CN102850982A - Adhesive composition, circuit connecting material using the same, method for connecting circuit members, and circuit connection structure - Google Patents

Adhesive composition, circuit connecting material using the same, method for connecting circuit members, and circuit connection structure Download PDF

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Publication number
CN102850982A
CN102850982A CN2012103394608A CN201210339460A CN102850982A CN 102850982 A CN102850982 A CN 102850982A CN 2012103394608 A CN2012103394608 A CN 2012103394608A CN 201210339460 A CN201210339460 A CN 201210339460A CN 102850982 A CN102850982 A CN 102850982A
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CN
China
Prior art keywords
circuit
circuit block
acrylic copolymer
adhesive composite
epoxy
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Pending
Application number
CN2012103394608A
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Chinese (zh)
Inventor
田中胜
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Publication of CN102850982A publication Critical patent/CN102850982A/en
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
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    • C09J9/02—Electrically-conducting adhesives
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    • 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
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/1901—Structure
    • H01L2924/1904—Component type
    • H01L2924/19041—Component type being a capacitor
    • 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
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/1901—Structure
    • H01L2924/1904—Component type
    • H01L2924/19043—Component type being a resistor

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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Abstract

The invention relates to an adhesive composition, a circuit connecting material using the same, a method for connecting circuit members, and a circuit connection structure. Disclosed is an adhesive composition which is used for bonding circuit members with each other and electrically connecting circuit electrodes of the circuit members with each other. This adhesive composition contains an adhesive component containing an epoxy resin, an epoxy resin curing agent, and an acrylic copolymer having a crosslinked structure and a weight average molecular weight of 30,000-80,000. Wherein, the glass transition temperature of the acrylic copolymer is -40-40 DEG C.

Description

The circuit junctional membrane of adhesive composite and use said composition, and the method for attachment of circuit block and circuit connecting body
The application is to be on September 30th, 2008 applying date of original application, application number is 2008801101962, denomination of invention is the dividing an application of Chinese patent application of " adhesive composite and use the circuit connection material of said composition, and the method for attachment of circuit block and circuit connecting body "
Technical field
The present invention relates to adhesive composite and use the circuit connection material of said composition, and the method for attachment of circuit block and the circuit connecting body of gained thus.
Background technology
As liquid crystal drive is installed in method on the face glass that liquid-crystal display uses with IC, is widely used CHIP-ON-GLASS (below, be called " COG installation ") is installed.COG installs, and is the method for using IC and face glass directly to engage liquid crystal drive.
In above-mentioned COG installs, as circuit connection material, usually use the adhesive composite with anisotropic conductive.This adhesive composite, the conducting particles that contains the caking agent composition and cooperate as required.Be configured on the part that is formed with electrode on the face glass by the circuit connection material that will comprise this adhesive composite, and the thereon semiconductor element such as pressing IC, LSI or package etc., can be electrically connected and mechanical set, to keep the conducting state between the comparative electrode, the insulation between the adjacent electrode.
In addition, as the caking agent composition of adhesive composite, use Resins, epoxy and imidazoles is the combination of solidifying agent all the time.The adhesive composite that has cooperated these compositions keeping about 5 seconds under 200 ℃ the temperature, makes epoxy resin cure usually, and the COG that carries out the IC chip installs.
Yet, in recent years, along with the maximization of liquid crystal panel and the development of thin-walled property, at the adhesive composite that uses in the past, and under the said temperature condition, carry out COG when installing, temperature head during owing to heating produces thermal expansion, and owing to shrinking the poor internal stress that produces, therefore the problem in IC chip and face glass generation warpage is arranged.
As the means that reduce the warpage that produces on the circuit block, in patent documentation 1, put down in writing and contained the potentiality solidifying agent that comprises sulfonium salt as the circuit connecting adhesive film of epoxy curing agent.And put down in writing by using this adhesive film, the Heating temperature when installing is low to moderate below 160 ℃, and can be reduced in the internal stress (referring to the paragraph [0019] of patent documentation 1) that generates in the circuit connecting body of circuit block.
Patent documentation 1: TOHKEMY 2004-221312 communique
Disclosure of the invention
The problem that invention will solve
Yet the adhesive film of putting down in writing in the patent documentation 1 although this has given play to excellent effect on the one hand in Heating temperature low temperatureization, because it has used special potentiality solidifying agent, therefore has shorter problem in work-ing life.Therefore, present present situation is, this adhesive film is that the material of solidifying agent is compared with in the past the imidazoles that is combined with, and its purposes is limited.
The present invention finishes in view of this practical situation, even being to provide, its purpose carries out circuit block under a kind of hot conditions about 200 ℃ when being connected to each other, the adhesive composite that also can fully suppress the circuit block warpage, and the circuit connection material that uses said composition.
In addition, the object of the invention also is to provide a kind of circuit connecting body with low contact resistance junction circuit parts, and the method for attachment that is used for obtaining the circuit block of this circuit connecting body.
For the method for dealing with problems
Adhesive composite of the present invention, its circuit electrode that is used for when being bonded to each other circuit block together each circuit block being had is electrically connected to each other together, and it contains Resins, epoxy, epoxy curing agent and has the crosslinking reaction group and weight-average molecular weight is 30000～80000 acrylic copolymer.Herein, the weight-average molecular weight of acrylic copolymer is by gel permeation chromatography, and the value of the working curve conversion gained of making based on the Application standard polystyrene.
In adhesive composite of the present invention, aforesaid propylene acid based copolymer has played the effect of stress negative catalyst.Therefore, use the imidazoles such as microcapsule-type or add-on type potentiality solidifying agent be solidifying agent as epoxy curing agent, even under the temperature about 200 ℃, be cured processing, also can effectively relax internal stress, and fully suppress the warpage of circuit block.
Adhesive composite of the present invention preferably further contains conducting particles.By using the adhesive composite that in the caking agent composition, has disperseed conducting particles, can make the circuit connecting body with excellent connection reliability.
The second-order transition temperature of aforesaid propylene acid based copolymer is preferably-40～40 ℃.If the second-order transition temperature of acrylic copolymer in above-mentioned scope, then can obtain having the adhesive composite of suitable viscosity.In addition, the second-order transition temperature of the cured article of adhesive composite is considered from the connection reliability viewpoint of connection section, is preferably 100～150 ℃.
In addition, aforesaid propylene acid based copolymer is by monomer component copolymerization contained in the raw material is obtained, and with respect to monomer component contained in this raw material 100 mass parts, the total amount of glycidyl acrylate and glycidyl methacrylate is preferably 1～7 mass parts.By in raw material, containing glycidyl acrylate and/or glycidyl methacrylate with above-mentioned scope, and in adhesive composite, cooperate acrylic copolymer by this raw material manufacturing, excellent stress retentivity can be obtained, and the warpage of circuit block can be suppressed more fully.
Adhesive composite of the present invention, the cured article of 1 hour gained of heating under 200 ℃ temperature, preferably the storage modulus in the time of-50 ℃ is 2.0～3.0GPa, storage modulus in the time of 100 ℃ is 1.0～2.0GPa, and the maximum value of the storage modulus in-50～100 ℃ of scopes and the difference of minimum value are below the 2.0GPa.Satisfy the cured article of the adhesive composite of this condition by use, can in wide temperature range, suppress the reduction of storage modulus, and, when using this adhesive composite that circuit block is interconnected, can make the circuit connecting body with excellent connection reliability.
Circuit connection material of the present invention comprises membranaceous base material and bond layer, and described bond layer comprises adhesive composite of the present invention and is arranged on the one side of described base material.By using the circuit connection material of this structure, can at an easy rate bond layer be configured on the circuit block, and can improve operation efficiency.In addition, when using circuit connection material, suitably peel off membranaceous base material.
Circuit connecting body of the present invention, it has a pair of circuit block and the connection section of relative configuration; Described connection section comprises the cured article of adhesive composite of the present invention, and between described a pair of circuit block and this circuit block is bonded to each other, so that the circuit electrode that each circuit block has is electrically connected to each other.
In circuit connecting body of the present invention, at least one party in a pair of circuit block can be the IC chip.In addition, in this circuit connecting body, the surface of at least one party in the circuit electrode that a pair of circuit block has separately can consist of by being selected from least a in gold and silver, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum and the indium tin oxide.
In addition, in circuit connecting body of the present invention, with at least one party of the bearing surface of a pair of circuit block of connection section butt, can contain the part that is consisted of by at least a above material that is selected from silicon nitride, silicoorganic compound and the polyimide resin.
The method of attachment of circuit block of the present invention, by making adhesive composite of the present invention between a pair of circuit block of relative configuration, integral body is carried out heating and pressurizing, and form that cured article by adhesive composite forms and between a pair of circuit block and circuit block is bonded to each other into the connection section that circuit electrode that circuit block separately has is electrically connected to each other, obtain thus having the circuit connecting body of a pair of circuit block and connection section.
The invention effect
According to the present invention, even carry out circuit block under the hot conditions about 200 ℃ when being connected to each other, also can fully suppress the warpage of circuit block.
Description of drawings
Fig. 1 is the sectional view of a kind of embodiment of expression circuit connection material of the present invention.
Fig. 2 is illustrated in to use circuit connection material of the present invention, the sectional view of junction circuit electrode state each other between circuit electrode.
Fig. 3 is a kind of process picture sheet of embodiment that is represented the method for attachment of circuit block of the present invention by summary sectional view.
Fig. 4 is the sectional view of other form of expression conducting particles.
Fig. 5 is the sectional view of other embodiment of expression circuit connection material of the present invention.
Nomenclature
5, the 15th, circuit connection material; 6,6a, 6b are base materials; 7a is the layer that contains conducting particles; 7b is the layer that does not contain conducting particles; The 8th, bond layer; The 9th, the caking agent composition; 10A, 10B are conducting particless; 30 is the 1st circuit blocks; 40 is the 2nd circuit blocks; 50a is connection section; The 100th, circuit connecting body.
Embodiment
Below, the preferred implementation that present invention will be described in detail with reference to the accompanying.In addition, in description of drawings, give same-sign for identical element, and the repetitive description thereof will be omitted.In addition, for the convenience of accompanying drawing, the dimension scale of accompanying drawing might not be consistent with description.
" (methyl) acrylate " expression " acrylate " and " methacrylic ester " corresponding with it in this specification sheets, " (methyl) vinylformic acid " expression " vinylformic acid " and " methacrylic acid " corresponding with it.
＜circuit connection material 〉
At first, describe for the circuit connection material in the present embodiment.Fig. 1 is the sectional view of the circuit connection material 5 in the expression present embodiment.Circuit connection material 5 contains membranaceous base material 6 and is arranged on bond layer 8 on the one side of base material 6.Bond layer 8 comprises adhesive composite, and this adhesive composite contains (a) Resins, epoxy, (b) epoxy curing agent and (c) comprises the caking agent composition 9 of acrylic copolymer and be dispersed in conducting particles 10A in the caking agent composition 9.
Circuit connection material 5, by use apparatus for coating with the solution coat of adhesive composite on membranaceous base material 6, and the warm air drying specified time form bond layer 8 and make.The bond layer 8 that comprises adhesive composite by formation than the situation of for example directly using the pasty state adhesive composite, is installed or COF has advantages of the operation efficiency raising when (CHIP-ON-FLEX installations) is installed at the COG that is used for IC chip etc.
As base material 6, can use by formed various base band such as polyethylene terephthalate (PET), PEN, polyethylene glycol isophthalate, polybutylene terephthalate, polyolefine, poly-acetic ester, polycarbonate, polyphenylene sulfide, polymeric amide, ethylene vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, synthetic rubber system, liquid crystalline polymerss.But the material of formation base material 6 is not limited thereto.In addition, as base material 6, can also use and implement the material of Corona discharge Treatment, anchoring coating processing, antistatic treatment etc. with the bearing surface of bond layer 8 etc.
In addition, when using circuit connection material 5, in order easily base material 6 to be peeled off from bond layer 8, can behind the surface of base material 6 coating stripping treatment agent, use.As stripping treatment agent, can use the various stripping treatment agents such as multipolymer, Synolac, the amino-alkyd resin of silicone resin, organosilicon and organic system resin, the resin with chain alkyl, the resin with fluoro-alkyl, lac resin.
The thickness of base material 6 is not particularly limited, but considers the keeping, the convenience when using etc. of circuit connection material 5, then is preferably 4～200 μ m, further, considers material cost and productivity, then 15～75 μ m more preferably.
The thickness of bond layer 8 gets final product according to suitable adjustment such as the circuit block shapes that connects, is preferably 5～50 μ m.If the thickness deficiency of bond layer 85 μ m then have the tendency of the quantity not sufficient that is filled in the adhesive composite between circuit block.On the other hand, if it surpasses 50 μ m, then have the tendency of the conducting between the circuit electrode that is difficult to guarantee to connect.
Form the adhesive composite of bond layer 8, be preferably formed the cured article that meets the following conditions in the time of 1 hour for heating under 200 ℃ temperature.That is to say, the cured article of adhesive composite considers that from the viewpoint of connection reliability the storage modulus in the time of-50 ℃ of using the Measurement of Dynamic Viscoelasticity device to measure is preferably 2.0～3.0GPa, and the storage modulus in the time of 100 ℃ is preferably 1.0～2.0GPa.And the maximum value of the storage modulus of this cured article in-50～100 ℃ of scopes and the difference of minimum value are preferably below the 2.0GPa.
When significantly reduced adhesive composite is as circuit connection material under the temperature condition that the storage modulus of using cured article is being stipulated, have the problem of the connection reliability variation of circuit block, as mentioned above, by in-50～100 ℃ wide temperature range, suppressing the reduction of storage modulus, can make the circuit connecting body with excellent connection reliability.In addition, the second-order transition temperature of the cured article of adhesive composite is considered from the connection reliability viewpoint of connection section, is preferably 100～150 ℃, more preferably 110～140 ℃, and more preferably 110～130 ℃.
The cured article of the adhesive composite in the present embodiment can be in the major cause of storage modulus acquisition excellent specific property, and supposition is because caking agent composition 9 contains (c) acrylic copolymer, and this acrylic copolymer has played the effect of stress negative catalyst.
(caking agent composition)
Then, to (a) Resins, epoxy contained in the caking agent composition 9, (b) epoxy curing agent and (c) acrylic copolymer describe.
As (a) Resins, epoxy, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bisphenol-A phenolic varnish type Resins, epoxy, bisphenol F phenolic varnish type Resins, epoxy, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glycolylurea type Resins, epoxy, isocyanuric acid ester type epoxy resin, aliphatics chain Resins, epoxy etc.These Resins, epoxy can halogenation, also can hydrogenation.These Resins, epoxy can use separately a kind, also can will be used in combination more than 2 kinds.
As (b) epoxy curing agent, can enumerate amine system, phenol system, acid anhydrides system, imidazoles system, hydrazides system, Dyhard RU 100, boron trifluoride-amine coordination compound, sulfonium salt, salt compounded of iodine, amine imide etc.Wherein, consider from the viewpoint in solidified nature and work-ing life, preferably using imidazoles is solidifying agent.Be solidifying agent as imidazoles, can enumerate 2-ethyl-4-methylimidazole, glyoxal ethyline, 1-cyano ethyl-2-phenylimidazole etc.They can use separately, or will be more than 2 kinds mix and use, and can mixed decomposition promotor, inhibitor etc. uses.In addition, for realize at high level long life and rapidly-curable the two, preferably use the potentiality curing catalyst, specifically, preferably use the addition compound (microcapsule-type or add-on type potentiality solidifying agent etc.) of imidazoles and Resins, epoxy.
(c) acrylic copolymer, having crosslinking reaction group and weight-average molecular weight is 30000～80000.Contain weight-average molecular weight less than the adhesive composite of 30000 acrylic copolymer, film-forming properties is not enough, and the stress alleviation effects is not enough simultaneously.On the other hand, contain the adhesive composite that weight-average molecular weight surpasses 80000 acrylic copolymer, illiquidity, the circuit fillibility is not enough, has simultaneously the tendency that the consistency with Resins, epoxy descends.The weight-average molecular weight of acrylic copolymer is preferably 40000～70000, and more preferably 40000～60000.
(c) acrylic copolymer, monomer that can be by having the crosslinking reaction group and the copolymerization of other monomer obtain.As the monomer with crosslinking reaction group, can enumerate (methyl) glycidyl acrylate, acrylamide, vinylformic acid hydroxyl butyl ester, methacrylic acid hydroxyl ethyl ester etc.
Preferred concrete example as (c) acrylic copolymer, can enumerate with respect to 100 mass parts monomer components, the total amount of glycidyl acrylate and glycidyl methacrylate is that the raw material supplying of 1～7 mass parts (more preferably 2～6 mass parts) is to the material of copolyreaction manufacturing.By the total amount of (methyl) glycidyl acrylate acrylic copolymer less than the copolymerization gained of the monomer component of 1 mass parts, can't fully obtain crosslinking structure, and, contain the adhesive composite of this acrylic copolymer, have the tendency of stress retentivity deficiency.On the other hand, contain the adhesive composite of acrylic copolymer of copolymerization gained that is surpassed the monomer component of 7 mass parts by the total amount of (methyl) glycidyl acrylate, storage modulus easily uprises, and has the tendency of stress retentivity deficiency.
(c) second-order transition temperature of acrylic copolymer (Tg) is preferably-40～40 ℃.Contain second-order transition temperature less than the adhesive composite of-40 ℃ acrylic copolymer, have the excessive tendency of viscosity (adhesivity).On the other hand, contain the adhesive composite that second-order transition temperature surpasses 40 ℃ acrylic copolymer, have the tendency of viscosity deficiency.(c) second-order transition temperature of acrylic copolymer more preferably-20～20 ℃.
(c) when making acrylic copolymer, as with other monomer of (methyl) glycidyl acrylate copolymerization, can enumerate butyl acrylate, vinyl cyanide, vinylformic acid hydroxy methyl, vinylbenzene, butyl methacrylate, acrylamide etc.In these monomers, can pass through to adjust the use level of butyl acrylate and/or vinyl cyanide, thereby optimize the second-order transition temperature of gained acrylic copolymer.More particularly, with respect to contained monomer component in the 100 mass parts raw materials, the total amount of butyl acrylate and vinyl cyanide is preferably more than 80 mass parts.
(a) content of Resins, epoxy based on the total mass of caking agent composition 9, is preferably 3～50 quality %, and 10～30 quality % more preferably.If (a) content of Resins, epoxy is less than 3 quality %, then curing reaction carries out insufficiently, and has the tendency that is difficult to obtain good bonding strength and contact resistance value.On the other hand, if it surpasses 50 quality %, the flowability that then has caking agent composition 9 descends the tendency that shortens work-ing life.In addition, also have the tendency that the contact resistance value of circuit connecting body connection section uprises.
(b) content of epoxy curing agent based on the total mass of caking agent composition 9, is preferably 5～60 quality %, and 10～40 quality % more preferably.If (b) content of epoxy curing agent is less than 5 quality %, then curing reaction carries out insufficiently, and has the tendency that is difficult to obtain good bonding strength and contact resistance value.On the other hand, if it surpasses 60 quality %, the flowability that then has caking agent composition 9 descends the tendency that shortens work-ing life.In addition, also have the tendency that the contact resistance value of circuit connecting body connection section uprises.
(c) content of acrylic copolymer based on the total mass of caking agent composition 9, is preferably 3～30 quality %, and 8～25 quality % more preferably.If (c) content of acrylic copolymer is less than 3 quality %, then have the tendency of stress alleviation effects deficiency.On the other hand, if it surpasses 25 quality %, the flowability that then has caking agent composition 9 descends the tendency that shortens work-ing life.In addition, also have the tendency that the contact resistance value of circuit connecting body connection section uprises.
Caking agent composition 9 can further contain the film-forming properties polymer.Based on the total mass of caking agent composition 9, the high molecular content of film-forming properties is preferably 2～80 quality %, 5～70 quality % more preferably, and 10～60 quality % more preferably.As the film-forming properties polymer, can use polystyrene, polyethylene, polyvinyl butyral acetal, polyvinyl formal, polyimide, polymeric amide, polyester, polyvinyl chloride, polyphenylene oxide, urea resin, melamine resin, resol, xylene resin, polyisocyanate resin, phenoxy resin, polyimide resin, polyester urethane resin etc.
(conducting particles)
Conducting particles 10A is dispersed in the caking agent composition 9.As conducting particles 10A, can enumerate the particle of metals such as Au, Ag, Pt, Ni, Cu, W, Sb, Sn, scolding tin or carbon.The median size of conducting particles 10A is considered from viewpoint dispersed, electroconductibility, is preferably 1～18 μ m.
The mixing ratio of conducting particles 10A, caking agent composition 100 parts by volume with respect to contained in the bond layer 8 are preferably 0.1～30 parts by volume, and 0.1～10 parts by volume more preferably.If this mixing ratio less than 0.1 parts by volume, then has the tendency that the contact resistance between comparative electrode uprises, and if it surpasses 30 parts by volume, then have the tendency that easily produces short circuit between adjacent electrode.
Further, form the adhesive composite of bond layer 8, can also contain packing material, tenderizer, anti-aging agent, tinting material, fire retardant, thixotropic agent, coupling agent, melamine resin, isocyanates etc.When containing packing material, owing to can obtain the raising of connection reliability, therefore preferred.As packing material, be preferably its maximum particle diameter less than the material of conducting particles particle diameter.In addition, the content of packing material based on the cumulative volume of adhesive composite, is preferably the scope of 5～60 volume %.If it surpasses 60 volume %, then have the tendency that connection reliability and adaptation descend.In addition, as coupling agent, consider from the viewpoint that cementability improves, preferably contain the compound of more than one groups that are selected from vinyl, acrylic, amino, epoxy group(ing) and isocyanate group.
＜circuit connecting body 〉
Then, the circuit connecting body that uses circuit connection material 5 to make is described.Fig. 2 is the summary sectional view of indication circuit electrode circuit connecting body connected to one another.Circuit connecting body 100 shown in Figure 2 has the 1st relative circuit block 30 and the 2nd circuit block 40, and between the 1st circuit block 30 and the 2nd circuit block 40, is provided with the connection section 50a that connects them.
The 1st circuit block 30 has circuit substrate 31 and formed circuit electrode 32 on the interarea 31a of circuit substrate 31.The 2nd circuit block 40 has circuit substrate 41 and formed circuit electrode 42 on the interarea 41a of circuit substrate 41.
As the concrete example of circuit block, can enumerate the chip parts such as semi-conductor chip (IC chip), resistance chip, electric capacity chip etc.These circuit blocks have circuit electrode, and usually have a plurality of circuit electrodes.As the concrete example that connects foregoing circuit circuit block parts, the opposing party, the circuit base plates such as glass substrate of indium tin oxide (ITO) of can having enumerated flexible belt with metal wiring, flexibility printed circuit board, evaporation.
Interarea 31a and/or interarea 41a can use the organic insulation materials such as polyimide resin of silicon nitride, silicoorganic compound and silicone resin and photosensitivity or non-photosensitive to be coated with.In addition, interarea 31a and/or interarea 41a can local contain the zone that is formed by above-mentioned material.Further, circuit substrate 31 and/or circuit substrate 41 also can be formed by above-mentioned material itself.Interarea 31a, 41a can be made of a kind in the above-mentioned material, also can be by consisting of more than 2 kinds.By the composition of suitable selection caking agent composition 9, can suitably connect and contain by the circuit substrate of above-mentioned material institute forming section each other.
Each circuit electrode 32,42 surface can be by at least a formations that is selected from gold and silver, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum and the indium tin oxide (ITO), also can be by consisting of more than 2 kinds.In addition, circuit electrode 32,42 Facing material can be identical in all circuit electrodes, also can be different.
Connection section 50a has the cured article 9A of caking agent composition 9 contained in the bond layer 8, and is dispersed in conducting particles 10A wherein.So, in circuit connecting body 100, relative circuit electrode 32 and circuit electrode 42,10A is electrically connected by conducting particles.That is to say that conducting particles 10A directly contacts with circuit electrode 32,42 both sides.Therefore, circuit electrode 32,42 contact resistance fully reduce, and can carry out good electrical connection circuit electrode 32,42.On the other hand, cured article 9A has electrical insulating property, has guaranteed adjacent circuit electrode insulativity each other.Therefore, circuit electrode 32,42 electric current are flowed smoothly, and can give full play to the function that circuit has.
The manufacture method of＜circuit connecting body 〉
Then, the manufacture method of circuit connecting body 100 described.Fig. 3 is a kind of process picture sheet of embodiment that is represented the manufacture method of circuit connecting body of the present invention by summary sectional view.In the present embodiment, make bond layer 8 thermofixations of circuit connection material 5, and finally make circuit connecting body 100.
At first, circuit connection material 5 is cut to specified length, simultaneously bond layer 8 is faced down, be arranged on (Fig. 3 (a)) on the one side the 1st circuit block 30, that be formed with circuit electrode 32.At this moment, peel off base material 6 from bond layer 8.
Then, pressurize in arrow A and the B direction of Fig. 3 (b), make bond layer 8 temporary transient be connected with the 1st circuit block 30 (Fig. 3 (c)).At this moment pressure is not so long as can to the scope of circuit block generation damage, just be not particularly limited, but usually be preferably 0.1～3.0MPa.In addition, pressurize while also can heat, and Heating temperature is the temperature that bond layer 8 can not solidify in fact.Heating temperature is preferably 50～100 ℃ usually.This heating and pressurization are preferably carried out with 0.1～10 second scope.
Then, shown in Fig. 3 (d), at bond layer 8 the 2nd circuit block 40 is set, and makes the 2nd circuit electrode 42 towards a side of the 1st circuit block 30.Therefore, on one side caking agent layer 8, on one side on the direction of the arrow A of Fig. 3 (d) and B to all pressurizeing.At this moment Heating temperature is the temperature that the caking agent composition 9 of bond layer 8 can solidify.Heating temperature is preferably 150～230 ℃, and more preferably 170～210 ℃, and more preferably 180～200 ℃.If Heating temperature, then has the slack-off tendency of curing speed less than 150 ℃, and if above 230 ℃, then have the tendency of the undesirable side reaction of easy generation.Be preferably 0.1～30 second heat-up time, and more preferably 1～25 second, and more preferably 2～20 seconds.
By the curing of caking agent composition 9, form connection section 50a, can obtain circuit connecting body shown in Figure 2 100.The condition that connects is suitably selected according to use, adhesive composite, circuit block.In addition, when cooperating the material that is cured by light as the caking agent composition of bond layer 8, bond layer 8 suitable radiation active rays or energy-ray are got final product.As active ray, can enumerate ultraviolet ray, visible light, infrared rays etc.As energy-ray, can enumerate electron rays, X ray, gamma-rays, microwave etc.
Above, be illustrated for preferred implementation of the present invention, but the present invention is not limited to above-mentioned embodiment.The present invention can carry out various changes in the scope that does not break away from its purport.
For example, in the above-described embodiment, take the adhesive composite that contains conducting particles 10A as example, but according to the shape of the circuit block of installing etc., adhesive composite also can not contain conducting particles 10A.In addition, can also use by the nuclear particle with electroconductibility and be arranged on the conducting particles that a plurality of insulativity particles on this particle surface consist of, replace conducting particles 10A.
Conducting particles 10B shown in Figure 4 has the nuclear particle 1 of electroconductibility and is arranged on this nuclear particle 1 lip-deep a plurality of insulativity particles 2.And nuclear particle 1 is by the substrate particle 1a that consists of centre portions and be arranged on the lip-deep conductive layer 1b of this substrate particle 1a and consist of.Below, 10B describes to conducting particles.
As the material of substrate particle 1a, can enumerate glass, pottery, organic high molecular compound etc.In these materials, preferably produce the material (for example, glass, organic high molecular compound) of distortion by heating and/or pressurization.If substrate particle 1a is deformable material, then at conducting particles 10B by circuit electrode 32,42 whens extruding, itself and the contact area increase of circuit electrode.In addition, can also absorbing circuit electrode 32,42 concave-convex surface.Therefore, the connection reliability between circuit electrode improves.
Considering from above-mentioned viewpoint, be suitable for consisting of the material of substrate particle 1a, for example is acrylic resin, styrene resin, benzoguanamine resin, silicone resin, polybutadiene or their multipolymer and their cross-linking agent.Substrate particle 1a can be the material of identical or different kind between particle, for same particle, can use separately a kind of material, the material that perhaps can be mixed with two or more.
The median size of substrate particle 1a can be according to the suitably design such as purposes, but is preferably 0.5～20 μ m, 1～10 μ m more preferably, and 2～5 μ m more preferably.When using median size to make conducting particles less than the substrate particle of 0.5 μ m, can produce the secondary aggegation of particle, have the tendency of the interelectrode insulativity deficiency of adjacent circuit, and when using the substrate particle that surpasses 20 μ m to make conducting particles, because its size, and have the tendency of the interelectrode insulativity deficiency of adjacent circuit.
Conductive layer 1b is layer that mode with the surface of covering substrates particle 1a arranges, that formed by the material with electroconductibility.Consider the whole surface of the preferred covering substrates particle of conductive layer 1b 1a from the viewpoint of fully guaranteeing electroconductibility.
As the material of conductive layer 1b, can enumerate, have the nonmetal of electroconductibility such as gold and silver, platinum, nickel, copper and their alloy, the alloy such as scolding tin that contains tin and carbon etc.The material of conductive layer 1b is preferably metal, because can carry out coating to substrate particle 1a by electroless plating.In addition, in order to obtain enough work-ing life, more preferably gold and silver, platinum or their alloy, and gold more preferably.In addition, they can use separately a kind, perhaps will be used in combination more than 2 kinds.
The thickness of conductive layer 1b can be according to the suitably design such as its employed material, purposes, and is preferably 50～200nm, and 80～150nm more preferably.If thickness less than 50nm, then has the tendency that can't obtain enough low-resistance values at connection section.On the other hand, thickness surpasses the conductive layer 1b of 200nm, has the tendency of making decrease in efficiency.
Conductive layer 1b, can by one deck or two-layer more than consist of.In any situation, to consider from the keeping quality viewpoint of the adhesive composite that uses this conductive layer made, the upper layer of nuclear particle 1 preferably is made of gold and silver, platinum or their alloy, and more preferably is made of gold.As conductive layer 1b, be by gold and silver, platinum or their alloy (below, be called " gold wait for metal ") when formed one deck consists of, in order to obtain enough low resistance values of connection portion, its thickness is preferably 10～200nm.
On the other hand, when conductive layer 1b is when consisting of more than two-layer, the outermost layer of conductive layer 1b preferably is made of metals such as gold, but the layer between outermost layer and the substrate particle 1a for example, can be made of the metal level that contains nickel, copper, tin or their alloys.At this moment, by the thickness that consists of the formed metal levels of metal such as the outermost gold of conductive layer 1b, consider from the keeping quality viewpoint of adhesive composite, be preferably 30～200nm.Nickel, copper, tin or their alloy are owing to redoxomorphism produces free free radical.Therefore, if by the formed outermost thickness of the metals such as gold less than 30nm, then with have free-radical polymerised caking agent composition and time spent, have the tendency that is difficult to fully to prevent free free radical impact.
As the method that forms conductive layer 1b on substrate particle 1a surface, can enumerate electroless plating processing or physics coating processing.Consider from the easiness viewpoint that conductive layer 1b forms, preferably form by the formed conductive layer 1b of metal by the surface of electroless plating at substrate particle 1a.
Insulativity particle 2 is made of organic high molecular compound.As organic high molecular compound, be preferably the material with thermal softening.The suitable material of insulativity particle for example is polyethylene, ethylene-acetate multipolymer, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate copolymer, polyester, polymeric amide, urethane, polystyrene, styrene diethylene benzene copoly mer, vinylbenzene-isobutylene copolymers, styrene-butadiene copolymer, vinylbenzene-(methyl) acrylic copolymer, ethylene-propylene copolymer, (methyl) acrylic ester rubber, styrene-ethylene-butylene copolymer, phenoxy resin, solid epoxy etc.They can use separately a kind, also can will be used in combination more than 2 kinds.In addition, consider from dispersity, solvent resistance and the stable on heating viewpoint of size-grade distribution, vinylbenzene-(methyl) acrylic copolymer is particularly suitable.As the manufacture method of insulativity particle 2, can enumerate seeding polymerization method etc.
Consist of the softening temperature of the organic high molecular compound of insulativity particle 2, more than the Heating temperature when being preferably circuit block and being connected to each other.If the Heating temperature of softening temperature when connecting, then since insulativity particle 2 excessive deformations when connecting therefore have and can't obtain the tendency that good electrical connects.
The median size of insulativity particle 2 can be according to the suitably design such as purposes, and is preferably 50～500nm, 50～400nm more preferably, and 100～300nm more preferably.If median size is less than 50nm, then have the tendency of the insulativity deficiency between adjacent circuit, on the other hand, if it surpasses 500nm, then have be difficult to realize the connection portion enough low initial stage resistance value and inhibition resistance value through the time the rise tendency of this two aspect.
In addition, circuit connection material of the present invention is not limited to form the single layer structure of individual layer bond layers 8 at base material 6 as the circuit connection material 5 of above-mentioned embodiment, its also can be at base material 6 superimposed layers the multilayered structure of a plurality of bond layers.The circuit connection material of multilayered structure can be made by kind or the different layer of its content of a plurality of caking agent compositions of lamination and conducting particles.For example, circuit connection material, can have contain conducting particles contain the conductive particle sublayer, and be arranged on this contain at least one of the conductive particle sublayer do not contain conducting particles do not contain the conductive particle sublayer.
Circuit connection material 15 as shown in Figure 5 has double-deck bond layer 7, and covers respectively this bond layer 7 two outmost base material 6a, 6b.The bond layer 7 of circuit connection material 10 is made of the conductive particle sublayer 7b that do not contain that contains conductive particle sublayer 7a and do not contain conducting particles that contains conducting particles.Circuit connection material 15 can contain conductive particle sublayer 7a by forming on the surface of base material 6a, and forms on the surface of base material 6b and not contain conductive particle sublayer 7b, and uses in the past these layers of applyings such as known laminating machine and make.When using circuit connection material 15, suitably peel off base material 6a, 6b.
According to circuit connection material 15, at bonding circuit block each other the time, can fully suppress because of the flow minimizing of conducting particles number on the circuit electrode that causes of caking agent composition.Thus, for example, when being connected to the IC chip on the substrate by COG installation or COF installation, can fully guarantee the number of the conducting particles on the IC chip metal protuberance.At this moment, preferably circuit connection material 7 is configured to, the IC chip has the one side of metal protuberance and does not contain conductive particle sublayer 7b, and, the substrate of IC chip is installed and contain conductive particle sublayer 7a, against each other.
Embodiment
(embodiment 1)
Following manufacturing has the nuclear particle of electroconductibility.That is to say, preparation crosslinked polystyrene particle (is combined and is ground chemistry manufacturing, trade(brand)name: SX series, median size: 4 μ m) as substrate particle, and process by electroless plating Ni layer (thickness is 0.08 μ m) is arranged on the surface of this particle.Further, process the outside that Au layer (thickness is 0.03 μ m) is arranged on this Ni layer by electroless plating, obtain having the nuclear particle by Ni layer and the formed conductive layer of Au layer.
Prepare crosslinked acrylic resin (combine and grind chemistry manufacturing, trade(brand)name: MP series), as the organic high molecular compound (insulation-coated) that is used for the tegmental nuclei particle surface.With this crosslinked acrylic resin of 4g and 20g nuclear particle, be directed into hydridization device (Nara Machinery Co., Ltd. makes, trade(brand)name: NHS series), make conducting particles.In addition, the treatment condition of hydridization device are, speed of rotation is 16000/ minute, and the reactive tank temperature is 60 ℃.
Then, use bisphenol A type epoxy resin and 9,9 '-two (4-hydroxy phenyl) fluorenes, the synthetic glass temperature is 80 ℃ phenoxy resin.This phenoxy resin of 50g is dissolved in the solvent, and the preparation solids component is the solution of 40 quality %.In addition, as solvent, the mixed solvent of use toluene and ethyl acetate (both mixing quality ratios=1:1).
On the other hand, carry out copolymerization by making the raw material monomer that forms shown in the table 1, make the acrylic copolymer with crosslinking reaction group.The molecular-weight average of the acrylic copolymer of making in the present embodiment is the 40000(polystyrene conversion), second-order transition temperature Tg is-10 ℃.This acrylic copolymer is dissolved in the ethyl acetate, and the preparation solids component is the solution of 40 quality %.
Phenoxy resin 45 mass parts (solids component), acrylic copolymer 15 mass parts (solids component) and liquid epoxy resin 40 mass parts (solids component) that contain microcapsule-type potentiality solidifying agent (imidazoles is solidifying agent) are mixed, obtain the solution of caking agent composition.With respect to 100 parts by volume caking agent compositions, cooperate the above-mentioned conducting particles of 5 parts by volume, and under 23 ℃ temperature, stir, obtain the solution of adhesive composite.
Use stripping treatment agent (silicone resin) implemented surface-treated PET film (film Co., Ltd. of Supreme Being people Du Pont makes, trade(brand)name: ピ ュ ー レ ッ Network ス, thickness: on the surface 50 μ m), the solution of coating adhesive composition.Then, it is carried out warm air drying (lower dry 5 minutes at 80 ℃), what obtain thickness by the support of PET film and be 10 μ m contains the conductive particle sublayer.
In addition, phenoxy resin 40 mass parts (solids component), acrylic copolymer 15 mass parts (solids component) and liquid epoxy resin 45 mass parts (solids component) that contain microcapsule-type potentiality solidifying agent (imidazoles is solidifying agent) are mixed, do not contained the solution of the caking agent composition of conducting particles.(film Co., Ltd. of Supreme Being people Du Pont makes, trade(brand)name: ピ ュ ー レ ッ Network ス, thickness: on the surface 50 μ m), be coated with the solution of this caking agent composition using stripping treatment agent (silicone resin) to implement surface-treated PET film.Then, it is carried out warm air drying (lower dry 5 minutes at 80 ℃), what obtain thickness by the support of PET film and be 15 μ m does not contain the conductive particle sublayer.
Use in the past known laminating machine, these adhesive films are bonded to each other.Thus, obtain double-deck circuit connection material shown in Figure 5.
(making of circuit connecting body)
Use the circuit connection material of as above manufacturing, (thickness is 0.7mm, and surface resistivity＜20 Ω/) and IC chip (thickness is 0.55mm) form circuit connecting body to connect ito substrate.The IC chip, it is 2500 μ m that use has the projection area 2(50 μ m * 50 μ m), spacing are 100 μ m, highly are the material of the golden projection of 20 μ m.Ito substrate uses at thickness and forms the material of ITO by evaporation on as the glass pane surface of 1.1mm.
Make circuit connection material between IC chip and ito substrate, and (Dongli Engineering Co., Ltd make, trade(brand)name: FC-1200) connect to use press binding device.Specifically, at first, peel off the PET film that contains conductive particle sublayer side, and circuit connection material is configured on the ito substrate, make to contain conductive particle sublayer and ito substrate butt.Then, use press binding device to carry out temporary transient pressing (75 ℃ of temperature, pressing is 2 seconds under the pressure 1.0MPa).Then, after peeling off the PET film that does not contain conductive particle sublayer side, the IC chip is set, makes golden projection and do not contain conductive particle sublayer butt.Use silica glass as substrate, and under 200 ℃ of temperature, pressure 80MPa heating and pressurizing 5 seconds, obtain thus having the circuit connecting body of connection section.
(mensuration of amount of warpage)
For the amount of warpage of the ito substrate behind the installation IC chip, (Keyemce company makes, trade(brand)name: LT-9000) measure to use non-contact laser type 3 d shape testing device.Make the IC chip side down, the back side of ito substrate is placed on circuit connecting body on the smooth table top up.Then, measure on the back side central part of ito substrate and this ito substrate back side difference of altitude apart from 5mm place, IC chip two ends.With the amount of warpage of this difference of altitude as glass substrate.
(mensuration of initial stage contact resistance)
(Advantest company makes, trade(brand)name: digital volt ohm-milliammeter), measure the as above initial stage resistance of the connection section of the circuit connecting body of made to use the resistance measurement machine.In addition, between electrode, flow through the electric current of 1mA, measure.
(evaluation of connection reliability)
For the connection reliability of the connection section of circuit connecting body, estimate by temperature cycling test.Temperature cycling test is following carries out, circuit connecting body is housed in the temperature cycle groove, and (ETAC makes, trade(brand)name: NT1020), and repeatedly be cooled to-40 ℃ from room temperature 500 times, be warming up to 100 ℃ from-40 ℃ again, and from 100 ℃ of temperature cycle that are cooled to room temperature.Hold-time under-40 ℃ and 100 ℃ all is 30 minutes.The resistance measurement of the connection portion after the temperature cycling test, and the mensuration of initial stage resistance is carried out equally.
(evaluation of the insulativity between adjacent electrode)
(Advantest company makes, trade(brand)name: digital volt ohm-milliammeter), measure in the following sequence the insulation resistance between adjacent electrode to use the resistance measurement machine.At first, apply 1 minute direct current (DC) 50V voltage at the connection section of circuit connecting body.Then, to applying the connection section behind the voltage, carry out the mensuration of insulation resistance by 2 terminals measurement methods.In addition, potentiometer (manufacturing of Advantest company, trade(brand)name: ULTRA HIGH RESISTANCE METER) are used in applying of above-mentioned voltage.
(mensuration of storage modulus and second-order transition temperature)
Under 200 ℃ to the present embodiment in the double-deck circuit connection material heating 1 hour of made, make its curing.From the cured article of circuit connection material, cut determined sample (wide 5mm, long 20mm, thickness 25 μ m), and following mensuration storage modulus and second-order transition temperature.That is to say, for the dynamic viscoelastic of determined sample, use Measurement of Dynamic Viscoelasticity device RASII(TA instrument company to make), be that 5 ℃/minute, frequency are that 10Hz, amplitude are to measure under the stretch mode condition of 3 μ m at heat-up rate.Then, the result by gained, obtain storage modulus under-50 ℃ and 100 ℃ and tan δ maximum value (second-order transition temperature, Tg).
In table 3, represent that determined sample (cured article of circuit connection material) is in the storage modulus under-50 ℃ and 100 ℃, maximum value and minimum value and the second-order transition temperature of storage modulus of determined sample in-50 ℃～100 ℃ scopes.In addition, in table 4, the measurement result of the amount of warpage of expression ito substrate, contact resistance value, insulating resistance value.
(embodiment 2)
Be 50 * 10 except using the weight-average molecular weight by the raw material monomer manufacturing shown in table 1 embodiment 2 hurdles 3Acrylic copolymer, replacing weight-average molecular weight is 40 * 10 3Acrylic copolymer outside, and same double-deck circuit connection material and the circuit connecting body made of embodiment 1.
(embodiment 3)
Be 70 * 10 except using the weight-average molecular weight by the raw material monomer manufacturing shown in table 1 embodiment 3 hurdles 3, second-order transition temperature is-5 ℃ acrylic copolymer, replacing weight-average molecular weight is 40 * 10 3, second-order transition temperature is outside-10 ℃ the acrylic copolymer, and embodiment 1 same double-deck circuit connection material and the circuit connecting body made.
(embodiment 4)
Be 60 * 10 except using the weight-average molecular weight by the raw material monomer manufacturing shown in table 1 embodiment 4 hurdles 3, second-order transition temperature is 0 ℃ acrylic copolymer, replacing weight-average molecular weight is 40 * 10 3, second-order transition temperature is outside-10 ℃ the acrylic copolymer, and embodiment 1 same double-deck circuit connection material and the circuit connecting body made.
(embodiment 5)
Be 70 * 10 except using the weight-average molecular weight by the raw material monomer manufacturing shown in table 1 embodiment 5 hurdles 3, second-order transition temperature is 10 ℃ acrylic copolymer, replacing weight-average molecular weight is 40 * 10 3, second-order transition temperature is outside-10 ℃ the acrylic copolymer, and embodiment 1 same double-deck circuit connection material and the circuit connecting body made.
(comparative example 1)
Except when making double-deck circuit connection material, in each solution, mismatch the acrylic copolymer with crosslinking reaction group, and form with the cooperation ratio shown in the table 2 and to contain the conductive particle sublayer and do not contain outside the conductive particle sublayer, and the embodiment 1 same double-deck circuit connection material of making and circuit connecting body.
[table 1]
Figure BDA00002133396300181
[table 2]
Figure BDA00002133396300182
[table 3]
The physical property of circuit connection material cured article Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1
Storage modulus under-50 ℃ (GPa) 2.1 2.3 2.4 2.6 2.8 3.5
Storage modulus under 100 ℃ (GPa) 1.1 1.3 1.5 1.6 1.8 2.2
Second-order transition temperature (℃) 118 123 130 133 135 145
[0135][table 4]
Figure BDA00002133396300191
Industrial applicibility
According to the present invention, even when carrying out each other connection of circuit block under the hot conditions about 200 ℃, also can fully suppress the warpage of circuit block.

Claims (19)

1. adhesive composite, it is used for being electrically connected circuit electrode that circuit block separately has each other when bonding circuit block each other, it contains Resins, epoxy, epoxy curing agent and has the crosslinking reaction group and weight-average molecular weight is 30000～80000 acrylic copolymer, wherein, the second-order transition temperature of described acrylic copolymer is-40～40 ℃.
2. adhesive composite, it is used for being electrically connected circuit electrode that circuit block separately has each other when bonding circuit block each other, it contains Resins, epoxy, epoxy curing agent, and to have crosslinking reaction group and weight-average molecular weight be 30000～80000 acrylic copolymer, wherein, the cured article of 1 hour gained of this adhesive composite of heating under 200 ℃ temperature, its storage modulus in the time of-50 ℃ is 2.0～3.0GPa, storage modulus in the time of 100 ℃ is 1.0～2.0GPa, and the maximum value of the storage modulus in-50～100 ℃ of scopes and the difference of minimum value are below the 2.0GPa.
3. adhesive composite as claimed in claim 2, wherein, the second-order transition temperature of described acrylic copolymer is-40～40 ℃.
4. such as each the described adhesive composite in the claim 1～3, it further contains conducting particles.
5. circuit junctional membrane, it possesses membranaceous base material and bond layer, and described bond layer comprises each the described adhesive composite in the claim 1～4 and is arranged on the face of described base material.
6. circuit connecting body, it possesses a pair of circuit block and the connection section of relative configuration, described connection section comprises the cured article of each the described adhesive composite in the claim 1～4, and between described a pair of circuit block and this circuit block is bonded to each other into the circuit electrode that circuit block separately has is electrically connected to each other.
7. circuit connecting body as claimed in claim 6, wherein, at least one party in the described a pair of circuit block is the IC chip.
8. the method for attachment of a circuit block, by making each described adhesive composite in the claim 1～4 between a pair of circuit block of relative configuration, integral body is carried out heating and pressurizing, comprise the cured article of described adhesive composite and between described a pair of circuit block and described circuit block is bonded to each other into the connection section that circuit electrode that circuit block separately has is electrically connected to each other, to obtain thus having the circuit connecting body of described a pair of circuit block and described connection section and form.
9. the manufacture method of a circuit connecting body, by making each described adhesive composite in the claim 1～4 between a pair of circuit block of relative configuration, integral body is carried out heating and pressurizing, comprise the cured article of described adhesive composite and between described a pair of circuit block and described circuit block is bonded to each other into the connection section that circuit electrode that circuit block separately has is electrically connected to each other, to obtain thus having the circuit connecting body of described a pair of circuit block and described connection section and form.
10. a composition is as the application that is electrically connected the circuit electrode caking agent each other that circuit block separately has when bonding circuit block each other, described composition contains Resins, epoxy, epoxy curing agent and has the crosslinking reaction group and weight-average molecular weight is 30000～80000 acrylic copolymer, wherein, the second-order transition temperature of described acrylic copolymer is-40～40 ℃.
11. a composition is as the application that is electrically connected the circuit electrode caking agent each other that circuit block separately has when bonding circuit block each other, described composition contains Resins, epoxy, epoxy curing agent, and to have crosslinking reaction group and weight-average molecular weight be 30000～80000 acrylic copolymer, wherein, the cured article of 1 hour gained of this adhesive composite of heating under 200 ℃ temperature, its storage modulus in the time of-50 ℃ is 2.0～3.0GPa, storage modulus in the time of 100 ℃ is 1.0～2.0GPa, and the maximum value of the storage modulus in-50～100 ℃ of scopes and the difference of minimum value are below the 2.0GPa.
12. application as claimed in claim 11, wherein, the second-order transition temperature of described acrylic copolymer is-40～40 ℃.
13. a composition is as the application that is electrically connected the circuit electrode caking agent each other that circuit block separately has when bonding circuit block each other, described composition contains Resins, epoxy, epoxy curing agent and has the crosslinking reaction group and weight-average molecular weight is 30000～80000 acrylic copolymer, wherein, the second-order transition temperature of the cured article of this adhesive composite is 110～140 ℃.
14. such as each the described application in the claim 10～13, described composition further contains conducting particles.
15. a composition is for the manufacture of the application that is electrically connected the circuit electrode caking agent each other that circuit block separately has when bonding circuit block each other, described composition contains Resins, epoxy, epoxy curing agent and has the crosslinking reaction group and weight-average molecular weight is 30000～80000 acrylic copolymer, wherein, the second-order transition temperature of described acrylic copolymer is-40～40 ℃.
16. a composition is for the manufacture of the application that is electrically connected the circuit electrode caking agent each other that circuit block separately has when bonding circuit block each other, described composition contains Resins, epoxy, epoxy curing agent, and to have crosslinking reaction group and weight-average molecular weight be 30000～80000 acrylic copolymer, wherein, the cured article of 1 hour gained of this adhesive composite of heating under 200 ℃ temperature, its storage modulus in the time of-50 ℃ is 2.0～3.0GPa, storage modulus in the time of 100 ℃ is 1.0～2.0GPa, and the maximum value of the storage modulus in-50～100 ℃ of scopes and the difference of minimum value are below the 2.0GPa.
17. application as claimed in claim 16, wherein, the second-order transition temperature of described acrylic copolymer is-40～40 ℃.
18. a composition is for the manufacture of the application that is electrically connected the circuit electrode caking agent each other that circuit block separately has when bonding circuit block each other, described composition contains Resins, epoxy, epoxy curing agent and has the crosslinking reaction group and weight-average molecular weight is 30000～80000 acrylic copolymer, wherein, the second-order transition temperature of the cured article of this adhesive composite is 110～140 ℃.
19. such as each the described application in the claim 15～18, described composition further contains conducting particles.
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WO2009044732A1 (en) 2009-04-09
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TWI394810B (en) 2013-05-01
CN101815769B (en) 2012-11-07
TW200932860A (en) 2009-08-01
JP2013058764A (en) 2013-03-28
CN102876277B (en) 2014-12-10
CN101815769A (en) 2010-08-25
KR20110066235A (en) 2011-06-16
JP5126233B2 (en) 2013-01-23
KR101376002B1 (en) 2014-03-19
KR20100009538A (en) 2010-01-27
JPWO2009044732A1 (en) 2011-02-10
KR20120073354A (en) 2012-07-04

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