical method and condition carries out heating crimping to it to make connection structural bodies when resistance and determining bonding strength.With with it is above-mentioned Identical method measures the connection resistance and adhesive strength of the connection structural bodies.
As above the connection resistance of the connection structural bodies measured and the measurement result of adhesive strength are shown in the following table 3.
Table 3
In addition, the connection structural bodies for using adhesive for circuit connection obtained in embodiment 3~6,8, also carries out With Examples 1 to 2,7 identical tests, as a result, with Examples 1 to 2,7 identical, curability at low temperatures and storage stability are good.
Using the connection structural bodies A of the FPC/ITO of adhesive for circuit connection obtained in Examples 1 to 8, whether Carry out storage stability test, after 120 DEG C of heating temperature connections immediately and 85 DEG C, protect in the constant temperature and humidity cabinet of 85%RH After holding 240 hours (after high temperature and humidity test), be demonstrated by about 4.0 Ω good connection resistance below and 580N/m with On good adhesive strength.In addition, in the connection structural bodies B of FPC/Ag, after 120 DEG C of heating temperature connections immediately, with And 85 DEG C, kept for 240 hours in the constant temperature and humidity cabinet of 85%RH after (after high temperature and humidity test), be also demonstrated by about 1.6 Ω with Under good connection resistance and 590N/m or more good adhesive strength.The electricity that Examples 1 to 8 obtains can be confirmed The curability at low temperatures and storage stability of road connecting adhesive are excellent.
In contrast, using the connection structural bodies of adhesive for circuit connection obtained in comparative example 1~2, although making Available good connection performance when with adhesive for circuit connection before storage stability test, but since circuit connection is used Bonding agent does not include the salt of (d) boracic, therefore in the adhesive for circuit connection after using storage stability test, can be true Recognize in constant temperature and humidity cabinet the connection resistance after being kept for 240 hours (after high temperature and humidity test) to increase.In addition, using comparative example 3 The connection structural bodies of adhesive for circuit connection obtained in~4, since adhesive for circuit connection does not include (d) boracic Salt, even therefore without storage stability test, it can be identified that being kept in constant temperature and humidity cabinet 240 small When after connection resistance (after high temperature and humidity test) increase.

Claims (82)

1. a kind of adhesive composite contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) radical polymerization Initiator and (d) salt of boracic are closed,
Wherein, the salt of (d) boracic is the following general formula (A) compound represented,
In formula (A), R1、R2、R3And R4Each independently represent the alkyl or aryl of hydrogen atom, carbon atom number 1~18, X+It indicates Cation comprising quaternary phosphonium atom,
The salt Bao Han phosphonium compounds of (d) boracic include the cation of quaternary phosphonium atom as described in,
Stated phosphonium compounds are from by three alkane base Phosphonium, two alkane Ji Fangji Phosphonium, the fragrant base Phosphonium of alkyl two, three fragrant base Phosphonium, four alkane base Phosphonium, three At least one selected in the group of the fragrant base Phosphonium of alkane Ji Fangji Phosphonium, dialkyl group two and the fragrant base Phosphonium composition of alkyl three.
2. adhesive composite according to claim 1, wherein as the salt of (d) boracic, contain the following general formula (A1) compound represented,
In formula (A1), R1、R2、R3、R4、R5a、R6a、R7aAnd R8aEach independently represent the alkane of hydrogen atom, carbon atom number 1~18 Base or aryl.
3. adhesive composite according to claim 2, wherein the R5a、R6a、R7aAnd R8aAny of and only one A is hydrogen atom.
4. adhesive composite described in any one of claim 1 to 3, wherein the salt of (d) boracic include from by Tetraalkyl borate, four aromatic yl acid salts, trialkyl aromatic yl acid salt, dialkyl group diarylborinic acid salt and alkyl triaryl boric acid At least one selected in the group of salt composition is as borate compound.
5. adhesive composite described in any one of claim 1 to 3, wherein the salt of (d) boracic includes to have The borate of aryl is as borate compound.
6. adhesive composite described in any one of claim 1 to 3, wherein the salt of (d) boracic includes four virtues Ylboronic acid salt is as borate compound.
7. adhesive composite described in any one of claim 1 to 3, wherein the fusing point of the salt of (d) boracic is 60 DEG C or more 300 DEG C or less.
8. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of the salt of (d) boracic is 0.1 mass % or more.
9. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of the salt of (d) boracic is 0.5 mass % or more.
10. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of the salt of (d) boracic is 20 mass % or less.
11. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of the salt of (d) boracic is 15 mass % or less.
12. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of the salt of (d) boracic is 10 mass % or less.
13. adhesive composite described in any one of claim 1 to 3, wherein (b) free-radical polymerisedization Closing object includes the free-radical polymerised compound other than vinyl compound and the vinyl compound with phosphate.
14. adhesive composite according to claim 13, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the vinyl compound with phosphate is 0.2 mass % or more.
15. adhesive composite according to claim 13, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the vinyl compound with phosphate is 0.3 mass % or more.
16. adhesive composite according to claim 13, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the vinyl compound with phosphate is 0.5 mass % or more.
17. adhesive composite according to claim 13, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the vinyl compound with phosphate is 15 mass % or less.
18. adhesive composite according to claim 13, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the vinyl compound with phosphate is 10 mass % or less.
19. adhesive composite according to claim 13, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the vinyl compound with phosphate is 5 mass % or less.
20. adhesive composite described in any one of claim 1 to 3, wherein (b) free-radical polymerisedization Closing object includes the N- ethylene base system selected from the group being made of N- vinyl compound and N, N- dialkyl group vinyl compound Free-radical polymerised compound other than compound and the N- vinyl compound.
21. adhesive composite according to claim 20, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the N- vinyl compound is 0.2 mass % or more.
22. adhesive composite according to claim 20, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the N- vinyl compound is 0.3 mass % or more.
23. adhesive composite according to claim 20, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the N- vinyl compound is 0.5 mass % or more.
24. adhesive composite according to claim 20, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the N- vinyl compound is 15 mass % or less.
25. adhesive composite according to claim 20, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the N- vinyl compound is 10 mass % or less.
26. adhesive composite according to claim 20, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the N- vinyl compound is 5 mass % or less.
27. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, in addition to meeting vinyl compound or N- ethylene base system with phosphate The use level of (b) free-radical polymerised compound other than the compound of compound is 5 mass % or more.
28. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, in addition to meeting vinyl compound or N- ethylene base system with phosphate The use level of (b) free-radical polymerised compound other than the compound of compound is 10 mass % or more.
29. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, in addition to meeting vinyl compound or N- ethylene base system with phosphate The use level of (b) free-radical polymerised compound other than the compound of compound is 15 mass % or more.
30. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, in addition to meeting vinyl compound or N- ethylene base system with phosphate The use level of (b) free-radical polymerised compound other than the compound of compound is 95 mass % or less.
31. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, in addition to meeting vinyl compound or N- ethylene base system with phosphate The use level of (b) free-radical polymerised compound other than the compound of compound is 80 mass % or less.
32. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, in addition to meeting vinyl compound or N- ethylene base system with phosphate The use level of (b) free-radical polymerised compound other than the compound of compound is 70 mass % or less.
33. adhesive composite described in any one of claim 1 to 3, wherein as (b) free radical polymerization Property compound, contains urethane acrylate.
34. adhesive composite according to claim 33, wherein as the urethane acrylate, containing following Urethane acrylate shown in general formula (N),
In formula (N), R23And R24Each independently represent hydrogen atom or methyl, R25Indicate ethylidene or propylidene, R26Indicate saturation Fatty group or saturated fat cyclic group, R27It indicates the representative examples of saturated aliphatic base containing ester group or saturated fat cyclic group or contains carbon The representative examples of saturated aliphatic base or saturated fat cyclic group of perester radical, k indicate 1~40 integer, here, in formula (N), R25Each other, R26That This can be respectively identical or different.
35. adhesive composite according to claim 33, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the urethane acrylate is 5 mass % or more.
36. adhesive composite according to claim 33, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the urethane acrylate is 10 mass % or more.
37. adhesive composite according to claim 33, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the urethane acrylate is 15 mass % or more.
38. adhesive composite according to claim 33, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the urethane acrylate is 95 mass % or less.
39. adhesive composite according to claim 33, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the urethane acrylate is 80 mass % or less.
40. adhesive composite according to claim 33, wherein to eliminate electroconductive particle in adhesive composite Ingredient all-mass on the basis of, the use level of the urethane acrylate is 70 mass % or less.
41. adhesive composite described in any one of claim 1 to 3, wherein as (c) free radical polymerization Initiator, the organic peroxide that containing 1 minute half life temperature be 90~175 DEG C and weight average molecular weight is 180~1000.
42. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (c) radical polymerization initiator be 0.5 mass % with On.
43. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (c) radical polymerization initiator be 1 mass % with On.
44. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (c) radical polymerization initiator be 2 mass % with On.
45. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (c) radical polymerization initiator be 40 mass % with Under.
46. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (c) radical polymerization initiator be 30 mass % with Under.
47. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (c) radical polymerization initiator be 20 mass % with Under.
48. adhesive composite described in any one of claim 1 to 3, wherein (a) thermoplastic resin includes From by phenoxy resin, polyurethane resin, butyral resin, acrylic resin, polyimide resin and polyamide and tool At least one selected in the group being made of vinylacetate as the copolymer of structural unit.
49. adhesive composite described in any one of claim 1 to 3, wherein (a) thermoplastic resin includes Polyester urethane resin.
50. adhesive composite described in any one of claim 1 to 3, wherein the weight of (a) thermoplastic resin Average molecular weight is 5000 or more.
51. adhesive composite described in any one of claim 1 to 3, wherein the weight of (a) thermoplastic resin Average molecular weight is 7000 or more.
52. adhesive composite described in any one of claim 1 to 3, wherein the weight of (a) thermoplastic resin Average molecular weight is 10000 or more.
53. adhesive composite described in any one of claim 1 to 3, wherein the weight of (a) thermoplastic resin Average molecular weight is 150000 or less.
54. adhesive composite described in any one of claim 1 to 3, wherein the weight of (a) thermoplastic resin Average molecular weight is 100000 or less.
55. adhesive composite described in any one of claim 1 to 3, wherein the weight of (a) thermoplastic resin Average molecular weight is 80000 or less.
56. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (a) thermoplastic resin is 5 mass % or more.
57. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (a) thermoplastic resin is 15 mass % or more.
58. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (a) thermoplastic resin is 80 mass % or less.
59. adhesive composite described in any one of claim 1 to 3, wherein to be eliminated in adhesive composite On the basis of the all-mass of the ingredient of electroconductive particle, the use level of (a) thermoplastic resin is 70 mass % or less.
60. adhesive composite described in any one of claim 1 to 3, wherein further contain (e) electric conductivity grain Son.
61. adhesive composite according to claim 60, wherein to eliminate electroconductive particle in adhesive composite Ingredient whole volumes on the basis of, the use level of (e) electroconductive particle is 0.1 volume % or more.
62. adhesive composite according to claim 60, wherein to eliminate electroconductive particle in adhesive composite Ingredient whole volumes on the basis of, the use level of (e) electroconductive particle is 0.2 volume % or more.
63. adhesive composite according to claim 60, wherein to eliminate electroconductive particle in adhesive composite Ingredient whole volumes on the basis of, the use level of (e) electroconductive particle is 30 volume % or less.
64. adhesive composite according to claim 60, wherein to eliminate electroconductive particle in adhesive composite Ingredient whole volumes on the basis of, the use level of (e) electroconductive particle is 10 volume % or less.
65. adhesive composite described in any one of claim 1 to 3 is used to make to be configured at the master of first substrate The first connection terminal on face is electrically connected with second connection end on the interarea for being configured at the second substrate.
66. adhesive composite described in any one of claim 1 to 3 is used to make the master with substrate is configured at The connection terminal and the distribution component of the solar battery cell of connection terminal on face are electrically connected.
67. adhesive composite described in any one of claim 1 to 3 becomes the interconnecting piece in connection structural bodies Part, the connection structural bodies have: with first substrate and the first connection terminal for being configured on the interarea of the first substrate First circuit block, the second circuit portion with the second substrate and the second connection end being configured on the interarea of the second substrate Part and the connecting component being configured between first circuit block and the second circuit component, described first connects Connecting terminal and second connection end are electrically connected.
68. adhesive composite described in any one of claim 1 to 3 becomes the interconnecting piece in connection structural bodies Part, the connection structural bodies have: the solar battery list with substrate and the connection terminal being configured on the interarea of the substrate Member, distribution component and the connecting component being configured between the solar battery cell and the distribution component, it is described Connection terminal and the distribution component are electrically connected.
69. a kind of film-like adhesive, it includes the adhesive composites described in any one of claim 1~64.
70. a kind of adhesive sheet has film-like adhesive described in substrate and claim 69, wherein the membranaceous bonding Agent is configured on the substrate.
71. a kind of anisotropic conductive film, it includes the adhesive composites described in any one of claim 1~64.
72. a kind of connection structural bodies, has: with first substrate and the first connection being configured on the interarea of the first substrate First circuit block of terminal, second with the second substrate and the second connection end being configured on the interarea of the second substrate Circuit block and the connecting component being configured between first circuit block and the second circuit component,
The connecting component contains the solidfied material of adhesive composite described in any one of claim 1~64,
First connection terminal and second connection end are electrically connected.
73. the connection structural bodies according to claim 72, wherein in the first substrate and the second substrate at least One side comprising the substrate that glass transition temperature is 200 DEG C of thermoplastic resins below by constituting.
74. the connection structural bodies according to claim 72, wherein in the first substrate and the second substrate at least One side is by comprising from by polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cyclic olefin polymer At least one substrate selected in the group of composition is constituted.
75. the connection structural bodies according to claim 72, wherein the first substrate is by comprising from by poly terephthalic acid It is selected in the group that glycol ester, polycarbonate, polyethylene naphthalate and cyclic olefin polymer form at least one Substrate is constituted, and the second substrate from the group being made of polyimide resin and polyethylene terephthalate by comprising selecting At least one substrate out is constituted.
76. a kind of connection structural bodies, has: the solar energy with substrate and the connection terminal being configured on the interarea of the substrate Battery unit, distribution component and the connecting component being configured between the solar battery cell and the distribution component,
The connecting component contains the solidfied material of adhesive composite described in any one of claim 1~64,
The connection terminal and the distribution component are electrically connected.
77. the manufacturing method of connection structural bodies, this method is by combining bonding agent described in any one of claim 1~64 Object is between the first circuit block and tool with first substrate and the first connection terminal being configured on the interarea of the first substrate There is the second substrate between the second circuit component of second connection end that is configured on the interarea of the second substrate, such Solidify the adhesive composite under state, is thus electrically connected first connection terminal and second connection end In the state of be bonded first circuit block and the second circuit component.
78. the manufacturing method of connection structural bodies, this method is by combining bonding agent described in any one of claim 1~64 Object between solar battery cell and distribution component with substrate and the connection terminal being configured on the interarea of the substrate, In such a state solidify the adhesive composite, is thus electrically connected the connection terminal and the distribution component In the state of be bonded the solar battery cell and the distribution component.
79. adhesive composite described in any one of claim 1~64 is in the interarea for making to be configured at first substrate The first connection terminal and second connection end that is configured on the interarea of the second substrate be electrically connected in application.
80. adhesive composite described in any one of claim 1~64 makes to be configured at the master of first substrate for manufacturing The connecting component that the first connection terminal on face is electrically connected with second connection end being configured on the interarea of the second substrate In application.
81. adhesive composite described in any one of claim 1~64 is for making with the interarea for being configured at substrate Connection terminal solar battery cell the connection terminal and distribution component be electrically connected in application.
82. adhesive composite described in any one of claim 1~64 makes the master with substrate is configured at for manufacturing In the connecting component that connection terminal and distribution component of the solar battery cell of connection terminal on face are electrically connected Using.
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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6123547B2 (en) * 2013-07-26 2017-05-10 日立化成株式会社 Circuit connection material, circuit connection structure, method for manufacturing circuit connection structure, adhesive composition, and adhesive sheet
JP6232855B2 (en) * 2013-08-30 2017-11-22 デクセリアルズ株式会社 Radical polymerization type adhesive composition and method for producing electrical connector
WO2015033834A1 (en) * 2013-09-05 2015-03-12 積水化学工業株式会社 Curable composition and connection structure
JP6330346B2 (en) * 2014-01-29 2018-05-30 日立化成株式会社 Adhesive composition, electronic member using adhesive composition, and method for manufacturing semiconductor device
KR101469199B1 (en) * 2014-04-15 2014-12-09 한상용 Solid label, and manufacture method thereof
JP2016044222A (en) * 2014-08-21 2016-04-04 日立化成株式会社 Adhesive composition and connection structure
JP6461577B2 (en) * 2014-11-28 2019-01-30 東洋アルミニウム株式会社 Inlet antenna for RFID, RFID and manufacturing method thereof
JP6487203B2 (en) * 2014-12-24 2019-03-20 スリーエム イノベイティブ プロパティズ カンパニー Design transfer sheet, decorative film and method for producing the same
CN107429143B (en) * 2015-04-23 2019-08-16 日立化成株式会社 Adhesive composite and connection structural bodies
JP6428716B2 (en) * 2016-07-12 2018-11-28 千住金属工業株式会社 Conductive adhesives, joints and joints
CN110582840A (en) * 2017-04-21 2019-12-17 日立化成株式会社 Semiconductor device and method for manufacturing the same
DE102019121371B4 (en) * 2018-08-08 2022-10-06 Lg Display Co., Ltd. Integrated circuit assembly and display device using same
JP2019026851A (en) * 2018-09-19 2019-02-21 日立化成株式会社 Adhesive composition and connection structure
KR102387071B1 (en) * 2019-08-06 2022-04-18 주식회사 비티엘첨단소재 Aluminium pouch film for the secondary battery and the manufacturing method thereof
JP2020111760A (en) * 2020-04-07 2020-07-27 日立化成株式会社 Adhesive composition and connection structure
WO2022190920A1 (en) * 2021-03-10 2022-09-15 富士フイルム株式会社 Underfill composition, coating film, cured film, multilayer wiring board, and production method for multilayer wiring board

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101857778A (en) * 2009-04-08 2010-10-13 日东电工株式会社 Thermosetting die bonding film
CN101925663A (en) * 2008-04-17 2010-12-22 日立化成工业株式会社 Adhesive composition, adhesive for circuit connection, connected structure, and semiconductor device

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2610900B2 (en) 1987-10-27 1997-05-14 ソニーケミカル 株式会社 Thermosetting anisotropic conductive adhesive sheet and method for producing the same
JP3998737B2 (en) * 1996-05-22 2007-10-31 株式会社トクヤマ Dental adhesive composition
AU6520798A (en) 1997-03-31 1998-10-22 Hitachi Chemical Company, Ltd. Circuit connecting material, and structure and method of connecting circuit terminal
EP0889360B1 (en) * 1997-06-30 2002-01-30 Siemens Aktiengesellschaft Reactive resin mixtures and their use
JPH11140383A (en) * 1997-11-07 1999-05-25 Tokuyama Corp Adhesive composition
US6045895A (en) * 1997-12-01 2000-04-04 3M Innovative Properties Company Multilayer films having pressure sensitive adhesive layers
JP4514848B2 (en) 1999-04-09 2010-07-28 サンメディカル株式会社 Polymerization initiator and dental material using the same
JP5527600B2 (en) * 2009-10-07 2014-06-18 日立化成株式会社 Epoxy resin composition and electronic component device using the same
JP4844677B2 (en) * 2010-01-27 2011-12-28 日立化成工業株式会社 Circuit connection material, circuit member connection structure, and circuit member connection method.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101925663A (en) * 2008-04-17 2010-12-22 日立化成工业株式会社 Adhesive composition, adhesive for circuit connection, connected structure, and semiconductor device
CN101857778A (en) * 2009-04-08 2010-10-13 日东电工株式会社 Thermosetting die bonding film

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CN103160238B (en) 2016-09-28
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CN105907355A (en) 2016-08-31
CN103160238A (en) 2013-06-19

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