CN108676520A - Anisotropically conducting adhesive, the application of adhesive composite and connector - Google Patents

Anisotropically conducting adhesive, the application of adhesive composite and connector Download PDF

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Publication number
CN108676520A
CN108676520A CN201810615121.5A CN201810615121A CN108676520A CN 108676520 A CN108676520 A CN 108676520A CN 201810615121 A CN201810615121 A CN 201810615121A CN 108676520 A CN108676520 A CN 108676520A
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CN
China
Prior art keywords
resin
compound
anisotropically conducting
free
conducting adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810615121.5A
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Chinese (zh)
Inventor
工藤直
松田和也
藤绳贡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to CN201810615121.5A priority Critical patent/CN108676520A/en
Publication of CN108676520A publication Critical patent/CN108676520A/en
Pending legal-status Critical Current

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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2224/29455—Nickel [Ni] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
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    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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    • 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
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
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    • H01L2224/832—Applying energy for connecting
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    • H01L2224/83203—Thermocompression bonding, e.g. diffusion bonding, pressure joining, thermocompression welding or solid-state welding
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    • 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
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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Abstract

A kind of anisotropically conducting adhesive, the application of adhesive composite and connector.The anisotropically conducting adhesive is arranged with circuit electrode and between oppositely disposed a pair of of circuit member, for the pair of circuit member to be bonded to each other, anisotropically conducting adhesive includes adhesive composite, the adhesive composite contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) radical polymerization initiator and (e) electroconductive particle, the thermoplastic resin includes to be selected from polyimide resin, polyamide, phenoxy resin, poly- (methyl) acrylate, polyester resin, one kind or two or more resin in polyurethane resin and polyvinyl butyral resin, the free-radical polymerised compound includes the compound with epoxy group, the radical polymerization initiator includes peroxide.

Description

Anisotropically conducting adhesive, the application of adhesive composite and connector
It is on 09 06th, 2011 that the application, which is the applying date, application No. is 201180073261.0, entitled " bonding The divisional application of the application for a patent for invention of agent composition and connector ".
Technical field
The present invention relates to the connectors of adhesive composite and circuit member.
Background technology
In semiconductor element and liquid crystal display element, for the purpose that the various components made in element combine, all the time Using various adhesive composites as circuit connection material.For the adhesive composite, it is desirable that using cementability as representative The diverse natures such as the reliability under heat resistance, humid tropical condition.
Glued adherend have printing distributing board and by the metals such as the organic materials such as polyimide film, copper and aluminium, Or ITO, SiN and SiO2Various surface that a variety of materials are formed as equal metallic compounds.Therefore, adhesive composite needs It is designed according to each adherend.
In the past, it as semiconductor element or adhesive composite used for liquid crystal display element, uses always high comprising display The compositions of thermosetting resin of the thermosetting resins such as cementability and the epoxy resin of high reliability (for example, referring to patent document 1). Such adhesive composite typically contains the curing agent such as epoxy resin, the phenolic resin reacted with epoxy resin and promotes ring The hot potentiality catalyst of oxygen resin and curing agent reacted.Wherein hot potentiality catalyst is to determine solidification temperature and solidification speed An important factor for spending.Therefore, as hot potentiality catalyst, from storage-stable at room temperature and curing rate when heating From the viewpoint of and use various compounds.The adhesive composite at a temperature of 170~250 DEG C generally by heating 1~3 Hour is cured, to play desirable cementability.
Include the radical-curable bonding agent of acrylate derivative or methacrylate derivative and peroxide It attracts attention (for example, referring to patent document 2).Radical polymerization mould assembly bonding agent is rich due to the free radical as reactivity kind Reactivity, therefore be advantageous in terms of short time solidification.Also have by radical polymerization mould assembly bonding agent and epoxy resin and the moon from The example (patent document 3) of sub- aggretion type curing agent.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 1-113480 bulletins
Patent document 2：International Publication No. 98/44067
Patent document 3：Japanese Unexamined Patent Publication 2007-224228 bulletins
Invention content
The subject that the invention solves
Along with the High precision of the highly integrated and liquid crystal cell of nearest semiconductor element, between interelement and wiring closet Away from narrowing.Therefore, for circuit connection solidification when heating cause dysgenic possibility to get higher surrounding member.
Further, in order to cost effective, it is necessary to improve production capacity, need more low temperature and in the short time it is cured viscous Connect agent composition, in other words " low-temperature fast-curing " adhesive composite.Low temperature in order to realize adhesive composite is quick Solidification, for example, also sometimes using the low hot potentiality catalyst of activation energy, but in this case, it is very difficult to maintain room Storage-stable near temperature.
Radical-curable bonding agent can relatively easily be realized low-temperature fast-curing.However, using radical-curable It, mostly can be in electricity especially after connector is exposed in hot and humid environment in the case of connector obtained from bonding agent The interface of road component and circuit connection material generates stripping bubble.As one of its reason, it is believed that radical-curable is bonded Agent has the tendency for generating the cure shrinkage of bigger compared with the bonding agent containing epoxy resin.
If reduce (methyl) acrylate compounds use level, can somewhat suppression circuit component with electricity The stripping at the interface of road connecting material.However, in this case, having the tendency that adhesive strength reduction, or there is connection reliability drop Low tendency.Further, opposite due to being difficult to fully exclude when carrying out circuit connection under lower pressure as such as 1MPa Interelectrode resin, therefore the electrical connection that cannot be satisfied with sometimes using pervious circuit connection material.It especially connects thin Circuit member when, in order to prevent the breakage of circuit member and need the circuit under lower pressure to connect.Be used in combination epoxy resin with When free-radical polymerised compound, free radical polymerization can be hindered, therefore is not easy short time solidification.
The main purpose of the present invention is to provide a kind of adhesive composites, although being radical-curable bonding agent, But it in the circuit connection material as connection circuit member, is able to maintain that under the condition of contact of low pressure adequately Connection reliability, and the generation of the interface peel under the conditions of high temperature and humidity can be inhibited.
The method to solve the problem
The present invention relates to cause containing (a) thermoplastic resin, (b) free-radical polymerised compound and (c) free radical polymerization The adhesive composite of agent.In a mode, the free-radical polymerised chemical combination in adhesive composite according to the present invention Object includes the compound with epoxy group.
According to involved adhesive composite, when being used as the circuit connection material of connection circuit member, even if in low pressure Condition of contact under be also able to maintain that sufficient connection reliability, and interface peel under the conditions of high temperature and humidity can be inhibited It generates.
Adhesive composite according to the present invention can further contain silane coupled represented by (d) following formula (1) Agent.
Change 1
In formula (1), R1、R2And R3Each independently represent hydrogen atom, the alkyl of carbon number 1~5, carbon number 1~5 alkoxy, The alkoxy carbonyl or aryl of carbon number 1~5.R1、R2And R3In it is at least one be alkoxy.R4Indicate (methyl) acryloyl group, second Alkenyl, isocyanate group, imidazole radicals, sulfydryl, amino, methylamino, dimethylamino, benzylamino, phenyl amino, cyclohexyl Amino, morpholinyl, piperazinyl, urea groups or glycidyl.A indicates 1~10 integer.
Adhesive composite according to the present invention can further contain (e) electroconductive particle.Thereby, it is possible to bonding Agent composition assigns electric conductivity or anisotropic conductive, therefore can adhesive composite be more appropriately used as to circuit and connected Material.In addition it is possible to more easily reduce the connection resistance between the circuit electrode that the adhesive composite is electrically connected.
In another way, the present invention relates to a kind of connectors, have：With circuit electrode and oppositely disposed a pair Circuit member and the connecting elements that a pair of of circuit member is bonded to each other between a pair of of circuit member is set.The electricity of one side The circuit electrode of road component is electrically connected with the circuit electrode of the circuit member of another party.A pair of of circuit member of composition connector Connecting elements is the solidfied material of adhesive composite according to the present invention.
In connector according to the present invention, can be the circuit member of a side has glass substrate, the circuit of another party Component has flexible base board.
Connector according to the present invention can fully inhibit circuit member and electricity after being placed in hot and humid environment The interface peel of road connecting material.And it is able to maintain that sufficient connection reliability.
The effect of invention
In accordance with the invention it is possible to a kind of adhesive composite is provided, although being radical-curable bonding agent, When as the circuit connection material for connecting circuit member, it is able to maintain that adequately connection can under the condition of contact of low pressure By property, and the generation of the interface peel under the conditions of high temperature and humidity can be inhibited.
Description of the drawings
Fig. 1 is the sectional view for an embodiment for indicating film-like adhesive.
Fig. 2 is the sectional view for an embodiment for indicating connector.
Fig. 3 is the sectional view of an embodiment of the method for indicating manufacture connector.
Fig. 4 is the plan view for being illustrated to compression joint area.
Specific implementation mode
Hereinafter, optionally the preferred embodiment of the present invention is described in detail on one side with reference to attached drawing on one side.But this hair Bright embodiment not limited to the following.In attached drawing, the same symbol is assigned to same or equivalent part, repeated explanation is suitably saved Slightly.In this specification, (methyl) acrylic acid refers to acrylic acid or corresponding methacrylic acid, and (methyl) acrylate refers to Acrylate or corresponding methacrylate, (methyl) acryloxy refer to acryloxy or methacryloxypropyl Base.
Adhesive composite involved by present embodiment contains (a) thermoplastic resin, (b) free-radical polymerised compound (c) radical polymerization initiator.
Thermoplastic resin contained by adhesive composite is not particularly limited, and is for example, selected from polyimide resin, polyamides Polyimide resin, phenoxy resin, poly- (methyl) acrylate, polyimide resin, polyester resin, polyurethane resin and polyethylene The one kind or two or more resin of polyvinyl butyral resin.Thermoplastic resin can contain siloxanes key and/or fluorine-based.Use 2 kinds When the above thermoplastic resin, it is suitably for mixing completely or microphase-separated occurs and generates the combination of gonorrhoea.
The weight average molecular weight of thermoplastic resin is not particularly limited, preferably 5000~20000, more preferably 10000~ 150000.The weight average molecular weight hour of thermoplastic resin has the tendency that the bonding force of adhesive composite reduces.Thermoplastic resin Weight average molecular weight it is big when, there is thermoplastic resin and the intermiscibility of other compositions to reduce or the mobility of bonding agent reduce Tendency.
On the basis of the total amount of thermoplastic resin and free-radical polymerised compound, the amount of thermoplastic resin is preferably 20 ~80 mass %, more preferably 30~70 mass %, further preferably 35~65 mass %.The quantitative change of thermoplastic resin is few When, have the tendency that bonding force reduces or the film forming of adhesive composite reduces.When the quantitative change of thermoplastic resin is more, there is bonding The tendency that the mobility of agent reduces.The upper limit value and lower limiting value of the amount of thermoplastic resin can be 58 mass %.
As thermoplastic resin rubber constituent can also be used for the purpose of stress mitigates and cementability improves.Rubber at Point for example selected from acrylic rubber, polyisoprene, polybutadiene, carboxyl terminal polybutadiene, C-terminal polybutadiene, 1, 2- polybutadiene, carboxyl terminal 1,2- polybutadiene, C-terminal 1,2- polybutadiene, SBR styrene butadiene rubbers, hydroxyl Base end SBR styrene butadiene rubbers, carboxyl, hydroxyl, carboxylated nitrile rubber, C-terminal poly- (oxypropylene), alkoxy first silicon Alkyl end poly- (oxypropylene), poly- (oxygen tetramethylene) glycol, polyolefin diols and poly- 6-caprolactone.It is improved from cementability From the viewpoint of, rubber constituent preferably has cyano or carboxyl as highly polar base as side chain radical or terminal groups.These rubbers Glue ingredient can be used alone or two or more is applied in combination.
Adhesive composite involved by present embodiment includes at least one kind of with epoxy group and free-radical polymerised insatiable hunger It is used as (b) free-radical polymerised compound with the compound of base.Free-radical polymerised unsaturated group is preferably (methyl) acryloyl Base (especially (methyl) acryloxy).
Free-radical polymerised compound with epoxy group and free-radical polymerised unsaturated group, such as can be to pass through tool Have that the multi-functional epoxy compounds of multiple epoxy groups is generating with reacting for (methyl) acrylic acid, has epoxy group and (methyl) third The compound of enoyl-.When the reaction, the equivalent of the acryloxy of (methyl) acrylic acid is relative to multiple epoxy groups The epoxide equivalent of compound is preferably 0.95~1.05, more preferably 1.
Free-radical polymerised compound with epoxy group and the epoxy of multi-functional epoxy compound that uses in order to obtain Equivalent (g/ equivalents) is preferably 130~250.By making epoxide equivalent within that range, connection can be particularly marked degree played The effect that the reliability of body improves.The upper limit value and lower limiting value of multi-functional epoxy compound can be 160,170,210 or 220.
Above-mentioned multi-functional epoxy compound is not particularly limited, such as the bis-phenol as bisphenol-A, Bisphenol F and bisphenol S The polyacids such as diglycidyl ether, alicyclic epoxy resin, hexahydrophthalic acid tetrahydrophthalic acid bunching water it is sweet The polyglycidyl ether of grease, phenolic resin varnish type epoxy resin and aliphatic polyol.
For example, according to 2 epoxy groups epoxide with and the epoxide epoxide equivalent equivalent third The reaction of olefin(e) acid, 1 can get in most cases in 2 epoxy groups are converted into the compound (i) of acryloxy, 2 rings Both oxygroups are converted into the compound (ii) of acryloxy and the mixture of unreacted initial feed (iii) as life At object.The mixture can be directly used in modulation adhesive composite, the refined products such as column can also be used as needed. It is more than or equal to 0.8, further preferably directly to use composition ratio when mixture, preferably (i)/(ii+iii) (molar ratio) More than or equal to 1.(i)/(ii+iii) when (molar ratio) is less than 0.8, there are interface peel inhibition and the connection reliability of connector The opposite tendency reduced of the effect of raising.From the same viewpoint, (ii)/(iii) (molar ratio) is preferably 0.95~1.05.
The molecular weight of free-radical polymerised compound with epoxy group is preferably greater than or equal to 300 and is less than 1000. The molecular weight hour has the tendency that the compound is readily volatilized in the manufacturing process of adhesive composite.It is special when molecular weight is big It is not to have the tendency that being difficult to obtain sufficient mobility in the case of connecting circuit member under low pressure.
Free-radical polymerised compound with epoxy group is preferably with 1 glycidyl and 1 (methyl) acryloyl Oxygroup.By using such compound, the effect of the present invention can be particularly marked degree played.
On the basis of the total amount of thermoplastic resin and free-radical polymerised compound, the free radical polymerization with epoxy group The amount of property compound is preferably 2.5~15 mass %, more preferably 5~12.5 mass %.Free radical polymerization with epoxy group Property compound amount it is few when, have the tendency that the effect that the interface peel of connector inhibits and connection reliability improves becomes smaller.Have When the amount of the free-radical polymerised compound of epoxy group is more, there is the effect that high temperature and humidity treated the interface peel of connector inhibits The tendency that fruit becomes smaller.The upper limit value and lower limiting value of the amount of free-radical polymerised compound with epoxy group can be 2.4 matter Measure %, 9.7 mass %, 15 mass % or 19 mass %.
Adhesive composite involved by present embodiment, in addition to the free-radical polymerised compound with epoxy group with Outside, other arbitrary compounds with free-radical polymerised functional group can also be contained and be used as (b) free-radical polymerised compound. The free-radical polymerised compound can be any of monomer and oligomer, or combination.
It is excellent as the free-radical polymerised compound that can be applied in combination with the free-radical polymerised compound with epoxy group Select one kind or two or more polyfunctional (methyl) acrylate compounds with 2 or more (methyl) acryloxy. Such (methyl) acrylate compounds, such as selected from epoxy (methyl) acrylate, carbamate (methyl) acrylic acid The monomers such as ester, polyethers (methyl) acrylate and polyester (methyl) acrylate or oligomer, trimethylolpropane tris (methyl) Acrylate, polyethylene glycol two (methyl) acrylate, polyalkylene glycol two (methyl) acrylate, dicyclopentenyl (first Base) acrylate, dicyclopentenyl oxygroup ethyl (methyl) acrylate, neopentyl glycol two (methyl) acrylate, two seasons penta 4 Alcohol six (methyl) acrylate, isocyanuric acid are modified 2 functions (methyl) acrylate, isocyanuric acid is modified 3 functions (methyl) third Olefin(e) acid ester, addition (methyl) acrylic acid and the epoxy (first that generates on 2 glycidyls of bisphenol fluorene diglycidyl ether Base) acrylate and addition ethylene glycol and/or propylene glycol institute on 2 glycidyls of bisphenol fluorene diglycidyl ether Compound made of (methyl) acryloxy is imported in the compound obtained.
For the purpose of adjusting of mobility etc., adhesive composite can contain simple function (methyl) acrylate compounds As (b) free-radical polymerised compound.Simple function (methyl) acrylate compounds, such as selected from pentaerythrite (methyl) third Olefin(e) acid ester, 2- cyano ethyls (methyl) acrylate, cyclohexyl (methyl) acrylate, dicyclopentenyl (methyl) acrylic acid Ester, dicyclopentenyl oxygroup ethyl (methyl) acrylate, 2- (2- ethoxy ethoxies) ethyl (methyl) acrylate, 2- Ethoxyethyl group (methyl) acrylate, 2- ethylhexyls (methyl) acrylate, n-hexyl (methyl) acrylate, 2- hydroxyls Base ethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, isobornyl (methyl) acrylate, isodecyl (first Base) acrylate, iso-octyl (methyl) acrylate, dodecyl (methyl) acrylate, 2- methoxy ethyls (methyl) Acrylate, 2- Phenoxyethyls (methyl) acrylate, tetrahydrofurfuryl (methyl) acrylate, 2- (methyl) acryloyl-oxy Base ethyl phosphonic acid ester, N, N- dimethyl aminoethyls (methyl) acrylate, N, N- dimethylaminopropyls (methyl) propylene Acid esters and (methyl) acryloyl morpholine.These compounds can be used alone, and can also combine two or more.
For the purpose of raising of crosslinking rate etc., other than above-mentioned acrylate compounds, adhesive composite can be with Contain the compound with the free-radical polymerised functional group such as allyl, dimaleoyl imino and vinyl and is used as (b) free radical Polymerizable compound.Such compound, such as selected from N- vinyl imidazoles, N- vinylpyridines, N- ethenyl pyrrolidones Ketone, N- vinyl formamides, N- caprolactams, 4,4 '-ethenylidenes bis- (N, accelerines), N- second Alkenyl acetamide, N, N- dimethacrylamide, n-isopropyl acrylamide and N, N- acrylamides.
For the purpose of the raising of bonding force, adhesive composite preferably comprises the free-radical polymerised chemical combination with phosphate Object is used as (b) free-radical polymerised compound.Free-radical polymerised compound with phosphate for example selected from following formula (2), (3) or the compound represented by (4).
Change 2
In formula (2), R5Indicate (methyl) acryloxy, R6Indicate that hydrogen atom or methyl, w and x each independently represent 1 ~8 integer.Multiple R in same molecule5、R6, w and x respectively can be the same or different.
Change 3
In formula (3), R7Indicate that (methyl) acryloxy, y and z each independently represent 1~8 integer.Same molecule In multiple R7, y and z respectively can be the same or different.
Change 4
In formula (4), R8Indicate hydrogen atom or methyl, R9Indicate (methyl) acryloxy, b and c each independently represent 1 ~8 integer.R in same molecule8It can be the same or different.
Free-radical polymerised compound with phosphate, such as selected from acid phosphonooxyethyl methacrylate (acid phosphoxy ethyl methacrylate), acid phosphonooxyethyl acrylate (acid phosphoxy Ethyl acrylate), acid phosphinylidyne oxygroup propyl methacrylate (acid phosphoxy propyl Methacrylate), acid phosphinylidyne oxygroup polyoxyethylene glycol monomethacrylates, acid phosphinylidyne oxygroup polyoxypropylene diols Monomethacrylates, 2,2 '-two (methyl) acryloxy diethylphosphates, EO modified phosphates dimethylacrylate, Phosphoric acid modification epoxy acrylate and phosphoric acid vinyl acetate.
On the basis of the total amount of thermoplastic resin and free-radical polymerised compound, the free radical polymerization with phosphate The amount of property compound is preferably 0.1~15 mass parts, more preferably 0.5~10 mass parts.When the amount is few, it is difficult to obtain high viscous The tendency of intensity is connect, when the amount is more, being easy to happen the physical property of the adhesive composite after solidification reduces, and is improved there are reliability The possibility that effect becomes smaller.
On the basis of the total amount of thermoplastic resin and free-radical polymerised compound, (b) contained by adhesive composite The total amount of free-radical polymerised compound is preferably 20~80 mass %, more preferably 30~70 mass %, further preferably 35~65 mass %.When the amount is few, have the tendency that heat resistance reduction, when the amount is more, has after being placed in hot and humid environment The tendency that the effect that stripping inhibits becomes smaller.The upper limit value and lower limiting value of the amount of free-radical polymerised compound can be 42 matter Measure %.
(c) radical polymerization initiator can arbitrarily be selected from the compounds such as peroxide and azo-compound.From From the viewpoint of stability, reactivity and intermiscibility, preferably 1 minute half life temperature is 90~175 DEG C and molecular weight is 180 ~1000 peroxide.It is 1 minute temperature that " 1 minute half life temperature ", which refers to the half-life period of peroxide,." half-life period " Refer to that the concentration of compound at an established temperature reduces the time until the half of initial value.
Radical polymerization initiator is for example, selected from the one kind or two or more compound of following compound：1,1,3,3- Tetramethyl butyl new decanoate ester peroxide, two (4- tert-butylcyclohexyls) peroxy dicarbonates, two (2- ethylhexyls) mistakes Aoxidize two carbonic esters, cumyl new decanoate ester peroxide, 1,1,3,3- tetramethyl butyls new decanoate ester peroxide, peroxidating February Osmanthus acyl, 1- cyclohexyl -1- Methylethyls new decanoate ester peroxide, tert-hexyl peroxide neodecanoic acid ester, tert-butyl hydroperoxide are new Decylate, t-butylperoxy pivarate, 1,1,3,3- tetramethyl butyls peroxidating -2 ethyl hexanoic acid ester, 2,5- bis- Methyl -2,5- two (2- ethylhexanoyl-peroxies) hexane, tert-hexyl peroxide -2 ethyl hexanoic acid ester, t-butyl peroxy Change -2 ethyl hexanoic acid ester, the new heptanoate of tert-butyl hydroperoxide, t-amyl peroxy -2 ethyl hexanoic acid ester, di-t-butyl Peroxidating hexahydro terephthalic acid ester, t-amyl peroxy -3,5,5 Trimethylhexanoic acid ester, 3- hydroxyl -1,1- dimethyl Butyl peroxy neodecanoic acid ester, 1,1,3,3- tetramethyl butyls peroxidating -2 ethyl hexanoic acid ester, the t-amyl peroxy new last of the ten Heavenly stems Acid esters, t-amyl peroxy -2 ethyl hexanoic acid ester, 3- methyl benzoyls peroxide, 4- methyl benzoyl peroxides Compound, two (3- methyl benzoyls) peroxide, dibenzoyl peroxide, two (4- methyl benzoyls) peroxidating Double -2,4- the methyl pentane nitriles of object, 2,2 '-azos, 1,1 '-azos bis- (1- acetoxyl group -1- diphenylphosphino ethanes), 2, 2 '-azobis isobutyronitriles, 2,2 '-azos bis- (2- methylbutyronitriles), dimethyl -2,2 '-azobis isobutyronitrile, 4,4 ' - Azo bis- (4- cyanopentanoic acids), 1,1 '-azos bis- (1- cyclohexane carbonitriles), tert-hexyl peroxide isopropyl monocarbonate, uncle Butyl peroxy maleic acid, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, tert-butyl hydroperoxide laurate, 2,5- Dimethyl -2,5- two (peroxidating of 3- methyl benzoyls) hexane, tert-butyl hydroperoxide -2- ethylhexyls monocarbonate, Tert-hexyl peroxide benzoic ether, 2,5- dimethyl -2,5- two (benzoylperoxy) hexane, tert-butyl hydroperoxide benzene Formic acid esters, dibutyl peroxidating trimethyladipic acid ester, t-amyl peroxy caprylic acid ester, t-amyl peroxy isononoate and T-amyl peroxy benzoic ether.
As radical polymerization initiator, the light irradiation by 150~750nm of wavelength can also be used to generate free radicals Compound.Such compound is not particularly limited, for example, Photoinitiation, Photopolymerization, and α-acetyl described in Photocuring, J.-P.Fouassier, Hanser Publishers (nineteen ninety-five), p17~p35 Amino benzophenone derivatives and phosphinoxide are more preferred due to the high sensitivity irradiated to light.These compounds can be single It solely uses a kind or two or more is applied in combination.These compounds can also be combined with above-mentioned peroxide and azo-compound. Alternatively, adhesive composite can also contain the radical polymerization initiator generated free radicals using ultrasonic wave, electromagnetic wave etc..
For the corrosion of the connection terminal (circuit electrode) of suppression circuit component, preferably contain in radical polymerization initiator Chlorion, organic acid amount be less than or equal to 5000ppm.From the same viewpoint, it is generated after preferably decomposing organic The few free-radical polymerised compound of acid.From the aspect of the stability for improving circuit connection material, preferably under room temperature, normal pressure Opening wide after placing 24 hours has the radical polymerization initiator of the quality retention more than or equal to 20 mass %.
On the basis of the total amount of thermoplastic resin and free-radical polymerised compound, the amount of radical polymerization initiator is excellent It is selected as 1~15 mass %, more preferably 2.0~10 mass %.
Adhesive composite involved by present embodiment can also contain silane coupling agent.Under silane coupling agent is preferably State the compound represented by chemical formula (1).
Change 5
In formula (1), R1、R2And R3Each independently represent hydrogen atom, the alkyl of carbon number 1~5, carbon number 1~5 alkoxy, The alkoxy carbonyl or aryl of carbon number 1~5.R1、R2And R3In it is at least one be alkoxy.R4Indicate (methyl) acryloyl group, second Alkenyl, isocyanate group, imidazole radicals, sulfydryl, amino, methylamino, dimethylamino, benzylamino, phenyl amino, cyclohexyl Amino, morpholinyl, piperazinyl, urea groups or glycidyl.A indicates 1~10 integer.
The silane coupling agent of formula (1), such as vinyltrimethoxysilane, vinyltriethoxysilane, 3- can be enumerated Glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyls diethoxy silane, 3- methacryloxypropyls Base hydroxypropyl methyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloxies third Ylmethyl diethoxy silane, 3- methacryloxypropyls, 3- acryloxypropyl trimethoxies Base silane, N-2 (amino-ethyl) 3- aminopropylmethyldimethoxysilanes, N- phenyl -3- aminopropyl trimethoxies Silane, 3- ureas propyl-triethoxysilicane, 3-mercaptopropyi trimethoxy silane and 3- isocyanates propyl triethoxies Silane.
On the basis of the total amount of thermoplastic resin and free-radical polymerised compound, the amount of silane coupling agent is preferably 0.1~10 mass %, more preferably 0.25~5 mass %.The amount of silane coupling agent has suppression circuit component to connect with circuit when few Connect the tendency that the effect of the stripping bubble generation at the interface of material becomes smaller.When the amount of silane coupling agent is more, there is adhesive composite The tendency that shortens of up time (pot life).
Adhesive composite involved by present embodiment can further contain electroconductive particle.Contain electroconductive particle Adhesive composite can be used as anisotropic conductive adhesive particularly suitablely.
Electroconductive particle is such as selected from containing the metallic Au, Ag, Pd, Ni, Cu and solder；Carbon particle；With by The nucleome particle that the non-conductive materials such as glass, ceramics and plastics are constituted includes metal, clipped wire with the coating nucleome particle The compound particle of son and the conductive layer of carbon etc..Metallic may be the grain of the silver layer with copper particle and coating copper particle Son.The nucleome particle of compound particle is preferably plastic pellet.
Above-mentioned compound particle has the morphotropism that is deformed because being heated and pressurizeed, therefore when circuit member is bonded to each other, The contact area of circuit electrode and electroconductive particle possessed by the circuit member can be increased.Therefore, using multiple containing these When closing adhesive composite of the particle as electroconductive particle, the superior connector in terms of connection reliability can be obtained.
Adhesive composite can also contain with above-mentioned electroconductive particle and its coating surface it is at least part of absolutely The insulation-coated electroconductive particle of edge layer or insulating properties particle.Insulating layer can be arranged by the methods of hydridization.Insulating layer is exhausted Edge particle can be formed by insulating materials such as macromolecule resins.By using such insulation-coated electroconductive particle, no The short circuit caused by the mutual contact of adjacent electroconductive particle easily occurs.
From the viewpoint of obtaining good dispersibility and electric conductivity, the average grain diameter of electroconductive particle is preferably 1~18 μ m。
The amount of electroconductive particle is not particularly limited, on the basis of whole volumes of adhesive composite, preferably 0.1~ 30 volume %, more preferably 0.1~10 volume %, further preferably 0.5~7.5 volume %.When the amount is few, conductive drop Low tendency.When the amount is more, has the tendency that the short circuit being easy to happen between circuit electrode.The amount (volume %) of electroconductive particle is based on Each ingredient for constituting adhesive composite before curing is determined in 23 DEG C of volume.The volume of each ingredient can by using than Mass conversion is found out at volume again.It can also will not make to be intended to volumetric ingredient dissolving or swelling, can fully soak The appropriate solvent (water, alcohol etc.) of the ingredient is put into graduated cylinder etc., finds out the ingredient and increased body of input measure object thereto Volume of the product as the ingredient.
Adhesive composite is other than containing electroconductive particle, organic fine particles and/or nothing that can also be containing insulating properties Machine particle.Inorganic particles are for example selected from silicon dioxide microparticle, alumina particulate, silica-alumina particle, titanium oxide Particle and zirconia particles etc. are the metal oxide microparticle and nitride particle of representative.Organic fine particles are for example selected from organic Silicon particle, metacrylate-butadiene-styrene particulate, acrylic acid-organic silicone microparticle, polyamide particles and polyamides are sub- Amine particle.These particles can have uniform structure, it is possible to have core-shell type structure.
On the basis of the total amount of thermoplastic resin and free-radical polymerised compound, the amount of organic fine particles and inorganic particles Preferably 2.5~30 mass %, more preferably 5~20 mass %.When the amount of inorganic particles is few, there is the electricity for being relatively difficult to maintain opposite The tendency of the electrical connection of interpolar.When the quantitative change of inorganic particles is more, have the tendency that the mobility of adhesive composite reduces.
In order to control curing rate, assign storage-stable, adhesive composite can contain stabilization agent.It is such steady Determine agent to be not particularly limited, is preferably selected from the quinone derivatives such as benzoquinones and quinhydrones, 4- metoxyphenols, 4- tert-butyl os benzene two The amphyls such as phenol, 2,2,6,6- tetramethyl piperidine -1- oxygroups and 4- hydroxyl -2,2,6,6- tetramethyl piperidines -1- The hindered amine derivatives such as the aminooxy groups such as oxygroup derivative and tetramethyl piperidine methyl acrylate.
On the basis of the total amount of thermoplastic resin and free-radical polymerised compound, the amount of stabilization agent is preferably 0.01 ~30 mass parts, more preferably 0.05~10 mass parts.The amount has the tendency that the effect of stabilization agent becomes smaller when few.The amount is more When, it is likely to decrease with the intermiscibility of other compositions.
Adhesive composite involved by present embodiment can be used as paste in the case where (25 DEG C) of room temperature is liquid Bonding agent uses.Adhesive composite is used in the case where (25 DEG C) of room temperature is solid after can heating, can also be by adding Enter solvent and is used after being gelatinized.As long as it (also includes addition that the solvent for gelatinization, which does not have substantially with adhesive composite, Agent) reactivity and can fully dissolve the solvent of adhesive composite and be just not particularly limited.The boiling of the solvent under normal pressure Preferably 50~150 DEG C of point.If the boiling point of solvent is less than 50 DEG C, there is the possibility of volatilization when being placed under room temperature (25 DEG C) Property, therefore the use in the system of opening wide may be limited.If the boiling point of solvent is more than 150 DEG C, it is difficult to that solvent is made to volatilize, it can The reason of effect that reliability improves after being bonded becomes smaller can be become.
Adhesive composite involved by present embodiment can also be shaped to membranaceous, be used as film-like adhesive.Film Shape bonding agent can for example obtain by the following method：Solvent etc. such as will be added at the operations as needed in adhesive composite Obtained solution coating is on the fissilities supporter such as fluororesin film, polyethylene terephthalate film, processing release paper, or makes Above-mentioned solution is containing being placed on fissility base material, and remove solvent after being immersed in the base materials such as non-woven fabrics etc..Film-like adhesive is from behaviour Property made etc. considers more convenient.
Fig. 1 is the sectional view of an embodiment of the stacked film for indicating to have film-like adhesive.Stacked film shown in FIG. 1 100 have supporter 8 and the film-like adhesive 40 on supporter 8.Film-like adhesive 40 be formed as it is membranaceous upper Adhesive composite is stated, is made of insulating properties adhesive layer 5 and the electroconductive particle 7 being scattered in insulating properties adhesive layer 5.Absolutely Edge adhesive layer 5 is made of the ingredient in above-mentioned adhesive composite in addition to electroconductive particle.Use the film-like adhesive When, operation is easy, and can be easy to set up in adherend, be can easily be done connection operation.Film-like adhesive can be with It is constituted with the multilayer comprising layer of more than two kinds.It, can be suitable by film-like adhesive when film-like adhesive contains electroconductive particle Ground is used as anisotropic conductive film.
When using adhesive composite and film-like adhesive involved by present embodiment, heating usually can be used together and add Pressure makes adherend be bonded to each other.Heating temperature is not particularly limited, preferably 100~250 DEG C.As long as pressure is not to being glued Junctor causes the range of damage to be just not particularly limited, it is often preferred that 0.1~10MPa.These are heated and pressurizeed preferably 0.5 Second~carried out in the range of 120 seconds.When using adhesive composite and film-like adhesive involved by present embodiment, i.e., Make for example under 150~200 DEG C, the lower pressure of 1MPa or so that 10 seconds short time were heated and pressurizeed, can also make to be glued Junctor is fully bonded each other.
It is different not that adhesive composite involved by present embodiment with film-like adhesive may be used as coefficient of thermal expansion The bonding agent of congener adherend.Specifically, can by adhesive composite be used as with anisotropically conducting adhesive, Silver paste and silverskin etc. be representative circuit connection material or with CSP elastomers, CSP underfills and LOC band etc. be The semiconductor element adhesives of representative.
Hereinafter, as that will have circuit board using the adhesive composite involved by present embodiment and be formed in circuit One example of the method that the circuit member of the circuit electrode on the interarea of substrate is connected to each other, to will be involved by present embodiment Film-like adhesive use an embodiment of the method to manufacture connector to illustrate as anisotropic conductive film.
Fig. 2 is the sectional view of an embodiment of the connector of indication circuit component.Connector 1 shown in Fig. 2 has The first oppositely disposed circuit member 20 and second circuit component 30.The first circuit member 20 and second circuit component 30 it Between, it is equipped with the connecting elements 10 that they are bonded and are connected.
First circuit member 20 have the first circuit board 21 and be formed on the interarea 21a of circuit board 21 first Circuit electrode 22.On the interarea 21a of circuit board 21, insulating layer could be formed with.
Second circuit component 30 have second circuit substrate 31 and be formed on the interarea 31a of circuit board 31 second Circuit electrode 32.On the interarea 31a of circuit board 31, insulating layer can also be formed with.
First and second circuit members 20,30 are not particularly limited as long as with the circuit electrode being electrically connected is needed.Electricity The substrate, polyimides and makrolon of the inorganic material such as selected from semiconductor, glass and ceramics of base board 21,31 etc. are organic Substrate, glass/epoxy of material etc. include the substrate of inorganic matter and organic matter.First circuit board 21 can be glass substrate, Second circuit substrate 31 can be flexible base board (the preferably resin films such as polyimide film).
As the concrete example of connected circuit member, can enumerate the formation used in liquid crystal display has the electrodes such as ito film Glass or plastic base, printing distributing board, ceramic wiring board, flexible wiring sheet, semiconductor silicon chips etc..These can basis It needs to be applied in combination.In this way, the adhesive composite involved by according to the present embodiment, in addition to printing distributing board and polyamides Except the component on the surface that imines film etc. is formed by organic material, bonding is can be also used for as having by the metals such as copper and aluminium, ITO (tin indium oxide, indium tin oxide), silicon nitride (SiNx) and silica (SiO2) etc. inorganic material formed surface Component like that with diversified surface state circuit member.
For example, the circuit member of a side be solar battery cell with the electrodes such as finger electrode and busbar electrode, it is another The circuit member of one side be TAB lines when, connector obtained from they are connected be have solar battery cell, TAB lines and The solar cell module for the connecting elements (solidfied material of adhesive composite) that they are bonded.
Connecting elements 10 is made of the solidfied material of the adhesive composite involved by present embodiment.Connecting elements 10 contains Insulating layer 11 and the electroconductive particle 7 being scattered in insulating layer 11.Electroconductive particle 7 is not only configured at opposite circuit electrode 22 Between circuit electrode 32, also it is configured between interarea 21a, 31a.Circuit electrode 22,32 is electrically connected by electroconductive particle 7. Both electroconductive particle 7 and circuit electrode 22,32 are in direct contact.Therefore, it is possible to fully reduce the connection between circuit electrode 22,32 Resistance.It can thus make the circulation of the electric current between circuit electrode 22,32 smooth, function possessed by circuit can be given full play to. In the case that connecting elements is free of electroconductive particle, it is electrically connected by circuit electrode 22 is in direct contact with circuit electrode 32 It connects.
Since connecting elements 10 is formed by the solidfied material of the adhesive composite involved by present embodiment, structure is connected Part 10 is sufficiently high for the adhesive strength of circuit member 20 or 30.Therefore, even if after reliability test (high temperature and humidity test) Also it can fully inhibit the reduction of adhesive strength and connect the increase of resistance.
Connector 1 can for example manufacture by the following method, and this method has following process：It will be by adhesive composite structure At film-like adhesive configure with being clipped in the middle with circuit electrode and the process of oppositely disposed a pair of of circuit member；And it is right In a pair of of circuit member and film-like adhesive, pressurizeing while heating on the thickness direction of film-like adhesive is cured, to By the solidfied material of adhesive composite by process (formally connecting process) that a pair of of circuit member is bonded.
Fig. 3 is the sectional view of an embodiment of the method for indicating manufacture connector 1.As shown in (a) of Fig. 3, by film Shape bonding agent 40 is placed on the interarea of 22 side of circuit electrode of the first circuit member 20.Film-like adhesive 40 is set to above-mentioned branch In the case of on support body, the direction of 20 side of the first circuit member is located at film-like adhesive 40, by film-like adhesive and supporter Laminated body be placed on circuit member.Film-like adhesive 40 for membranaceous thus operation due to being easy.Therefore, it is possible to easily make Film-like adhesive 40 can easily be done the first circuit member between the first circuit member 20 and second circuit component 30 20 with the connection operation of second circuit component 30.
Film-like adhesive 40 is to be formed as membranaceous above-mentioned adhesive composite (circuit connection material), conductive Particle 7 and insulating properties adhesive layer 5.When adhesive composite is free of electroconductive particle, in order to which anisotropic conductive is bonded It may be used as circuit connection material.Circuit connection material without electroconductive particle be also sometimes referred to as NCP (non-conductive adhesive, Non-Conductive Paste).When adhesive composite contains electroconductive particle, sometimes using its circuit connection material Also referred to as ACP (anisotropy conductiving glue, Anisotropic Conductive Paste).
The thickness of film-like adhesive 40 is preferably 10~50 μm.The thickness hour of film-like adhesive 40, have circuit electrode 22, The tendency of glued dose of filling is difficult between 32.When the thickness of film-like adhesive is big, be unable to fully ground completely exclude circuit electrode 22, Adhesive composite between 32 has the tendency that the conducting being difficult to ensure between circuit electrode 22,32.
As shown in (b) of Fig. 3, pressure A, B of the thickness direction by applying film-like adhesive 40,40 quilt of film-like adhesive Temporarily it is connected on the first circuit member 20.At this point, can also pressurize in heating.Wherein, heating temperature is set as membranaceous viscous The temperature phase for connecing the not cured temperature of the adhesive composite in agent 40, drastically being generated free radicals with radical polymerization initiator Than substantially low temperature.
Then, as shown in (c) of Fig. 3, second circuit component 30 is located at the first circuit member 20 with second circuit electrode The direction of side is placed on film-like adhesive 40.When film-like adhesive 40 is set on supporter, by second after stripping supporter Circuit member 30 is placed on film-like adhesive 40.
Film-like adhesive 40 is heated while pressurizeing from its thickness direction A, B.Heating temperature at this time It is set as the temperature that radical polymerization initiator fully generates free radicals.It is generated free radicals as a result, by radical polymerization initiator, Cause the polymerization of free-radical polymerised compound.By being heated to film-like adhesive 40, to substantially reduce circuit Insulating properties bonding agent is solidified to form insulating layer 11 in the state of the distance between electrode 22 and circuit electrode 32.As a result, First circuit member 20 is securely connected with second circuit component 30 by the connecting elements 10 comprising insulating layer 11.Just by this Formula connects, and obtains connector shown in Fig. 2.
Formal connection preferably heating temperature is 100~250 DEG C, pressure is 0.1~10MPa, pressing time be 0.5~ It is carried out under conditions of 120 seconds.These conditions can according to use purposes, adhesive composite, circuit member suitable for selection.According to Adhesive composite involved by present embodiment, even if can be had if under lower pressure as 1.0~1.5MPa There is the connector of sufficient reliability.After formal connection, cure after can also carrying out as needed.
The pressure formally connected passes through formula by the load and compression joint area that apply：Load/compression joint area calculates.Pressure When junction product is in terms of the thickness direction of film-like adhesive (adhesive composite), the first circuit electrode and second circuit electricity are surrounded The area of part is pressurized in the minimum rectangular area of all parts of pole overlapping.
With reference to the plan view of Fig. 4, the computation of compression joint area is more particularly described.(a) of Fig. 4 is indication circuit The plan view of the film-like adhesive of component 20 and stacking (temporarily connection) on circuit member 20.With the rectangular of length y Multiple first circuit electrodes 22 are in the way of respective end substantially arrangement point-blank in the first circuit board 21 Interarea 21a on entire width x be arranged side by side.Film-like adhesive 40 is to cover all sides of multiple first circuit electrodes 22 Formula is placed.
As shown in (b) of Fig. 4, second circuit substrate 31 is according to the second circuit electrode and the first circuit on its interarea The opposite mode of electrode 22 is placed on film-like adhesive 40.It is surrounded when to comprising in terms of the thickness direction of film-like adhesive 40 The region of minimum area is (hereinafter referred to as in the rectangular area of the first circuit electrode all parts Chong Die with second circuit electrode " electrode opposite direction region ".) all region 50a apply pressure.In (b) of Fig. 4, electrode opposite direction region is with width x and length Spend y1(=y) rectangular area.When pressurizeing in this way to electrode opposite direction region entirety, compression joint area is the width in electrode opposite direction region X and length y1Product.
As shown in (c) of Fig. 4, when applying pressure to the region 50b of the part comprising electrode opposite direction region, compression joint area For the length y of the width x and pressurized part in electrode opposite direction region in electrode opposite direction region2Product.
In the case that film-like adhesive contains the radical polymerization initiator generated free radicals using light irradiation, in order to formal When connecting and curing film-like adhesive, as long as replacing heating and carrying out light irradiation.It is pre-prepd alternatively, it is also possible to replace Film-like adhesive and use the adhesive composite of such as paste as circuit connection material.For example, can be by comprising as follows The method of process forms film-like adhesive：The coating fluid for dissolving adhesive composite in a solvent as needed and modulating is applied It is distributed on the first circuit member 20 or second circuit component 30, makes dried coating film.
Embodiment
Hereinafter, enumerating embodiment and comparative example, the present invention is more particularly described.But the present invention is not limited to following implementations Example.
(inquiring into I)
1. the synthesis of polyurethane resin
In the removable flask for having reflux cooler, thermometer and blender, it is added as the glycol with ester bond 1000 mass parts of polypropylene glycol (Mn=2000) and 4000 parts by weight of methyl ethyl ketone as solvent, 30 points are stirred at 40 DEG C Clock.After solution is warming up to 70 DEG C, the stannous methide laurate 12.7mg as catalyst is added.Then, for the solution, 4,4- diphenyl methanes -125 mass parts of diisocyanate are dissolved in 125 parts by weight of methyl ethyl ketone with dripping within 1 hour and The solution of modulation.Then, it persistently stirs at such a temperature, until the absorption peak of NCO is not observed with infrared spectrophotometer, from And obtain the methyl ethyl ketone solution of polyurethane resin.According to the solution solid component concentration (concentration of polyurethane resin) at Mode for 30 mass % is adjusted.The weight average molecular weight of the polyurethane resin of gained is using the result that GPC is measured 320000 (standard polystyren scaled values).The analysis condition of GPC is recorded below.
Table 1
Device TOSOH Co., Ltd GPC-8020
Detector TOSOH Co., Ltd RI-8020
Column Hitachi Chemical Co., Ltd. Gelpack GL-A-160-S+GL-A150-SG2000Hhr
Sample solution concentration 120mg/3ml
Solvent Tetrahydrofuran
Injection rate 60μl
Pressure 30kgf/cm2
Flow 1.00ml/min
2. the synthesis of urethane acrylate
In 2 liters of four-hole boiling flask for being equipped with thermometer, blender, non-active gas introducing port and reflux cooler, Put into polycarbonate glycol (Aldrich system, number-average molecular weight 2000) 4000 mass parts, 2- hydroxyethylmethacry,ates 238 mass parts, 0.49 mass parts of Hydroquinone monomethylether and 4.9 mass parts of tin series catalysts and modulate reaction solution.For being heated to 70 DEG C of reaction solution was reacted with 3 hours 666 mass parts of isophorone diisocyanate (IPDI) of equably dripping.It drips After the reaction was continued 15 hours, by NCO% be less than or equal to 0.2% at the time of be regarded as reaction terminate, obtain carbamic acid Ester acrylate.It is that the weight average molecular weight of urethane acrylate is 8500 (standards using the result that GPC is analyzed Polystyrene scaled value).
3. the synthesis of the acrylate compounds with epoxy group
(acrylate compounds A)
In the reactor for being equipped with agitating device, reflux cooler and thermometer, input bisphenol f type epoxy resin is (double Diglycidyl ether, JER806 (product name), Mitsubishi Chemical Ind's system, the epoxide equivalent 160~170 of phenol F) 330 mass parts, third 72 mass parts of olefin(e) acid (relative to 2 moles of epoxy group in epoxy resin, the ratio that 1 mole of acrylic acid), benzyl triethyl ammonium chlorination 0.1 mass parts of 1 mass parts of ammonium and tert-butyl catechol modulate reaction solution.Reaction solution is stirred 3 hours at 100 DEG C, simultaneously Progress epoxy group is reacted with acrylic acid.After reaction, reaction solution is made to restore to room temperature, addition 300 mass parts of benzene make life It is dissolved in wherein at object.Then, aqueous sodium carbonate, distilled water are added successively, solution are respectively washed 3 times.Then benzene is abundant It is distilled off, obtains crude product.Crude product is analyzed by liquid chromatography, as a result it is found that in crude product, in addition to conduct Also include 2 functional acrylics without epoxy group other than the acrylate compounds with 1 epoxy group of target compound The bisphenol f type epoxy resin of ester compounds and raw material.Then crude product is refined, obtaining epoxy group and acryloxy respectively has One and the acrylate compounds A with Bisphenol F skeleton.
(acrylate compounds B)
It is (HBE-100 (product name), new using the diglycidyl ether of hydrogenated bisphenol A instead of bisphenol f type epoxy resin Japan Chemical Co., Ltd., epoxide equivalent 210~220) 430 mass parts, in addition to this, according to same with acrylate compounds B The step of sample, obtains there are one epoxy group and each tools of acryloxy and has the acrylate compounds of hydrogenated bisphenol A skeleton B。
4. the making of electroconductive particle
The nickel layer of 0.2 μm of thickness is formed on the surface of polystyrene particle, further forms thickness in the outside of the nickel layer 0.04 μm of layer gold.Thus the electroconductive particle of 4 μm of average grain diameter is made.
5. film-like adhesive is made
Raw material shown in table 2 is mixed with mass ratio shown in table 2.Make above-mentioned electroconductive particle with the ratio of 1.5 volume % Example is dispersed therein, and obtains the coating fluid for being used to form film-like adhesive.Using apparatus for coating by the coating solution in thickness On 50 μm polyethylene terephthalate (PET) film.Film is subjected to 10 minutes heated-air dryings at 70 DEG C, forms thickness 18 μm film-like adhesive.
Polyurethane resin, urethane acrylate, acrylate compounds A and acrylate chemical combination shown in table 2 Object B is synthesized as described above.Phenoxy resin is with by PKHC (Union Carbide corporations trade name, average molecular weight 45000) The form of 40 mass % solution that 40g is dissolved in methyl ethyl ketone 60g and modulates uses.Acrylate compounds C is simple function Acrylate compounds (CHA, Toagosei Co., Ltd's trade name).Acrylate compounds D is two functional acrylates Compound (chemical company of the village ABE-300, Xin Zhong trade name).As phosphate, 2- methacryloxyethyls are used Phosphate ester acid (LIGHT ESTER P-2M, common prosperity society Co. Ltd. system trade name).As silane coupling agent, 3- first is used Base acryloyloxypropyltrimethoxysilane (KBM-503, chemical industrial company of SHIN-ETSU HANTOTAI trade name).As radical polymerization Initiator is closed, is used tert-hexyl peroxide -2 ethyl hexanoic acid ester (PERHEXYL O, You societies trade name).Make as nothing Silicon dioxide granule (R104, Japan's AEROSIL trade names) 10g of machine object particle is scattered in toluene 45g and ethyl acetate 45g In the mixed solvent, modulate 10 mass % dispersion liquid, coordinated in coating fluid.Cooperation for silicon dioxide granule Than the total amount relative to phenoxy resin, polyurethane resin, urethane acrylate and acrylate compounds A~D 100 mass parts are 20 mass parts.
Table 2
6. connector
Using above-mentioned film-like adhesive as circuit connection material, will have 2,200 75 μm of line widths, 150 μm of spacing and thickness The flexible PCB (FPC) of the copper circuit of 18 μm of degree, with glass substrate and 0.2 μm of thickness being formed on glass substrate The ito substrate (thickness 1.1mm, 20 Ω of sheet resistance/) of the thin layer of indium oxide (ITO) connects.Connection uses thermo-compression bonding device (mode of heating：Thermostatic type, Dongli Engineering Co., Ltd's system), by heating in 5 seconds and add at 180 DEG C, 3MPa or 1MPa Pressure carries out.It is produced on entire width 1.5mm and FPC and ito substrate is formed by connecting as a result, by the solidfied material of film-like adhesive Connector.The pressure of pressurization is 4.95cm with compression joint area2It is calculated.In addition, being used with glass instead of ito substrate The SiN substrates (thickness 0.7mm) of the thin layer of the silicon nitride (SiN) of substrate and 0.2 μm of thickness being formed on glass substrate, 180 DEG C, the connector that FPC and SiN substrates are made by being heated and pressurizeed under 3MPa by 5 seconds.
(connection resistance, adhesive strength measurement)
Utilize the resistance value (connection resistance) between the adjacent circuit of the connector obtained by multitester measuring.Resistance value is with 37 points The average expression of resistance between adjacent circuit.In addition, measuring the viscous of the connector using 90 degree of stripping methods according to JIS-Z0237 Relay.As the measurement device of adhesive strength, Tensilon UTM-4 (the stripping speed of Japan's Baldwin Co. Ltd. systems is used Spend 50mm/min, 25 DEG C).About connection resistance and bonding force intensity, to after newly connection and in 85 DEG C, the high temperature height of 85%RH The connector after 250 hours high temperature and humidity tests is kept to be measured in wet sump.
(observation of connector appearance)
Use microscope (trade name：ECLIPSE L200, (strain) Nikon system), the connection for ito substrate and SiN substrates Body, observe the stripping at solidfied material and the FPC of the circuit connection material after high temperature and humidity test and the interface of glass whether there is or not.It will be unbounded Face remove the case where be determined as " A ", with the degree of no problem in practicality slightly visible interface peel the case where be determined as " B ", with (problematic in practicality) is determined as " C " the case where problematic degree visible interface peel in practicality.
Table 3
By connector evaluation result is shown in table 3.It is confirmed according to the film-like adhesive of each embodiment：By low pressure, low The condition of cure of temperature and short time all show that good connection is electric under the either case after newly connection and after high temperature and humidity test Resistance (being less than or equal to 5 Ω) and adhesive strength (being greater than or equal to 8N/cm).In contrast, it is entirely free of third with epoxy group In the case of the film-like adhesive of the comparative example of enoic acid ester compounds, especially in the lower pressure of 1MPa, connection resistance is high Or observe the stripping after high temperature and humidity test.
(inquiring into II)
As described below, prepare similarly electric with the embodiment described in Japanese Unexamined Patent Publication 2007-224228 bulletins Road connecting material evaluates the connector for using it to make.
By imidazoles system microcapsule mixed type epoxy resin (HX-3941HP, Asahi Chemical Industry's chemistry (strain) system) 44 mass parts, make For free-radical polymerised compound glycol diacrylate (village A-600, Xin Zhong chemical industry (strain) system) 16 mass parts, 2,5- dimethyl -2,5- bis- (2- ethyl hexyls) hexane (PERHEXA 25O, day as radical polymerization initiator Oily (strain) system) (since PERHEXA 25O are 50% solution, the use level of PERHEXA 25O is 6 mass to 3 mass parts Part.) and PKHC 40 mass % of concentration 100 mass parts of toluene/ethyl acetate solution mixing, coordinate 4 mass parts thereto Polystyrene spherical particles with 4 μm of average grain diameter and 0.1 μm of the Ni layers and Au layers of electroconductive particle set on its surface. γ-glycidoxypropyltrime,hoxysilane (SH6040, beautiful DOW CORNING organosilicon (strain) system in east) 1 is further added Mass parts obtain the mixed solution for being used to form film-like adhesive.The solution coating is passed through on PET film using applicator Film is dried in 70 DEG C of 10 minutes heated-air dryings, forms the film-like adhesive of 20 μ m-thicks.
Film-like adhesive obtained by use was heated and pressurizeed using 180 DEG C, 3MPa, 5 seconds, by with to inquire into 1 same Operation make FPC and ito substrate connector.Connection resistance after the newly connection of the connector is 5.8 Ω, and bonding force is 3.6N/cm, it is clearly worse compared with inquiring into 1 connector of embodiment.
Symbol description
1：Connector, 5：Insulating properties adhesive layer, 7：Electroconductive particle, 8：Supporter, 10：Connecting elements, 11：Insulation Layer, 20：First circuit member, 21：First circuit board, 21a：Interarea, 22：First circuit electrode, 30：Second circuit component, 31：Second circuit substrate, 31a：Interarea, 32：Second circuit electrode, 40：Film-like adhesive, 100：Stacked film.

Claims (31)

1. a kind of anisotropically conducting adhesive, be arranged with circuit electrode and oppositely disposed a pair of of circuit member it Between, the anisotropically conducting adhesive for the pair of circuit member to be bonded to each other, the anisotropically conducting adhesive packet Containing adhesive composite, the adhesive composite contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) certainly By base polymerization initiator and (e) electroconductive particle,
The thermoplastic resin includes selected from polyimide resin, polyamide, phenoxy resin, poly- (methyl) acrylate tree One kind or two or more resin in fat, polyester resin, polyurethane resin and polyvinyl butyral resin,
The free-radical polymerised compound includes the compound with epoxy group,
The radical polymerization initiator includes peroxide.
2. anisotropically conducting adhesive according to claim 1, the adhesive composite further contains insulating properties Organic fine particles, insulating properties inorganic particles or the two.
3. anisotropically conducting adhesive according to claim 1 or 2, the thermoplastic resin includes to be selected from polyamide resin 1 in fat, phenoxy resin, poly- (methyl) acrylate, polyester resin, polyurethane resin and polyvinyl butyral resin Kind or resin of more than two kinds.
4. anisotropically conducting adhesive according to claim 3, the thermoplastic resin contains phenoxy resin and poly- ammonia Ester resin.
5. anisotropically conducting adhesive according to claim 1 or 2, with the thermoplastic resin and the radical polymerization On the basis of the total amount of conjunction property compound, the amount of the free-radical polymerised compound with epoxy group is 2.5~15 Quality %.
6. anisotropically conducting adhesive according to claim 1 or 2, with the thermoplastic resin and the radical polymerization On the basis of the total amount of conjunction property compound, the amount of the free-radical polymerised compound with epoxy group is 5~12.5 matter Measure %.
7. anisotropically conducting adhesive according to claim 1 or 2, the free-radical polymerised compound further wraps Containing one kind or two or more multifunctional (methyl) propylene with 2 or more (methyl) acryloxies and without epoxy group Ester compound.
8. anisotropically conducting adhesive according to claim 7, one kind or two or more multifunctional (methyl) third Enoic acid ester compounds include carbamate (methyl) acrylate.
9. anisotropically conducting adhesive according to claim 1 or 2, free-radical polymerisedization with epoxy group It includes the compound with epoxy group and (methyl) acryloyl group to close object.
10. anisotropically conducting adhesive according to claim 9, described with epoxy group and (methyl) acryloyl group Compound includes the compound for reacting generation with (methyl) acrylic acid by multi-functional epoxy compound.
11. anisotropically conducting adhesive according to claim 10, the epoxide equivalent of the multi-functional epoxy compound For 130~250g/ equivalents.
12. anisotropically conducting adhesive according to claim 10, the epoxide equivalent of the multi-functional epoxy compound For 160~220g/ equivalents.
13. anisotropically conducting adhesive according to claim 10, the multi-functional epoxy compound includes selected from double The diglycidyl ether of phenol, alicyclic epoxy resin, the poly glycidyl ester of polyacid, phenolic resin varnish type epoxy resin and At least one of polyglycidyl ether of aliphatic polyol.
14. anisotropically conducting adhesive according to claim 1 or 2, the free-radical polymerised compound is further Including the free-radical polymerised compound with phosphate and without epoxy group.
15. anisotropically conducting adhesive according to claim 1 or 2, with the thermoplastic resin and the free radical On the basis of the total amount of polymerizable compound, the total amount of the free-radical polymerised compound is 20~80 mass %.
16. the weight average molecular weight of anisotropically conducting adhesive according to claim 1 or 2, the thermoplastic resin is 5000~20000.
17. the weight average molecular weight of anisotropically conducting adhesive according to claim 1 or 2, the thermoplastic resin is 10000~150000.
18. anisotropically conducting adhesive according to claim 1 or 2, with the thermoplastic resin and the free radical On the basis of the total amount of polymerizable compound, the amount of the thermoplastic resin is 20~80 mass %.
19. anisotropically conducting adhesive according to claim 1 or 2, the radical polymerization initiator includes 1 minute The peroxide that half life temperature is 90~175 DEG C and molecular weight is 180~1000.
20. anisotropically conducting adhesive according to claim 1 or 2, with the thermoplastic resin and the free radical On the basis of the total amount of polymerizable compound, the amount of the radical polymerization initiator is 1~15 mass %.
21. anisotropically conducting adhesive according to claim 1 or 2, the adhesive composite further contains (d) Silane coupling agent represented by following formula (1),
In formula (1), R1、R2And R3Each independently represent hydrogen atom, the alkyl of carbon number 1~5, the alkoxy of carbon number 1~5, carbon number 1~5 alkoxy carbonyl or aryl, R1、R2And R3In at least one alkoxy for carbon number 1~5, R4Indicate (methyl) propylene Acyloxy, vinyl, isocyanate group, imidazole radicals, sulfydryl, amino, methylamino, dimethylamino, benzylamino, phenylamino Base, Cyclohexylamino, morpholinyl, piperazinyl, urea groups or glycidyl, a indicate 1~10 integer.
22. anisotropically conducting adhesive according to claim 21, with the thermoplastic resin and the radical polymerization On the basis of the total amount of conjunction property compound, the amount of the silane coupling agent is 0.1~10 mass %.
23. anisotropically conducting adhesive according to claim 1 or 2, the average grain diameter of the electroconductive particle is 1~ 18μm。
24. anisotropically conducting adhesive according to claim 1 or 2, with whole volumes of the adhesive composite On the basis of, the amount of the electroconductive particle is 0.1~30 volume %.
25. anisotropically conducting adhesive according to claim 1 or 2, with whole volumes of the adhesive composite On the basis of, the amount of the electroconductive particle is 0.1~10 volume %.
26. anisotropically conducting adhesive according to claim 1 or 2, with whole volumes of the adhesive composite On the basis of, the amount of the electroconductive particle is 0.5~7.5 volume %.
27. anisotropically conducting adhesive according to claim 1 or 2, the adhesive composite be shaped to it is membranaceous and It obtains.
28. application of the adhesive composite as anisotropically conducting adhesive, the adhesive composite contain (a) thermoplasticity Resin, (b) free-radical polymerised compound, (c) radical polymerization initiator and (e) electroconductive particle,
The thermoplastic resin includes selected from polyimide resin, polyamide, phenoxy resin, poly- (methyl) acrylate tree One kind or two or more resin in fat, polyester resin, polyurethane resin and polyvinyl butyral resin,
The free-radical polymerised compound includes the compound with epoxy group,
The radical polymerization initiator includes peroxide.
29. adhesive composite is used to manufacture the application of anisotropically conducting adhesive,
The adhesive composite contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) free radical polymerization initiation Agent and (e) electroconductive particle,
The thermoplastic resin includes selected from polyimide resin, polyamide, phenoxy resin, poly- (methyl) acrylate tree One kind or two or more resin in fat, polyester resin, polyurethane resin and polyvinyl butyral resin,
The free-radical polymerised compound includes the compound with epoxy group,
The radical polymerization initiator includes peroxide.
30. a kind of connector, has：
With circuit electrode and oppositely disposed a pair of of circuit member；With
It is arranged between the pair of circuit member, the connecting elements that the pair of circuit member is bonded to each other,
The circuit electrode of the circuit electrode of the circuit member of one side and the circuit member of another party is electrically connected It connects,
The connecting elements is the solidfied material of adhesive composite,
The adhesive composite contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) free radical polymerization initiation Agent and (e) electroconductive particle,
The thermoplastic resin includes selected from polyimide resin, polyamide, phenoxy resin, poly- (methyl) acrylate tree One kind or two or more resin in fat, polyester resin, polyurethane resin and polyvinyl butyral resin,
The free-radical polymerised compound includes the compound with epoxy group,
The radical polymerization initiator includes peroxide.
31. the circuit member of connector according to claim 30, a side has glass substrate, another party's is described Circuit member has flexible base board.
CN201810615121.5A 2011-09-06 2011-09-06 Anisotropically conducting adhesive, the application of adhesive composite and connector Pending CN108676520A (en)

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CN114585704A (en) * 2019-10-25 2022-06-03 日本化学工业株式会社 Conductive adhesive, adhesive structure using same, and electronic component
CN114585704B (en) * 2019-10-25 2024-01-30 日本化学工业株式会社 Conductive adhesive, adhesive structure using same, and electronic component
CN115232573A (en) * 2021-04-23 2022-10-25 大洲电子材料（株） High-temperature-separable conductive adhesive and solar cell module
CN115232573B (en) * 2021-04-23 2024-03-26 大洲电子材料（株） High-temperature separable conductive adhesive and solar cell module
CN114702908A (en) * 2022-04-29 2022-07-05 常州德创高新材料科技有限公司 Adhesive film for flexible circuit board
CN114927256A (en) * 2022-04-29 2022-08-19 常州德创高新材料科技有限公司 Circuit connecting material
CN114702908B (en) * 2022-04-29 2023-12-22 常州德创高新材料科技有限公司 Adhesive film for flexible circuit board

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KR20140059828A (en) 2014-05-16
JP5867508B2 (en) 2016-02-24

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