CN1906265A - Circuit connection material, film-shaped circuit connection material using the same, circuit member connection structure, and manufacturing method thereof - Google Patents

Circuit connection material, film-shaped circuit connection material using the same, circuit member connection structure, and manufacturing method thereof Download PDF

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Publication number
CN1906265A
CN1906265A CNA200580001944XA CN200580001944A CN1906265A CN 1906265 A CN1906265 A CN 1906265A CN A200580001944X A CNA200580001944X A CN A200580001944XA CN 200580001944 A CN200580001944 A CN 200580001944A CN 1906265 A CN1906265 A CN 1906265A
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CN
China
Prior art keywords
circuit
connection material
electrode
connection
film
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Pending
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CNA200580001944XA
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Chinese (zh)
Inventor
竹田津润
渡边伊津夫
后藤泰史
山口一夫
藤井正规
藤井绫
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to CN201010245654.2A priority Critical patent/CN101944659B/en
Publication of CN1906265A publication Critical patent/CN1906265A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
    • H01L2224/83101—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus as prepeg comprising a layer connector, e.g. provided in an insulating plate member
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A circuit member connection structure 10 according to the invention is provided with circuit members 20,30 having a plurality of circuit electrodes 22,32 formed on the main surfaces 21a,31a of circuit boards 21,31. A circuit connecting member 60 which connects together the circuit members 20,30 with the circuit electrodes 22,32 opposing each other is comprising a cured circuit connecting material of the invention. The circuit connecting material of the invention comprises an adhesive composition and covered particles 50 comprising conductive particles 51 with portions of their surfaces 51a covered by insulating fine particles 52, wherein the mass of the insulating fine particles 52 constitutes 2/1000 to 26/1000 of the mass of the conductive particles 51.

Description

The connection structure and the manufacture method thereof of circuit connection material, the film-shaped circuit connection material that uses it, circuit member
Technical field
The present invention relates to circuit connection material, use the film-shaped circuit connection material of this material, the connection structure and the manufacture method thereof of circuit member.
Background technology
Liquid-crystal display with face glass on, the structure dress liquid crystal drive IC by COG (Chip-On-Glass) structure dress or COF (Chip-On-Flex) structure dress etc.In COG structure dress, use comprises the circuit connection material of conducting particles and liquid crystal drive directly is engaged on the face glass with IC.In COF structure dress, have upward joint liquid crystal drive IC of the flexible band of metal wiring (Flexible Tape), use contains the circuit connection material of conducting particles and these is engaged in face glass.
Yet, follow the height of liquid-crystal display in recent years to become more meticulous, use golden projection (gold bump) narrow spacing (pitch) change, the narrow areaization of the circuit electrode of IC as liquid crystal drive, so existence between adjacent circuit electrode, makes the problem of short circuit generation as the flow of conductive particle in the circuit connection material.In addition, conducting particles outflow between adjacent circuit electrode then exists as the conducting particles number in the circuit connection material that is trapped between golden projection and the face glass and reduces, and the connection resistance between the circuit electrode of subtend rises and the problem of generation bad connection.
So, as the method that addresses these problems, exploitation: form the adhesive coating of insulativity with one side at least, prevent method (for example :) that the joint quality in COG structure dress or COF structure dress descends or with the whole surface of conducting particles method (for example :) with reference to Japanese documentation 2 with the coating film of insulativity with reference to Japanese documentation 1 in circuit connection material.
Japanese documentation 1: Japanese kokai publication hei 8-279371 communique
Japanese documentation 2: Japan's special permission No. 2794009 communique (Fig. 2)
Summary of the invention
Yet, to form the method for the adhesive coating of insulativity in the one side of circuit transom, at the projection area for being lower than 3000 μ m 2, increase the situation of conducting particles number in order to obtain stable connection resistance, also have the leeway of improvement about the interelectrode insulativity of adjacent circuit.In addition, with the whole surface of conducting particles method, there is the connection resistance between the circuit electrode of subtend to rise, can not obtains the problem of stable resistance with the coating film of insulativity.
Therefore, purpose of the present invention is for providing: can lower the connection resistance between the circuit electrode of subtend fully, and, between adjacent circuit electrode, can improve the connection structure and the manufacture method thereof of the circuit connection material of insulativity, the film-shaped circuit connection material that uses these, circuit member fully.
In order to solve above-mentioned problem, circuit connection material of the present invention is in order and to form the second circuit member of a plurality of second circuit electrodes on the interarea of second circuit substrate in first circuit member that forms a plurality of first circuit electrodes on the interarea of first circuit substrate, so that the state of first and second circuit electrode subtend and the circuit connection material that connects, contain binder composition, and the coated particle that is covered by insulating fine particles of the part surface of conducting particles, the quality of insulating fine particles be conducting particles quality 2/1000～26/1000.
Make this circuit connection material, be present between first and second circuit member, heat via first and second circuit member and pressurization, solidification treatment, obtain the connection structure of circuit member with in the structure that is connected of the circuit member that obtains, connection resistance between the circuit electrode of subtend is lowered fully, improves the insulativity between adjacent circuit electrode simultaneously fully.
At this, if the quality of insulating fine particles be lower than conducting particles quality 2/1000, then become can not the lining fully by insulating fine particles for conducting particles.Therefore, the insulativity between adjacent circuit electrode, that is become insufficient in the insulativity of the face direction of circuit substrate.On the one hand, if the quality of insulating fine particles surpass conducting particles quality 26/1000, then insulating fine particles becomes superfluous coated electroconductive particles.Therefore, even the circuit electrode of conducting particles connection subtend is mutual, also increase the connection resistance of the thickness direction of circuit substrate.
In addition, circuit connection material of the present invention is in order to form first circuit member of a plurality of first circuit electrodes on the interarea of first circuit substrate, with the second circuit member that on the interarea of second circuit substrate, forms a plurality of second circuit electrodes, so that the state of first and second circuit electrode subtend and the circuit connection material that connects, contain binder composition, and the part surface of conducting particles is by the sub coated particle that is covered of insulating fine particles, conducting particles is to have the nucleome that is made of macromolecular compound, and the quality of insulating fine particles is 7/1000～86/1000 of a nucleome quality.
Make this circuit connection material, be present between first and second circuit member, heat via first and second circuit member and pressurization, solidification treatment, obtain the connection structure of circuit member with in the structure that is connected of the circuit member that obtains, connection resistance between the circuit electrode of subtend is lowered fully, improves the insulativity between adjacent circuit electrode simultaneously fully.
At this, if the quality of insulating fine particles be lower than nucleome quality 7/1000, then conducting particles becomes and can not be covered fully by insulating fine particles.Therefore, the insulativity between adjacent circuit electrode, that is become insufficient in the insulativity of the face direction of circuit substrate.On the one hand, if the quality of insulating fine particles surpass nucleome quality 86/1000, then insulating fine particles becomes superfluous coated electroconductive particles.Therefore, mutual even conducting particles connects the circuit electrode of subtend, also increase the connection resistance on the thickness direction of circuit substrate.
In addition, circuit connection material of the present invention is in order and to form the second circuit member of a plurality of second circuit electrodes on the interarea of second circuit substrate in first circuit member that forms a plurality of first circuit electrodes on the interarea of first circuit substrate, the circuit connection material that connects in the mode of first and second circuit electrode subtend, contain binder composition, and the coated particle that is covered by insulating fine particles of the part surface of conducting particles, the proportion of coated particle be conducting particles proportion 97/100～99/100.
Make this circuit connection material, be present between first and second circuit member, heat via first and second circuit member and pressurization, solidification treatment, obtain the connection structure of circuit member with in the structure that is connected of the circuit member that obtains, connection resistance between the circuit electrode of subtend is lowered fully, improves the insulativity between adjacent circuit electrode simultaneously fully.
At this, if the proportion of coated particle be lower than conducting particles proportion 97/100, then insulating fine particles becomes superfluous coated electroconductive particles.Therefore, mutual even conducting particles connects the circuit electrode of subtend, also increase the connection resistance on the thickness direction of circuit substrate.On the one hand, if the proportion of coated particle surpass conducting particles proportion 99/100, then conducting particles becomes and can not be covered fully by insulating fine particles.Therefore, the insulativity between adjacent circuit electrode, that is become insufficient in the insulativity of the face direction of circuit substrate.
In addition, in coated particle, 5～60% of the surface of preferred conducting particles is covered by insulating fine particles.
If the surface of coated electroconductive particles is lower than 5%, then, conducting particles can not be covered fully by insulating fine particles because becoming, compared with quilt situation about being covered 5% or more on the surface, the interelectrode insulativity of adjacent circuit, that is become insufficient in the insulativity of the face direction of circuit substrate.On the one hand, if the surface of conducting particles is covered above 60%, then because the superfluous coated electroconductive particles of insulating fine particles, so even conducting particles connects between the circuit electrode of subtend, compared with in the situation of lining surface below 60%, increase the connection resistance on the thickness direction of circuit substrate.
In addition, the median size of preferred insulating fine particles be conducting particles median size 1/40～1/10.
As the median size of insulating fine particles in above-mentioned scope, compared with the situation that has broken away from this scope in median size, the surface of conducting particles becomes easy insulating fine particles by majority and is covered, make the connection structure of circuit member if use circuit connection material so, then can more improve the insulativity between adjacent circuit electrode, that is in the insulativity of the face direction of circuit substrate.
In addition, preferred insulating fine particles is that polymkeric substance by free-radical polymerised material constitutes.In this situation, because insulating fine particles becomes the surface that is attached to conducting particles easily, so make the connection structure of circuit member if use circuit connection material so, then can more improve the insulativity between adjacent circuit electrode, that is the insulativity on the face direction of circuit substrate.
In addition, binder composition preferably contains free-radical polymerised material and is produced the solidifying agent of free free radical by heating.By comprising so circuit connection material of binder composition, first and second circuit member is connected when heating easily.
In addition, foregoing circuit connects material and preferably also contains the film that is made of phenoxy group (phenoxy) resin and form material.Thus, circuit connection material can be machined to film like.In addition, circuit connection material be difficult to produce break, the broken or problem that is clamminess etc., become easy function circuit and connect material.
In addition, preferred phenoxy resin contains the molecular configuration that is derived from polycyclc aromatic compound at intramolecularly.Thus, can be at good circuit connection materials in aspect such as tackiness, intermiscibility, thermotolerance, physical strengths.
In addition, polycyclc aromatic compound is preferably fluorenes (Fluorene).
In addition, film-shaped circuit connection material of the present invention is circuit connection material of the present invention to be formed film like form.Thus, circuit connection material be difficult to produce break, the broken or problem that is clamminess etc., become easy function circuit and connect material.
In addition, the connection of circuit member of the present invention structure is to possess: in first circuit member that forms a plurality of first circuit electrodes on the interarea of first circuit substrate and in the second circuit member that forms a plurality of second circuit electrodes on the interarea of second circuit substrate, be arranged at first circuit substrate the interarea of interarea and second circuit substrate between and the connection that is connected the circuit member of the mutual circuit transom of first and second circuit member at the state that makes the mutual subtend of first and second circuit electrode construct; The circuit transom is that the cured article by circuit connection material of the present invention constitutes, and first circuit electrode and second circuit electrode are for being electrically connected via coated particle.
In the connection structure of circuit member so, can fully reduce the connection resistance between the circuit electrode of subtend, fully improve the insulativity between adjacent circuit electrode simultaneously.
In addition, in the situation of the volts DS that applies 50V between adjacent circuit electrode, the resistance value between preferred adjacent circuit electrode is 10 9More than the Ω.
As connection structure by circuit member so because when it moves the insulativity between adjacent circuit electrode, that is in the insulativity of the face direction of circuit substrate for very high, so become the short circuit that can fully prevent between adjacent circuit electrode.
In addition, at least one side IC chip (chip) preferably among first and second circuit member.
In addition, preferred first circuit electrode is below 1 Ω with the resistance that is connected between the second circuit electrode.Can fully reduce the connection resistance between the circuit electrode of subtend with the connection structure of circuit member so, that is the connection resistance of the thickness direction of circuit substrate.
In addition, for the connection structure of foregoing circuit member, preferably at least one side has the electrode surface layer that constitute to select at least a the group that constitutes from metal and indium tin oxide by gold and silver, tin, platinum family in first and second circuit electrode.
In addition, for the connection structure of foregoing circuit member, preferably at least one side has the substrate surface layer that constitute to select at least a in first and second circuit member from the group that is made of silicon nitride, silicon oxide compound and polyimide resin.Thus, compared with being situation about not constituting at the substrate surface layer, more improve the adhesion strength of circuit member and circuit transom with above-mentioned materials.
In addition, the manufacture method of the connection structure of circuit member of the present invention, possess: in first circuit member that forms a plurality of first circuit electrodes on the interarea of first circuit substrate with in forming on the interarea of second circuit substrate between the second circuit member of a plurality of second circuit electrodes, make first circuit electrode and second circuit electrode pair to state, make circuit connection material of the present invention be held the operation of existence; And by the heating and the pressurization circuit connection material make its solidified operation.
As use this manufacture method, can fully reduce the connection resistance between the circuit electrode of subtend, and, can get the connection structure of the circuit member that the insulativity between adjacent circuit electrode improves fully.
As by the present invention, can provide: in COG structure dress or COF structure dress, low-resistance electrical connection that can be stable between the circuit electrode of subtend, and, between the adjacent circuit electrode, can suppress the circuit connection material of short circuit production rate; Use this film-shaped circuit connection material; The connection structure and the manufacture method thereof of circuit member.
In addition, as by the present invention, can provide: though between adjacent circuit electrode that is bump pitch from narrow driving IC, the circuit connection material that connection reliability is also high; Use this film-shaped circuit connection material; The connection structure and the manufacture method thereof of circuit member.
Description of drawings
Fig. 1 is the sectional view of an embodiment of the connection structure of expression circuit member of the present invention.
Fig. 2 is the sectional view of an example that expression is used in the coated particle of circuit connection material of the present invention.
Fig. 3 is the sectional view of an embodiment of expression film-shaped circuit connection material of the present invention.
Fig. 4 is the sectional view of an operation of manufacture method of the connection structure of expression circuit member of the present invention.
Fig. 5 is the graphic representation of expression for the calibration curve (calibration curve) of the mass ratio A that obtains embodiments of the invention 1,2 and comparative example 2.
Fig. 6 is the graphic representation of expression for the calibration curve of the mass ratio B that obtains embodiments of the invention 1,2 and comparative example 2.
Fig. 7 is the graphic representation of expression for the calibration curve of the mass ratio A that obtains embodiments of the invention 3.
Fig. 8 is the graphic representation of expression for the calibration curve of the mass ratio B that obtains embodiments of the invention 3.
Fig. 9 is the coated particle C for embodiments of the invention 3, the pyrogram (pyrogram) that the result who measures by thermolysis gas chromatography (gas chromatography) obtains.Among the figure: 10: the connection structure of circuit member, 20: circuit member (first circuit member), 21: circuit substrate (first circuit substrate), 21a: interarea, 22: circuit electrode (first circuit electrode), 24,34: electrode surface layer, 30: circuit member (second circuit member), 31: circuit substrate (second circuit substrate), 31a: interarea, 32: circuit electrode (second circuit electrode), 35: the substrate surface layer, 50: coated particle, 51: conducting particles, 51x: nucleome, 51y: skin, 51a: surface, 52: insulating fine particles, 60: circuit transom, 61: film-shaped circuit connection material.
Embodiment
Embodiment
Below, circuit connection material of the present invention is described, uses the film-shaped circuit connection material of this material, the connection structure of circuit member and the embodiment of manufacture method thereof.And, in whole accompanying drawing, use prosign for same key element, the repetitive description thereof will be omitted.
(the 1st embodiment)
(the connection structure of circuit member)
Fig. 1 is the sectional view of the 1st embodiment of the connection structure (below, be called " connecting structure ") of expression circuit member of the present invention.The connection structure 10 of present embodiment possesses: the circuit member 20 (first circuit member) and the circuit member 30 (second circuit member) of mutual subtend between circuit member 20 and circuit member 30, are provided with the circuit transom 60 that connects these.
Circuit member 20 possesses: circuit substrate 21 (first circuit substrate) and be formed at a plurality of circuit electrodes 22 (first circuit electrode) on the interarea 21a of circuit substrate 21.A plurality of circuit electrodes 22 for example are configured to striated.On the other hand, circuit member 30 possesses: circuit substrate 31 (second circuit substrate), be formed at a plurality of circuit electrodes 32 (second circuit electrode) on the interarea 31a of circuit substrate 31.A plurality of circuit electrodes 32 also for example are configured to striated.
As the concrete example of circuit member 20,30, can enumerate: the substrate of the chip element of semi-conductor chip, resistive element chip or electric capacity chip etc. or printed base plate etc.Connection form as connecting structure 10 also has: being connected of IC chip and chip load board, connection that electric circuit is mutual, the IC chip adorned in COG structure dress or COF structure and glass substrate or with being connected of flexible band (Flexible Tape) etc.
Particularly, at least one side is the IC chip among the preferred circuit member 20,30.
Circuit electrode 22 is made of electrode part 23 on the interarea 21a that is formed at circuit substrate 21 and the electrode surface layer 24 that is formed on the electrode part 23; Circuit electrode 32 also is made of electrode part 33 on the interarea 31a that is formed at circuit substrate 31 and the electrode surface layer 34 that is formed on the electrode part 33.At this, preferred electrode upper layer 24,34 is respectively by metal or indium tin oxide (ITO) or these constituting more than two kinds of gold and silver, tin, platinum family.That is preferred circuit electrode 22,32 has metal or indium tin oxide (ITO) or these electrode surface layers that constitutes 24,34 more than two kinds of gold and silver, tin, platinum family respectively on electrode part 23,33.
Circuit member 30 has substrate surface layer 35 on circuit substrate 31 and circuit electrode 32.At this, substrate surface layer 35 preferably with silicon nitride, silicon oxide compound or polyimide resin or these more than two kinds combination and constitute.That is, preferred circuit member 30 have with silicon nitride, silicon oxide compound or polyimide resin or these more than two kinds combination and the substrate surface layer 35 that constitutes.Substrate surface layer 35 covers (coating) circuit substrate 31 and circuit electrode 32 or is attached to circuit substrate 31 and circuit electrode 32.By this substrate surface layer 35, improve the adhesion strength of circuit member 30 and circuit transom 60.
Particularly, circuit member 30 or circuit substrate 31 are the situation of flexible band (Flexible Tape), and preferable substrate upper layer 35 is made of the organic insulation material of polyimide resin etc.In addition, be the situation of glass substrate at circuit substrate 31, substrate surface layer 35 preferably with silicon nitride, silicon oxide compound, polyimide resin or silicone resin or these more than two kinds combination and constitute.
Circuit transom 60 is arranged between the interarea 31a of the interarea 21a of circuit substrate 21 and circuit substrate 31, so that the state junction circuit member 20,30 of circuit electrode 22,32 subtends is mutual.In addition, circuit transom 60 possesses insulating component 40 and coated particle 50.Coated particle 50 is used to be electrically connected circuit electrode 22 and circuit electrode 32, constitutes with insulating fine particles 52 of the part of the surperficial 51a of conducting particles 51 and coated electroconductive particles 51.In the present embodiment, the quality of insulating fine particles 52 be conducting particles 51 quality 2/1000～26/1000.
As constructing 10 by so connecting, the connection resistance that the circuit electrode of subtend is 22,32 reduces and stabilization fully, and the insulativity that simultaneously adjacent circuit electrode is 22,32 also fully improves.
If the quality of insulating fine particles 52 be lower than conducting particles 51 quality 2/1000, then become can not the fully lining by insulating fine particles 52 for conducting particles 51.Therefore, the insulativity that adjacent circuit electrode is 22,32, that is become insufficient in the insulativity of the face direction of circuit substrate 21,31.On the other hand, if the quality of insulating fine particles 52 surpass conducting particles 51 quality 26/1000, then insulating fine particles 52 becomes superfluous coated electroconductive particles 51.Therefore, even the circuit electrode 22,32 of conducting particles 51 connection subtends is mutual, also increase the connection resistance of the thickness direction of circuit substrate 21,31.
If be conceived to the insulativity of 22,32 of adjacent circuit electrodes, then in connecting structure 10, apply 22,32 of adjacent circuit electrodes under the situation of volts DS of 50V, the resistance value that preferred adjacent circuit electrode is 22,32 is 10 9More than the Ω.In so connecting structure 10 because when this moves the insulativity of 22,32 of adjacent circuit electrodes, that is very high in the insulativity of the face direction of circuit substrate 21,31, so become the short circuit that can prevent 22,32 of adjacent circuit electrodes fully.
If be conceived to the connection resistance of 22,32 of adjacent circuit electrodes, then in connecting structure 10, preferred circuit electrode 22 is below 1 Ω with the resistance that is connected between the circuit electrode 32.In so connecting structure 10, can fully reduce the connection resistance of 22,32 of the circuit electrodes of subtend, that is the connection resistance of the thickness direction of circuit substrate 21,31.
In addition, in coated particle 50, the median size d of preferred insulating fine particles 52 iMedian size d for conducting particles 51 c1/40～1/10.Median size d iAnd d cBe to measure major diameter respectively with the insulating fine particles of observing son 52 and conducting particles 51 by various microscopes for each particle more than 10, and the mean value of measured value.In addition, as the microscope that is used to observe, be suitable for using scanning electron microscope.
Median size d as insulating fine particles 52 iIn above-mentioned scope, than median size d iFor in this extraneous situation, the surperficial 51a of conducting particles 51 becomes easy insulating fine particles 52 by majority and covers, so connecting in the structure 10, can further improve the insulativity of 22,32 of adjacent circuit electrodes, that is the insulativity of the face direction of circuit substrate 21,31.
As conducting particles 51, can enumerate the metallics that constitutes by Au, Ag, Ni, Cu, scolding tin etc. or the particle that constitutes by carbon etc. etc.Conducting particles 51 is preferably the hot molten metal particle.In this situation, because heating by junction circuit electrode 22,32 each other time the and pressurization and conducting particles 51 easy deformation, so the contact area of conducting particles 51 and circuit electrode 22,32 increases, and connection reliability improves.
Insulating fine particles 52 preferably is made of the polymkeric substance of free-radical polymerised material.In this situation, because insulating fine particles 52 becomes the surperficial 51a that is attached to conducting particles 51 easily, so connecting in the structure 10, can further improve the insulativity of 22,32 of adjacent circuit electrodes, that is the insulativity of the face direction of circuit substrate 21,31.
Free-radical polymerised material is the material with polymeric functional group by free radical, can enumerate as so free-radical polymerised material: acrylate (acrylate) (also comprises corresponding methacrylic ester (methacrylate), below identical) compound, maleic anhydride imines (Maleimide) compound etc. that contracts.Free-radical polymerised material both can use with the state of monomer or oligomer, in addition, also can and use monomer and oligomer.
Concrete example as acrylic compound, can enumerate: methyl acrylate, ethyl propenoate, isopropyl acrylate, isobutyl acrylate, glycol diacrylate, diethylene glycol diacrylate, Viscoat 295 (trimethylolpropane triacrylate), tetramethylol methane tetraacrylate (tetramethylolmethane tetracrylate), 2-hydroxyl 1,3-two propylene acyloxy propane, 2, two (4-(acryloyl-oxy ylmethoxy) phenyl) propane of 2-, 2, two (4-(acryloxy polyethoxye) phenyl) propane of 2-, the dicyclopentenyl acrylate, tristane base acrylate, three (acryloxy ethyl) isocyanic ester (tris-(acryloyloxyethyl) isocyanuate), vinylformic acid urethane esters etc., these can separately or mix more than 2 kinds and use.In addition, also can use inhibitor of polymerizations such as Resorcinol (hydroquinone), methyl ether Resorcinol (methyl ether hydroquinone) class according to necessity, in addition, from the viewpoint that thermotolerance is improved, the preferred acrylate compound have from by dicyclopentenyl, tristane base (tricyclodecanyl), and the group that constitutes of triazine (triazine) ring at least 1 substituting group selecting.
Maleic anhydride contracts group with imine moiety for contain the contract compound of imido grpup of 2 above maleic anhydrides at least in molecule, as the group with imine moiety that contracts of maleic anhydride so, for example can enumerate: 1-methyl-2, the 4-span comes the acid anhydrides imines benzene that contracts, N, N '-m-phenylene span comes the acid anhydrides imines (phenylenebismaleimide) that contracts, N, N '-p-phenylene span comes the acid anhydrides imines (phenylene bismaleimide) that contracts, N, a N '-toluene span comes the acid anhydrides imines that contracts, N, N '-4,4-diphenylene span comes the acid anhydrides imines (biphenylene bismaleimide) that contracts, N, N '-4,4-(3,3 '-dimethyl diphenylene) span comes the acid anhydrides imines that contracts, N, N '-4,4-(3,3 '-dimethyl diphenylmethane) span comes the acid anhydrides imines that contracts, N, N '-4,4-(3,3 '-diethyl ditan) span comes the acid anhydrides imines that contracts, N, N '-4,4-ditan span comes the acid anhydrides imines that contracts, N, N '-4,4-diphenyl propane span comes the acid anhydrides imines that contracts, N, N '-3,3 '-phenylbenzene sulfo group span comes the acid anhydrides imines (diphenyl sulfon bismaleimide) that contracts, N, N '-4,4-phenyl ether span comes the acid anhydrides imines that contracts, 2,2-two (4-(4-maleic anhydride contract imines phenoxy group) phenyl) propane, 2, two (the 3-s-butyl-4 of 2-, 8-(4-maleic anhydride contract imines phenoxy group) phenyl) propane, 1,1-two (4-(4-maleic anhydride contract imines phenoxy group) phenyl) decane, 4,4 '-cyclohexylene (cyclohexylidene)-two (1-(4-maleic anhydride contract imines phenoxy group)-2-phenylcyclohexane, 2,2-two (4-(4-maleic anhydride contract imines phenoxy group) phenyl) HFC-236fa etc.These can separately or mix more than 2 kinds and use.
In addition, as shown in Figure 2, conducting particles 51 can have the surface of nucleome 51x and lining nucleome 51x and the outer 51y that forms.And Fig. 2 is the sectional view of an example of expression coated particle.The conducting particles 51 of conducting particles 51 to Fig. 2 that also can permutation graph 1.
Nucleome 51x is made of macromolecular compound, as this macromolecular compound, be suitable for using: the various rubber-like of various plastics classes, styrene butadiene rubbers or the silicone rubber etc. of polystyrene, polydivinylbenezene (polydivinyl benzene), polyacrylic ester, Resins, epoxy, phenol resins, benzo trimeric cyanamide (benzoguanamine) resin etc. etc.In addition, these as principal constituent, also can be used the various additives of linking agent, solidifying agent, age resister etc.In this situation, because heating by junction circuit electrode 22,32 each other time the and pressurization and conducting particles 51 easy deformation, so the contact area of conducting particles 51 and circuit electrode 22,32 increases, and connection reliability improves.
In the present embodiment, the quality of insulating fine particles 52 be nucleome 51x quality 7/1000～86/1000.If the quality of insulating fine particles 52 be lower than nucleome 51x quality 7/1000, then conducting particles 51 becomes and can not be covered fully by insulating fine particles 52.Therefore, the insulativity that adjacent circuit electrode is 22,32, that is the insulativity of the face direction of circuit substrate 21,31 becomes insufficient.On the one hand, if the quality of insulating fine particles 52 surpass nucleome 51x quality 86/1000, then insulating fine particles 52 becomes superfluous ground coated electroconductive particles 51.Therefore, even the circuit electrode 22,32 of conducting particles 51 connection subtends is mutual, also increase the connection resistance of the thickness direction of circuit substrate 21,31.
In addition, nucleome 51x also can be made of dielectric glass, pottery, plastics etc.Even situation for this reason, because heating by junction circuit electrode 22,32 each other time the and pressurization and conducting particles 51 easy deformation, so the contact area of conducting particles 51 and circuit electrode 22,32 increases, and connection reliability improves.In addition, preferred conducting particles 51 is formed with the outer 51y that is made of precious metal on the nucleome 51x surface that is made of dielectric glass, pottery, plastics etc.
Outer 51y does not preferably use the transition metal-type of Ni, Cu etc. to constitute, but is made of the precious metal of Au, Ag, platinum family etc. in order to obtain the sufficient serviceable time, more preferably is made of Au.In addition, the outer 51y lining that constitutes with precious metal of the conducting particles 51 nucleome 51x that also transition metal-type by Ni etc. can be constituted by Au etc.
The thickness of the outer 51y of precious metal is preferably more than 100 dusts (Angstrom).In this situation, at 22,32 connection resistance that can get well of circuit electrode.In addition, the surface of the nucleome 51x that constitutes at the transition metal by Ni etc. forms the situation of the outer 51y of precious metal, and the thickness of the outer 51y of precious metal is preferably more than 300 dusts.If the thickness of the outer 51y of precious metal is lower than 300 dusts, then for example when blending dispersion conducting particles 51, produce damaged etc. at outer 51y.Producing the situation of this defective etc., produce free free radical, the doubt that has the keeping quality that makes circuit connection material to descend based on redoxomorphism.Then, because to the thickness thickening of outer 51y and the effect of outer 51y is saturated gradually, so the thickness of outer 51y is preferably below 1 micron (micrometer).
And, the quality of insulating fine particles 52 is with respect to the value of the ratio (mass ratio A) of the quality of conducting particles 51 of the present invention, and the quality of insulating fine particles 52 is used the value of measuring by the thermolysis gas chromatography with respect to the value of the ratio (mass ratio B) of the quality of nucleome 51x.The thermolysis gas chromatography, the composition of the known qualitative analysis that is used in various plastics or elastomeric material and those multipolymers or mixing (blend) thing quantitatively waits (reference, Han Chuan likes that three youths, Da Li directly firmly write, " the thermolysis gas chromatography is crossed the threshold ", P121～P176, a skill newspaper hall publishing company).
Discoveries such as the inventor as the method for quality measurement than the value of A and mass ratio B, have been used the result of thermolysis gas chromatography, can get quantitative property well.Therefore, in the present invention, the value of mass ratio A and mass ratio B is used the value of obtaining by the calibration curve of thermolysis gas chromatography.At this moment, the calibration curve that is used, be not limited to conducting particles 51 identical materials, with nucleome 51x identical materials or the calibration curve that makes with insulating fine particles son 52 identical materials, also can be the polymkeric substance of the plastics class that substitutes same kind, rubber-like, radical polymerization syzygy material and the calibration curve that makes.
The peak value (peak) of the thermolysis gas chromatography that uses in the mensuration of the value of mass ratio A and mass ratio B is not particularly limited, and can use the peak value from the thermolysis composition of conducting particles 51, nucleome 51x and insulating fine particles 52.Among these thermolysis compositions, if use to constitute the peak value of thermolysis composition of the main monomer of plastics class, rubber-like, free-radical polymerised material, then because the quantitative property raising of the value of mass ratio A and mass ratio B but ideal.
(circuit connection material)
Foregoing circuit transom 60 is made of the cured article of circuit connection material.At this, describe for circuit connection material.This circuit connection material contains coated particle and binder composition.In addition, as described later, circuit connection material also can further contain film formation material, other contains to become to grade.
＜coated particle 〉
The formation that is contained in the coated particle in the circuit connection material constitutes identical with above-mentioned coated particle 50.Constitute the conducting particles 51 of coated particle 50, preferably add 0.1～30 parts by volume with respect to binder composition 100 parts by volume, its addition uses according to purposes.And, in order to prevent based on the short circuit of the adjacent circuit electrode of the conducting particles 51 of surplus etc., preferably make conducting particles 51 add 0.1～10 parts by volume.
＜binder composition 〉
Binder composition preferably contains free-radical polymerised material and produces the solidifying agent of free free radical by heating.By containing so circuit connection material of binder composition, circuit member 20,30 is connected when heating easily.
As free-radical polymerised material, but illustration and the identical material of free-radical polymerised material that is used in insulating fine particles 52.Free-radical polymerised material can use with the state of monomer or oligomer, in addition, also can and with monomer or oligomer.
Produce the solidifying agent of free free radical by heating, for producing the solidifying agent of free free radical by thermal degradation,, can enumerate: peralcohol, azo based compound etc. as solidifying agent so.Solidifying agent so connects temperature, tie-time, serviceable time (pot life) by purpose and waits and suit to select.Wherein, reactive from improving, as to make serviceable time raising viewpoint, the temperature of preferred 10 hours transformation period is more than 40 ℃ and the temperature of 1 minute transformation period is a organo-peroxide below 180 ℃, and more preferably the temperature of 10 hours transformation period is more than 60 ℃ and the temperature of 1 minute transformation period is a organo-peroxide below 170 ℃.
The use level of solidifying agent, in the tie-time is situation below 10 seconds, in order to obtain sufficient reactivity, with respect to free-radical polymerised material and as required and the film that cooperates forms material and 100 weight parts, be preferably 0.1～30 weight part, 1～20 weight part more preferably.
The use level of solidifying agent can not obtain sufficient reactivity under the situation that is lower than 0.1 weight part, exist to become the tendency that is difficult to obtain good adhesion strength or little connection resistance.If the use level of solidifying agent surpasses 30 weight parts, then the flowability of binder composition descends, connects the tendency that serviceable time (pot life) that resistance rises, exists binder composition shortens.
More particularly, as the solidifying agent that produces free free radical by heating, can enumerate: diacyl peroxide, peroxy dicarbonate, peroxyester, ketal peroxide, dialkyl peroxide, hydroperoxide, silylation superoxide etc.In addition, by the corrosive viewpoint that suppresses circuit electrode 22,32, solidifying agent is preferably the chlorion that contains in the solidifying agent or organic acid concentration below 5000ppm, and the few solidifying agent of the organic acid that more preferably produces after thermal degradation.So solidifying agent specifically, is selected from peroxyester, dialkyl peroxide, hydroperoxide, silylation superoxide, preferably can get the peroxyester of hyperergy.Above-mentioned solidifying agent can suit to mix and use.
As diacyl peroxide; can enumerate: isobutyl peroxide, 2; 4-dichloro-benzoyl superoxide, 3; 5,5-trimethyl acetyl base superoxide, sim peroxides, lauroyl superoxide, stearyl-superoxide, succinyl superoxide (succinic peroxide), benzoyl peroxidation toluene, benzoyl peroxide.
As peroxy dicarbonate, can enumerate: two-n-propyl group peroxy dicarbonate, diisopropyl peroxydicarbonate, two (4-t-butyl cyclohexyl) peroxy dicarbonate, two-2-oxyethyl group methoxy base peroxy dicarbonate, two (peroxidation of 2-ethylhexyl), two carbonic ethers, dimethoxy butyl peroxyization two carbonic ethers, two (3-methyl-3 methoxyl group butyl peroxyization) two carbonic ethers etc.
As peroxyester; can enumerate: the cumyl new decanoate ester peroxide; 1; 1; 3; 3-tetramethyl butyl new decanoate ester peroxide; 1-cyclohexyl-1-methylethyl new decanoate ester peroxide; t-hexyl new decanoate ester peroxide; t-butyl peroxy propionic ester; 1; 1; 3; 3-tetramethyl butyl peroxidation-2-ethylhexanoate; 2; 5-dimethyl-2; 5-two (peroxidation of 2-ethyl hexanoyl base) hexane; 1-cyclohexyl-1-methylethyl peroxidation-2-ethylhexanoate; t-hexyl peroxidation-2-ethylhexanoate; t-butyl peroxyization-2-ethylhexanoate; t-butyl peroxy isobutyrate; 1; two (t-butyl peroxyization) hexanaphthenes of 1-; t-hexyl peroxidation sec.-propyl list carbonate; t-butyl peroxyization-3; 5; 5-tri-methyl hexanoic acid ester; t-butyl peroxy laurate; 2; 5-dimethyl-2,5-two (peroxidation of m-toluyl) hexane; t-butyl peroxy sec.-propyl monocarbonate; t-butyl peroxyization-2-ethylhexyl monocarbonate; t-hexyl peroxide benzoate; t-butyl peroxy acetic ester etc.
As ketal peroxide, can enumerate: 1, two (peroxidation of t-hexyl)-3,3 of 1-, 5-trimethyl-cyclohexane, 1, two (peroxidation of the t-hexyl) hexanaphthenes, 1 of 1-, two (the t-butyl peroxyization)-3,3 of 1-, 5-trimethyl-cyclohexane, 1,1-(t-butyl peroxyization) cyclododecane, 2, two (t-butyl peroxyization) decane of 2-etc.
As dialkyl peroxide, can enumerate: α, α '-two (t-butyl peroxyization) diisobutyl benzene, dicumyl peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxyization) hexane, t-butyl cumyl peroxide etc.
As hydroperoxide, can enumerate: diisopropyl benzene hydroperoxide, cumene hydroperoxide etc.
As the silylation superoxide, can enumerate: t-butyl TMS superoxide, two (t-butyl) dimethylsilyl superoxide, t-butyl trivinyl silylation superoxide, two (t-butyl) divinyl silylation superoxide, three (t-butyl) vinyl silanes base superoxide, t-butyl triallyl silylation superoxide, two (t-butyl) diallylsilane base superoxide, three (t-butyl) allyl silicane base superoxide.
These solidifying agent can separately or mix more than 2 kinds and use, also can mixed decomposition promotor, inhibitor etc. and using.In addition, with this solidifying agent with lining such as the polymer substance of polyurethane series, polyester system micro encapsulation because prolong the serviceable time but ideal.
In addition, above-mentioned circuit connection material preferably further contains the film that is made of phenoxy resin and forms material.Thus, becoming processing circuit connection material to be film like, can get film-shaped circuit connection material.
Fig. 3 is the sectional view of the 1st embodiment of expression film-shaped circuit connection material of the present invention.The film-shaped circuit connection material 61 of present embodiment possesses: the film like insulating component 41 and the coated particle 50 that are made of above-mentioned binder composition.This film-shaped circuit connection material 61 is to be formed up to film like with above-mentioned circuit connection material to form.
Form material if circuit connection material contains film, then circuit connection material be difficult to produce break, the broken or problem that is clamminess etc., become easy function circuit at common state (normal temperature and pressure) and connect material.In addition, film-shaped circuit connection material 61, if cut apart the layer and more than 2 layers of layer that contain coated particle 50 that produces the solidifying agent of free free radical by heating to containing, then the serviceable time improves.
＜film forms material 〉
So-called film forms material, be meant in solid shape fraction and will constitute the situation of composition as film shape, make the processing ease of this film, give be not easy to break, the material of broken, the mechanical characteristics that is clamminess etc., also be meant the material that can operate as film down at common state (normal temperature and pressure).Form material as film, can enumerate: phenoxy resin, polyvinyl methylal (polyvinyl formal) resin, polystyrene resin, polyvinyl butyral resin, vibrin, polymeric amide (Polyamide) resin, dimethylbenzene (xylene) resin, urethane resin etc.Wherein, from tackiness, intermiscibility, thermotolerance, the good angle of physical strength, preferred phenoxy resin.
Phenoxy resin be instigate 2 officials can phenols and epihalohydrins (epihalohydrin) react to high molecular, or make 2 officials can Resins, epoxy and 2 officials can phenols addition polymerization (polyaddition) and the resin that obtains.Phenoxy resin can be by for example: can 1 mole of phenols and 0.985～1.015 mole of Epicholorohydrin with 2 officials, and in the presence of the catalyzer of alkali metal hydroxide etc., in non-reactive solvent, 40～120 ℃ temperature makes its reaction and get.In addition, as phenoxy resin, from the characteristic of the machinery of resin or the viewpoint of thermal property, especially preferably 2 functionality Resins, epoxy are made as epoxy group(ing)/phenol hydroxy=1/0.9～1/1.1 with the equivalence ratio that cooperates of 2 functionality phenols, be in the organic solvent of acid amides system, ether system, ketone system, lactone system, alcohol system etc. more than 120 ℃ in the presence of the catalyzer of alkali metal compound, organophosphorus based compound, cyclic amine based compound etc., at boiling point, and be divided into condition below 50 weight parts and be heated to 50～200 ℃ and make its addition polymerization and obtain to react solid shape.
As 2 officials energy Resins, epoxy, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, bisphenol-s epoxy resin etc.2 officials can phenols be the phenols with 2 phenol hydroxys, can phenols as 2 officials so, for example can enumerate: the bisphenols of dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S etc. etc.
In addition, phenoxy resin preferably contains at its intramolecularly and results from the molecular configuration of polycyclc aromatic compound.Thus, can be at good circuit connection materials in aspect such as tackiness, intermiscibility, thermotolerance, physical strengths.
As polycyclc aromatic compound, for example can enumerate: the dihydroxy compound of naphthalene (Naphthalene), biphenyl, acenaphthene (Acenaphthene), fluorenes, diphenylene-oxide, anthracene, phenanthrene etc. etc.At this, polycyclc aromatic compound is preferably fluorenes.And polycyclc aromatic compound is preferably 9,9 '-two (4-hydroxyphenyl) fluorenes especially.
And phenoxy resin also can the modification by free-radical polymerised functional group.In addition, phenoxy resin can use separately, also can mix more than 2 kinds and use.
＜other contain composition
The circuit connection material of present embodiment can also further comprise selects at least a polymkeric substance or multipolymer as monomer component in the group that will be made of vinylformic acid, acrylate, methacrylic ester and vinyl cyanide.Relax good angle at this from stress, preferred and with comprising the epihydric alcohol acrylic ester that contains glycidyl ether or the copolymerization system acrylic rubber of epihydric alcohol methylpropenoic acid ester.The molecular weight of these acrylic rubbers (weight-average molecular weight) from improving the cohesive force viewpoint of tackiness agent, is preferably more than 200,000.
In addition, also can in the circuit connection material of present embodiment, further contain weighting agent, tenderizer, promotor, age resister, fire retardant, pigment, thixotroping (thixotropic) agent, coupler, phenol resins, melamine resin, isocyanates etc.
Containing in circuit connection material under the situation of weighting agent, owing to improve connection reliability etc., is ideal therefore.For weighting agent,, then can use its maximum diameter as long as being lower than the median size of conducting particles 51.The use level of weighting agent is preferably 5～60 parts by volume with respect to binder composition 100 parts by volume.If use level surpasses 60 parts by volume, then there is connection reliability to improve the saturated tendency of effect, on the other hand, become inadequate tendency in the effect that is lower than 5 parts by volume and has weighting agent to add.
As coupler, for the compound that contains ketoimine (ketimine), vinyl, propenyl, amino, epoxy group(ing) or isocyanate group, because can improve tackiness thereby be ideal.
Concrete conduct has amino silane coupling agent, can enumerate: N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) gamma-amino propyl group methyl dimethoxysilane, γ-An Jibingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane etc.As silane coupling agent, can enumerate: the material that the ketone compound that makes acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc. must obtain with the silane coupling agent reaction with above-mentioned amino with ketoimine.
Then, about the manufacture method of above-mentioned connection structure 10, use Fig. 1, Fig. 3 and Fig. 4 and illustrate.Sectional view, Fig. 4 that Fig. 3 is illustrated in the film-shaped circuit connection material that uses in the manufacturing that connects structure 10 is the sectional view of an operation of the expression manufacture method that connects structure 10.
(manufacture method of the connection structure of circuit member)
At first, prepare circuit member 20,30.On the other hand, prepare to be configured as the film-shaped circuit connection material 61 (with reference to Fig. 3) that film like forms.Then, between circuit member 20 and circuit member 30, make above-mentioned circuit connection material is configured as the film-shaped circuit connection material 61 clampings existence that film like forms.That is, between circuit member 20 and circuit member 30, be the state of subtend with circuit electrode 32 at circuit electrode 22, film-shaped circuit connection material 61 clampings are existed.Particularly, for example: mounting film-shaped circuit connection material 61 on circuit member 30, then upload circuits member 20 at film-shaped circuit connection material 61.At this moment, make circuit electrode 22 and circuit electrode 32 mutually relatively, configuration circuit member 20 and circuit member 30.At this, because film-shaped circuit connection material 61 is film like operation easily.Therefore, can make film-shaped circuit connection material 61 clampings be present in 20,30 of circuit members easily, the connection operation of circuit member 20,30 is become easily.
Then, via circuit member 20,30 heating film-shaped circuit connection material 61, simultaneously implement solidification treatment (with reference to Fig. 4) in the arrow A of Fig. 4 and the heating of B direction and pressurization, form circuit transom 60 (with reference to Fig. 1) 20,30 of circuit members.Solidification treatment is for being undertaken by general method, and its method is the selection suitable by binder composition.And, also can be in heating and when pressurization, by either party's side of circuit member 20,30, irradiates light and carry out the location of circuit electrode 22,32.
If make to connect structure 10 in this way, then can get and fully reduce and the connection resistance of 22,32 of the circuit electrodes of stabilization subtend, fully improve the connection structure 10 of the insulativity of 22,32 at adjacent circuit electrode simultaneously.
(the 2nd embodiment)
(the connection structure of circuit member)
The connection structure 10 of present embodiment possesses: the circuit member 20 (first circuit member) and the circuit member 30 (second circuit member) of mutual subtend between circuit member 20 and circuit member 30, are provided with the circuit transom 60 that connects these.
Circuit member 20,30 has and the 1st embodiment identical construction, and preferably is made of identical materials.
Circuit transom 60 is arranged between the interarea 31a of the interarea 21a of circuit substrate 21 and circuit substrate 31, and is mutual with circuit electrode 22,32 subtends ground junction circuit member 20,30.In addition, circuit transom 60 possesses: the part of the surperficial 51a of insulating component 40, conducting particles 51 is by the coated particle 50 of insulating fine particles 52 linings.In the present embodiment, the proportion of coated particle 50 is 97/100～99/100 of the proportion of conducting particles 51.Through coated particle 50 thus, be electrically connected circuit electrode 22 and circuit electrode 32.
At this, circuit transom 60, because the cured article by circuit connection material described later constitutes, thus in connecting structure 10, can reduce fully 22,32 of the circuit electrodes of subtend connection resistance, also fully improve the insulativity of 22,32 at adjacent circuit electrode simultaneously.
(circuit connection material)
The circuit connection material of present embodiment contains binder composition and coated particle 50.If this circuit connection material is present between the circuit member 20,30, heating and pressurization via circuit member 20,30, solidification treatment, construct 10 and obtain connecting, then in the connection that obtains structure 10, reduce the connection resistance of 22,32 of the circuit electrodes of subtend fully, fully improve the insulativity of 22,32 at adjacent circuit electrode simultaneously.
＜binder composition 〉
As binder composition, but illustration with at the identical material of the binder composition of the 1st embodiment.
＜coated particle 〉
The coated particle that coated particle 50 is covered by insulating fine particles 52 for the part of the surperficial 51a of conducting particles 51.The proportion of the coated particle 50 of present embodiment be conducting particles 51 proportion 97/100～99/100.
If the proportion of coated particle 50 be lower than conducting particles 51 proportion 97/100, then insulating fine particles 52 becomes superfluous ground coated electroconductive particles 51.Therefore, even conducting particles 51 is that to connect the circuit electrode 22,32 of subtend mutual, also increase the connection resistance of the thickness direction of circuit substrate 21,31.On the other hand, if the proportion of coated particle 50 surpass conducting particles 51 proportion 99/100, then conducting particles 51 becomes and can not be covered fully by insulating fine particles 52.Therefore, the insulativity that adjacent circuit electrode is 22,32, that is the insulativity of the face direction of circuit substrate 21,31 becomes insufficient.
In addition, in coated particle 50,5～60% of the surperficial 51a of preferred conducting particles 51 is covered by insulating fine particles 52.
If the surperficial 51a of coated electroconductive particles 51 is lower than 5%, then, conducting particles 51 can not be covered fully by insulating fine particles 52 because becoming, compared with at surperficial 51a being situation about being covered more than 5%, the insulativity that the adjacent circuit electrode is 22,32, that is the insulativity of the face direction of circuit substrate 21,31 becomes insufficient.On the other hand, if the surperficial 51a of conducting particles 51 is covered above 60%, then because insulating fine particles 52 superfluous ground coated electroconductive particles 51, so even conducting particles 51 connects 22,32 of the circuit electrodes of subtends, compared with being situation 60% below at the surperficial 51a of lining, the connection resistance of the thickness direction of increase circuit substrate 21,31.
Conducting particles 51 and insulating fine particles 52 preferably have and the 1st embodiment identical construction, and are made of identical materials.
＜film forms material 〉
The circuit connection material of present embodiment preferably further contains with film at the 1st embodiment and forms the identical film formation material of material.Thus, become and to connect material to film like by processing circuit, can get film-shaped circuit connection material.
＜other contain composition
The circuit connection material of present embodiment further preferably contains and contains the identical material of composition at other of the 1st embodiment.
(manufacture method of the connection structure of circuit member)
As the manufacture method of the connection structure of the circuit member of present embodiment preferably with the identical method of manufacture method at the connection structure of the circuit member of the 1st embodiment.
More than, explain preferred embodiment of the present inventionly, and the present invention is not limited to the respective embodiments described above.
For example: in the above-mentioned the 1st and the 2nd embodiment, in connecting structure 10, also can electrode surface layer 24,34 all be arranged circuit electrode 22,32, and the either party of circuit electrode 22,32 has the electrode surface layer.In addition, can all there be the electrode surface layer by circuit electrode 22,32 yet.That is, in the above-mentioned the 1st and the 2nd embodiment, also can all have electrode surface layer 24,34 by circuit electrode 22,32, and at least one side there is the electrode surface layer among the circuit electrode 22,32.
In addition, in the above-mentioned the 1st and the 2nd embodiment, the circuit member 30 that also can connect structure 10 has substrate surface layer 35, and only circuit member 20 has the substrate surface layer.In addition, also can all have the substrate surface layer by circuit member 20,30.And circuit member 20,30 does not have the substrate surface layer.That is, in the above-mentioned the 1st and the 2nd embodiment, also can have substrate surface layer 35 by circuit member 30, and at least one side has the substrate surface layer among the circuit member 20,30.
In addition, in the above-mentioned the 1st and the 2nd embodiment, use film-shaped circuit connection material 61 and manufacturing connection structure 10, also can be not limited to film-shaped circuit connection material 61, use not comprise the circuit connection material that film forms material.Even in this situation, make circuit connection material be dissolved in solvent, as its solution coat is made its drying in circuit member 20,30 either party, can make the circuit connection material clamping be present in 20,30 of circuit members.
In addition, in the above-mentioned the 1st and the 2nd embodiment, circuit connection material contains conducting particles 51, also can not contain conducting particles 51.Even in this case, also the circuit electrode by subtend 22,32 each directly contact obtain being electrically connected.And, under the situation that contains conducting particles 51,, can connect than stable electrical compared with the situation that does not contain conducting particles 51.
Embodiment
Below, use embodiment that content of the present invention is described more specifically, and the present invention is not defined to these embodiment.
(embodiment 1)
(1) making of coated particle
At first, surface at the crosslinked polystyrene particle (PSt) of median size 5 μ m, with electroless plating the nickel dam of thickness 0.2 μ m is set, and, obtains being equivalent to the plated film plastic pellet (PSt-M) of conducting particles 51 by gold layer at the arranged outside thickness 0.04 μ m of this nickel dam.Some with the surface of this plated film plastic pellet, by being equivalent to the Polymerization of Methyl thing of insulating fine particles 52, that is be covered by polymethylmethacrylate (PMMA), obtain coated particle A with the median size 5.2 μ m of the insulating fine particles lining of median size 0.2 μ m.Coated particle A is 20% being covered of surface of conducting particles, serves as that 98/100 mode of the proportion before the lining is covered with the proportion after the lining.And median size is the value from the measured value that obtains calculated based on retouching the observation of sweeping the type electron microscope.
(2) the thermolysis gas chromatography is measured
At first, to carry out the thermolysis gas chromatography about the calibration curve of mass ratio A (quality of insulating fine particles is to the ratio of the quality of conducting particles) and measure in order to make.In measurement result, the peak value (peak) as the thermolysis composition of plated film plastic pellet (PSt-M) has used cinnamic peak value (peak) area I StIn addition, as the peak value (peak) of the thermolysis composition of polymethylmethacrylate (PMMA), used the peak area I of methyl methacrylate (MMA) MMACalculated peak area than (I by these MMA/ I St).
In addition, the quality W of plated film plastic pellet (PSt-M) PST-MThe quality that is equivalent to conducting particles 51, the quality W of polymethylmethacrylate (PMMA) PMMAThe quality that is equivalent to insulating fine particles 52.Calculated mass ratio A (W thus PMMA/ W PST-M).Then, about peak area than (I MMA/ I St) and mass ratio A (W PMMA/ W PST-M) relation, made the calibration curve that is shown in Fig. 5.The calibration curve of Fig. 5 has good rectilinearity.
Then, to carry out the thermolysis gas chromatography about the calibration curve of mass ratio B (quality of insulating fine particles is to the ratio of the quality of nucleome) and measure in order to make.In measurement result, the peak value (peak) as the thermolysis composition of crosslinked polystyrene particle (PSt) has used cinnamic peak value (peak) area I StIn addition, as polymethylmethacrylate (P MMA) the peak value (peak) of thermolysis composition, used the peak area I of methyl methacrylate (MMA) MMACalculated peak area than (I by these MMA/ I St).
In addition, the quality W of polymethylmethacrylate (PMMA) PMMAThe quality that is equivalent to insulating fine particles 52, the quality W of crosslinked polystyrene particle (PSt) PStThe quality that is equivalent to nucleome 51x.Calculated mass ratio B (W by these PMMA/ W PSt).Then, about peak area than (I MMA/ I St) and mass ratio B (W PMMA/ W PSt) relation, made the calibration curve that is shown in Fig. 6.The calibration curve of Fig. 6 has good rectilinearity.
Then,, carry out the thermolysis gas chromatography with the condition determination that is shown in table 1 and measure, calculated peak area than (I about coated particle A MMA/ I St).Then, according to this peak area ratio, calculate the result of mass ratio A by the calibration curve of Fig. 5, mass ratio A is 9/1000, calculates the result of mass ratio B by the calibration curve of Fig. 6, and mass ratio B was 29/1000 (with reference to table 2).
(table 1)
Pattern or condition determination
Thermal decomposer Japan's analytical industry corporate system Curie temperature thermo-cracking instrument-JHP-5 type
Gas chromatograph Agilent corporate system 6890N type
Detector Flame ionization ditector
Chromatography column Agilent corporate system capillary chromatography post HP-5MS (internal diameter 0.25mm, long 30m)
Chromatography column intensification condition By 50 ℃ to 300 ℃, after 10 ℃ of intensifications of per minute, kept 10 minutes
Carrier gas Helium (flow 1ml/ branch in the chromatography column)
Injection method Shunting injection method (splitting ratio 50: 1)
(table 2)
Embodiment 1 (coated particle A) Embodiment 2 (coated particle B) Embodiment 3 (coated particle C) Comparative example 1 (conducting particles) Comparative example 2 (coated particle E)
Mass ratio A 9/1000 18/1000 11/1000 0/1000 30/1000
Mass ratio B 29/1000 58/1000 34/1000 0/1000 101/1000
(3) making of circuit connection material
At first, shifting (glasstransition) temperature by bisphenol A type epoxy resin and dihydroxyphenyl propane (bisphenol A) synthetic glass is 80 ℃ phenoxy resin.With this phenoxy resin 50g, being dissolved in weight ratio is the mixed solvent of toluene (110.6 ℃ of boiling points, SP value 8.90)/ethyl acetate (77.1 ℃ of boiling points, SP value 9.10)=50/50, divides the solution of 40 weight % as solid shape.Then, being adjusted into solid shape branch weight ratio is the solution of phenoxy resin 60g, dicyclopentenyl omega-diol diacrylate (dicyclopentenyldialcoholdiacrylate) 39g, phosphoric acid ester (phosphate) type acrylate 1g, uncle's hexyl peroxidation-2-ethylhexanoate (t-hexyl peroxy-2-ethyl hexanonate) 5g.
Then, coated particle A being cooperated disperses 5 volume % to adjust solution in above-mentioned solution.Then,, use apparatus for coating and coat PET (polyethylene terephthalate) film of the thickness 80 μ m of the one side of surface treatment,, on the PET film, obtain the 1st film like material of thickness 10 μ m by 70 ℃, 10 minutes warm air drying with this solution.
In addition, being adjusted into solid shape branch weight ratio is other solution of phenoxy resin 60g, dicyclopentenyl omega-diol diacrylate 39g, phosphoric acid ester (phosphate) type acrylate 1g, uncle's hexyl peroxidation-2-ethylhexanoate 5g.With this solution, use apparatus for coating and coat PET (polyethylene terephthalate) film of the thickness 80 μ m of the one side of surface treatment, by 70 ℃, 10 minutes warm air drying, on the PET film, obtain the 2nd film like material that constitutes by the sticking agent composition of thickness 10 μ m.
The 1st above-mentioned film like material and the 2nd film like material is bonding with laminating machine (Laminater), obtain the film-shaped circuit connection material of two layers of formation.
(4) making of the connection of circuit member structure
At first, as first circuit member, prepared to have disposed the IC chip of the golden projection of projection area 50 μ m * 50 μ m, spacing 100 μ m, height 20 μ m.Then, as the second circuit member, be ready for the circuit of evaporation indium tin oxide (ITO) on the glass substrate of thickness 1.1mm and the ito substrate that forms (surface resistivity＜20 Ω/).
Then, above-mentioned film-shaped circuit connection material clamping is present between IC chip and the ito substrate, IC chip, film-shaped circuit connection material and ito substrate is seized on both sides by the arms with silica glass and polishing head, with 200 ℃, 100MPa heats for 10 seconds and pressurize.So effect connects IC chip and ito substrate via film-shaped circuit connection material.At this moment, on ito substrate in advance with a side's of film-shaped circuit connection material bonding plane with 70 ℃, 0.5MPa heats for 5 seconds and pressurize and be stained with.Afterwards, peel off the PET film, the opposing party's of film-shaped circuit connection material bonding plane is connected with the IC chip.By as upper type, make the connection structure A of circuit member.
(embodiment 2)
(1) making of coated particle
At first, surface in the crosslinked polystyrene particle of median size 5 μ m, with electroless plating the nickel dam of thickness 0.2 μ m is set, and passes through to obtain being equivalent to the plated film plastic pellet (PSt-M) of conducting particles 51 in the gold layer of the arranged outside thickness 0.04 μ m of this nickel dam.Some with the surface of this plated film plastic pellet is covered by the polymethylmethacrylate (PMMA) that is equivalent to insulating fine particles 52, obtains the coated particle B with the median size 5.2 μ m of the insulating fine particles lining of median size 0.2 μ m.Coated particle B is 40% being covered of surface of conducting particles, serves as the mode of the proportion 97/100 before the lining with the proportion after the lining, by insulating fine particles by coated electroconductive particles.And median size is the value from the measured value that obtains calculated based on retouching the observation of sweeping the type electron microscope.Measure similarly to Example 1 about the lining rate in addition.
(2) the thermolysis gas chromatography is measured
About coated particle B, carry out the thermolysis gas chromatography with the condition determination that is shown in table 1 and measure.Calculate the result of mass ratio A by the calibration curve of Fig. 5, mass ratio A is 18/1000, calculates the result of mass ratio B by the calibration curve of Fig. 6, and mass ratio B was 58/1000 (with reference to table 2).
(3) making of circuit connection material
At first, by bisphenol A type epoxy resin and 9,9 '-two (4-hydroxyphenyl) fluorenes, the synthetic glass tansition temperature is 80 ℃ a phenoxy resin.With this phenoxy resin 50g, being dissolved in weight ratio is the mixed solvent of toluene (110.6 ℃ of boiling points, SP value 8.90)/ethyl acetate (77.1 ℃ of boiling points, SP value 9.10)=50/50, divides the solution of 40 weight % as solid shape.Then, being adjusted into solid shape branch weight ratio is the solution of phenoxy resin 60g, dicyclopentenyl omega-diol diacrylate 39g, phosphate type acrylate 1g, uncle's hexyl peroxidation-2-ethylhexanoate 5g.
Then, coated particle B being cooperated disperses 5 volume % to adjust solution in above-mentioned solution.Then,, use apparatus for coating and coat PET (polyethylene terephthalate) film of the thickness 80 μ m of the one side of surface treatment,, on the PET film, obtain the 1st film like material of thickness 10 μ m by 70 ℃, 10 minutes warm air drying with this solution.
In addition, being adjusted into solid shape branch weight ratio is other solution of phenoxy resin 60g, dicyclopentenyl omega-diol diacrylate 39g, phosphate type acrylate 1g, uncle's hexyl peroxidation-2-ethylhexanoate 5g.With this solution, use apparatus for coating and coat PET (polyethylene terephthalate) film of the thickness 80 μ m of the one side of surface treatment, by 70 ℃, 10 minutes warm air drying, on the PET film, obtain the 2nd film like material that constitutes by binder composition of thickness 10 μ m.
The 1st above-mentioned film like material and the 2nd film like material is bonding with laminating machine, obtain the film-shaped circuit connection material of two layers of formation.
(4) making of the connection of circuit member structure
Use above-mentioned film-shaped circuit connection material, identical with embodiment 1 and make the connection structure B of circuit member.
(embodiment 3)
(1) making of coated particle
As coated particle C, use the AUL-704GD of ponding chemical company system.The nucleome 51x of coated particle C is made of the plastics of polyacrylic ester system, and the median size of conducting particles 51 is 4 μ m.Insulating fine particles 52 is made of polymethylmethacrylate (PMMA), and its median size is 0.2 μ m.
(2) the thermolysis gas chromatography is measured
At first, to carry out the thermolysis gas chromatography about the calibration curve of mass ratio A and measure in order to make.When measuring, the conducting particles 51 of the nucleome 51y that constitutes as the plastics that have by polyacrylic ester system has used the AUL-704 (PAc-M) of ponding chemical company system.
In measurement result,, use peak value (peak) the area I of polyacrylic ester (Ac) as the peak value (peak) of the thermolysis composition of AUL-704 (PAc-M) AcIn addition, as the peak value of the thermolysis composition of polymethylmethacrylate (PMMA), used the peak area I of methyl methacrylate (MMA) MMACalculated peak area than (I by these MMA/ I St).
In addition, the quality W PAc-M of AUL-704 (PAc-M) is equivalent to the quality of conducting particles 51, the quality W of polymethylmethacrylate (PMMA) PMMAThe quality that is equivalent to insulating fine particles 52.Calculated mass ratio A (W by these PMMA/ W PAc-M).Then, about peak area than (I MMA/ I St) and mass ratio A (W PMMA/ W PAc-M) relation, made the calibration curve that is shown in Fig. 7.The calibration curve of Fig. 7 has good rectilinearity.
Then, to carry out the thermolysis gas chromatography about the calibration curve of mass ratio B and measure in order to make.When measuring, used LP-704 (PAc) as the ponding chemical company system of polyacrylic ester particle.
In measurement result,, used peak value (peak) the area I of polyacrylic ester (Ac) as the peak value of the thermolysis composition of LP-704 (PAc) ACIn addition, as the peak value of the thermolysis composition of polymethylmethacrylate (PMMA), used the peak area I of methyl methacrylate (MMA) MMACalculated peak area than (I by these MMA/ I AC).
In addition, the quality W of polymethylmethacrylate (PMMA) PMMAThe quality that is equivalent to insulating fine particles 52, the quality WPAc of LP-704 (PAc) is equivalent to the quality of nucleome 51x.Calculated mass ratio B (W by these PMMA/ W PAc).Then, about peak area than (I MMA/ I AC) and mass ratio B (W PMMA/ W PAc) relation, made the calibration curve that is shown in Fig. 8.The calibration curve of Fig. 8 has good rectilinearity.
Then,, carry out the result that the thermolysis gas chromatography is measured, obtain being shown in the pyrogram of the 9th figure with the condition determination that is shown in table 1 about coated particle C.The peak area of acrylate (Ac) and methyl methacrylate (MMA) is than (I MMA/ I AC) be 1: 90.Use this value, calculate the result of mass ratio A by the calibration curve of Fig. 7, mass ratio A is 11/1000, calculates the result of mass ratio B by the calibration curve of Fig. 8, and mass ratio B was 34/1000 (with reference to table 2).
(3) making of circuit connection material
Except replacing and use the coated particle C in the coated particle A of embodiment 1, identical with embodiment 1, obtain the film-shaped circuit connection material of two layers of formation.
(4) making of the connection of circuit member structure
Use above-mentioned film-shaped circuit connection material, identical with embodiment 1 and make the connection structure C of circuit member.
(comparative example 1)
(1) making of conducting particles
The conducting particles that uses the surface not to be covered with insulating fine particles.That is the lining rate of conducting particles is 0%.
(2) the thermolysis gas chromatography is measured
The result that calculates of mass ratio A and mass ratio B is shown in table 2.
(3) making of circuit connection material
Except replacing coated particle A, and use not beyond the conducting particles with the lining of insulating fine particles in embodiment 1, identical with embodiment 1, obtain the film-shaped circuit connection material of two layers of formation.
(4) making of the connection of circuit member structure
Use above-mentioned film-shaped circuit connection material, identical with embodiment 1 and make the connection structure D of circuit member.
(comparative example 2)
(1) making of coated particle
At first,, the nickel dam of thickness 0.2 μ m is set, and, obtains plated film plastic pellet (PSt-M) by in the gold layer of the arranged outside thickness 0.04 μ m of this nickel dam with electroless plating in the surface of the crosslinked polystyrene particle (PSt) of median size 5 μ m.With the some on the surface of this plated film plastic pellet, (PMMA) is covered by polymethylmethacrylate, obtains the coated particle E with the median size 5.2 μ m of the insulating fine particles lining of median size 0.2 μ m.And median size is for from based on retouching the value that measured value that the observation of sweeping the type electron microscope obtains is calculated.
(2) the thermolysis gas chromatography is measured
About coated particle E, carry out the thermolysis gas chromatography with the condition determination that is shown in table 1 and measure.Calculate the result of mass ratio A by the calibration curve of Fig. 5, mass ratio A is 30/1000, calculates the result of mass ratio B by the calibration curve of Fig. 6, and mass ratio B was 101/1000 (with reference to table 2).
(3) making of circuit connection material
Except replacing and use the coated particle E in the coated particle A of embodiment 1, identical with embodiment 1, obtain the film-shaped circuit connection material of two layers of formation.
(4) making of the connection of circuit member structure
Use above-mentioned film-shaped circuit connection material, identical with embodiment 1 and make the connection structure E of circuit member.
(mensuration of the connection resistance between the circuit electrode of subtend)
Connection structure A～E about circuit member, connection resistance to the initial stage (after the connection), connection resistance after will keeping 500 circulations (cycle) in-40 ℃ of 30 minutes and 100 ℃ of temperature cycle grooves of 30 minutes uses 2 terminals measurement methods and measures with universal meter (multimeter).The results are shown in table 3.At this, the so-called resistance that connects between the circuit electrode that resistance means subtend.
(mensuration of the insulation resistance between adjacent circuit electrode)
About the connection of circuit member structure A～E, will apply the insulation resistance of voltage after one minute of direct current (DC) 50V, use 2 terminals measurement methods and measure with universal meter (multimeter).The results are shown in table 3.At this, so-called insulation resistance is meant the resistance between adjacent circuit electrode.
(table 3)
Embodiment 1 (connecting structure A) Embodiment 2 (connecting structure B) Embodiment 3 (connecting structure C) Comparative example 1 (connecting structure D) Comparative example 2 (connecting structure E)
Connect resistance Initial stage (Ω) ＜1 ＜1 ＜1 ＜1 2
After the temperature cycle (Ω) ＜1 ＜1 ＜1 ＜1 ＞20
Insulation resistance (Ω) ＞10 12 ＞10 12 ＞10 12 ＜10 4 ＞10 12
For the connection structure A～C of the circuit member of embodiment 1～3, in the early stage, arbitrary connection resistance all is suppressed very lowly after the temperature cycle, it is very high that insulation resistance also becomes.
To this, for the connection structure D of the circuit member of comparative example 1, compared with connecting structure A～C, insulation resistance step-down.In addition, the connection of the circuit member of comparative example 2 structure E, in the early stage, arbitraryly after the temperature cycle connect resistance compared with connecting structure A～C and all uprise.
The foregoing description 1～3 and comparative example 1,2 are the 1st embodiment.Confirmed by above, make at the circuit connection material that uses the 1st embodiment under the situation of connection structure of circuit member, in the connection of the circuit member that obtains structure, but the connection resistance between the circuit electrode of subtend fully reduces and stabilization, the insulativity between adjacent circuit electrode that can fully improve simultaneously.
(embodiment 4)
At first, be 80 ℃ phenoxy resin by bisphenol A type epoxy resin and dihydroxyphenyl propane (bisphenol A) synthetic glass tansition temperature.With this phenoxy resin 50g, being dissolved in weight ratio is the mixed solvent of toluene (110.6 ℃ of boiling points, SP value 8.90)/ethyl acetate (77.1 ℃ of boiling points, SP value 9.10)=50/50, divides the solution of 40 weight % as solid shape.Then, being adjusted into solid shape branch weight ratio is the solution of phenoxy resin 60g, dicyclopentenyl omega-diol diacrylate 39g, phosphate type acrylate 1g, uncle's hexyl peroxidation-2-ethylhexanoate 5g.
On the other hand, insulating fine particles that uses the polymkeric substance by free-radical polymerised material (acrylate monomer) to constitute, the proportion after the lining for the proportion before the lining relatively be 98/100 ground coated electroconductive particles the surface 20%, obtained coated particle.And conducting particles has the nickel dam of thickness 0.2 μ m on the surface of the nucleome that is made of polystyrene, has the gold layer of thickness 0.04 μ m in the outside of this nickel dam.In addition, as conducting particles, having used median size is the conducting particles of 5 μ m.
This coated particle is cooperated disperse 5 volume % to adjust solution in above-mentioned solution.Then,, use apparatus for coating and coat PET (polyethylene terephthalate) film of the thickness 80 μ m of the one side of surface treatment,, on the PET film, obtain the 1st film like material of thickness 10 μ m by 70 ℃, 10 minutes warm air drying with this solution.
In addition, being adjusted into solid shape branch weight ratio is other solution of phenoxy resin 60g, dicyclopentenyl omega-diol diacrylate 39g, phosphate type acrylate 1g, uncle's hexyl peroxidation-2-ethylhexanoate 5g.With this solution, use apparatus for coating and coat PET (polyethylene terephthalate) film of the thickness 80 μ m of the one side of surface treatment, by 70 ℃, 10 minutes warm air drying, on the PET film, obtain the 2nd film like material that constitutes by binder composition of thickness 10 μ m.
The 1st above-mentioned film like material and the 2nd film like material is bonding with laminating machine, obtain the film-shaped circuit connection material of two layers of formation.
(embodiment 5)
At first, ' two (4-hydroxyphenyl) fluorenes, the synthetic glass tansition temperature is 80 ℃ a phenoxy resin by bisphenol A type epoxy resin and 9,9.With this phenoxy resin 50g, being dissolved in weight ratio is the mixed solvent of toluene (110.6 ℃ of boiling points, SP value 8.90)/ethyl acetate (77.1 ℃ of boiling points, SP value 9.10)=50/50, divides the solution of 40 weight % as solid shape.Then, being adjusted into solid shape branch weight ratio is the solution of phenoxy resin 60g, dicyclopentenyl omega-diol diacrylate 39g, phosphate type acrylate 1g, uncle's hexyl peroxidation-2-ethylhexanoate 5g.
On the other hand, use insulating fine particles by the polymkeric substance formation of free-radical polymerised material (acrylate monomer), 40% of the surface that the relative preceding proportion that is covered of the proportion after the lining is 97/100 ground coated electroconductive particles has obtained coated particle.And conducting particles has the nickel dam of thickness 0.2 μ m on the surface of the nucleome that is made of polystyrene, has the gold layer of thickness 0.04 μ m in the outside of this nickel dam.In addition, as conducting particles, having used median size is the conducting particles of 5 μ m.
This coated particle is cooperated disperse 5 volume % to adjust solution in above-mentioned solution.Then,, use apparatus for coating and coat PET (polyethylene terephthalate) film of the thickness 80 μ m of the one side of surface treatment,, on the PET film, obtain the 1st film like material of thickness 10 μ m by 70 ℃, 10 minutes warm air drying with this solution.
In addition, being adjusted into solid shape branch weight ratio is other solution of phenoxy resin 60g, dicyclopentenyl omega-diol diacrylate 39g, phosphate type acrylate 1g, uncle's hexyl peroxidation-2-ethylhexanoate 5g.With this solution, use apparatus for coating and coat PET (polyethylene terephthalate) film of the thickness 80 μ m of the one side of surface treatment, by 70 ℃, 10 minutes warm air drying, on the PET film, obtain the 2nd film like material that constitutes by binder composition of thickness 10 μ m.
The 1st above-mentioned film like material and the 2nd film like material is bonding with laminating machine, obtain the film-shaped circuit connection material of two layers of formation.
(comparative example 3)
Except replacing in the coated particle of embodiment 4, used not beyond the conducting particles with the lining of insulating fine particles, identical with embodiment 4 and obtain the film-shaped circuit connection material of two layers of formation.That is the lining rate of conducting particles is 0%.
(comparative example 4)
Except replacing in the coated particle of embodiment 4, used beyond the following coated particle, identical with embodiment 4 and obtain the film-shaped circuit connection material of two layers of formation.
Use is by insulating fine particles of the polymkeric substance formation of free-radical polymerised material (acrylate monomer), and 70% of the surface that the relative preceding proportion that is covered of the proportion after the lining is 95/100 ground coated electroconductive particles has obtained coated particle.And conducting particles has the nickel dam of thickness 0.2 μ m on the surface of the nucleome that is made of polystyrene, has the gold layer of thickness 0.04 μ m in the outside of this nickel dam.In addition, as conducting particles, having used median size is the conducting particles of 5 μ m.
(making of the connection structure of circuit member)
At first, as first circuit member, prepared to have disposed the IC chip of the golden projection of projection area 50 μ m * 50 μ m, spacing 100 μ m, height 20 μ m.Then, as the second circuit member, be ready for the circuit of evaporation indium tin oxide (ITO) on the glass substrate of thickness 1.1mm and the ito substrate that forms (surface resistivity＜20 Ω/).
Then, the film-shaped circuit connection material clamping of embodiment 4,5 and comparative example 3,4 is present between IC chip and the ito substrate, IC chip, film-shaped circuit connection material and ito substrate are seized on both sides by the arms with silica glass and polishing head, with 200 ℃, the heating of 100MPa, 10 seconds and pressurization.So effect connects IC chip and ito substrate via film-shaped circuit connection material.At this moment, on ito substrate, in advance a side's of film-shaped circuit connection material bonding plane is stained with 70 ℃, 0.5MPa, heating in 5 seconds and pressurization.Afterwards, peel off the PET film, the opposing party's of film-shaped circuit connection material bonding plane is connected with the IC chip.
By as upper type, made the connection structure F～I of circuit member.And the connection structure F～I of circuit member uses the film-shaped circuit connection material of embodiment 4,5 and comparative example 3,4 respectively and makes.
(mensuration of proportion)
Each film-shaped circuit connection material about embodiment 4,5 and comparative example 3,4, with the coated particle after conducting particles before the lining and the lining, 3.5cc takes a sample respectively, in room temperature, helium atmosphere with specific gravity hydrometer (Shimadzu Seisakusho Ltd.'s corporate system, Accupyc 1330-01) measures proportion, obtain the coated particle ratio of the proportion of the conducting particles before the lining (proportion than) relatively after the lining.The results are shown in table 4.
(mensuration of the connection resistance between the circuit electrode of subtend)
Connection structure F～I about circuit member, connection resistance to the initial stage (after the connection), connection resistance after will keeping 500 circulations (cycle) in-40 ℃ of 30 minutes and 100 ℃ of temperature cycle grooves of 30 minutes uses 2 terminals measurement methods and measures with universal meter (multimeter).The results are shown in table 5.At this, the so-called resistance that connects between the circuit electrode that resistance is meant subtend.
(mensuration of the insulation resistance between adjacent circuit electrode)
About the connection of circuit member structure F～I, will apply the insulation resistance of voltage after one minute of direct current (DC) 50V, use 2 terminals measurement methods and measure with universal meter (multimeter).The results are shown in table 5.At this, so-called insulation resistance is meant the resistance between adjacent circuit electrode.
(table 4)
Embodiment 4 Embodiment 5 Comparative example 3 Comparative example 4
Proportion ratio before and after the lining 98/100 97/100 - 95/100
Lining rate (%) 20 40 0 70
(table 5)
Embodiment 4 (connecting structure F) Embodiment 5 (connecting structure G) Comparative example 3 (connecting structure H) Comparative example 4 (connecting structure I)
Connect resistance Initial stage (Ω) ＜1 ＜1 ＜1 2
After the temperature cycle (Ω) ＜1 ＜1 ＜1 ＞20
Insulation resistance (Ω) ＞10 12 ＞10 12 ＜10 4 ＞10 12
Connection structure F, the G of the circuit member that obtains for the film-shaped circuit connection material that uses embodiment 4,5, in the early stage, in after the temperature cycle any, connect resistance all to be suppressed very lowly, it is very high that insulation resistance also becomes.
To this, the connection structure H of the circuit member that obtains at the film-shaped circuit connection material that uses comparative example 3, insulation resistance step-down compared with connecting structure F, G.In addition, use the film-shaped circuit connection material of comparative example 4 and the connection structure I of the circuit member that obtains, in the early stage, in after the temperature cycle any, connect resistance and all uprise compared with connecting structure F, G.
The foregoing description 4,5 and comparative example 3,4 are the 2nd embodiments.Can confirm by above, make at the circuit connection material that uses the 2nd embodiment under the situation of connection structure of circuit member, in the connection structure of the circuit member that obtains, the connection resistance between the circuit electrode of subtend fully reduces and can fully improve the insulativity between adjacent circuit electrode.

Claims (18)

1. circuit connection material, be used to make first circuit member that on the interarea of first circuit substrate, is formed with a plurality of first circuit electrodes,
With the second circuit member that on the interarea of second circuit substrate, is formed with a plurality of second circuit electrodes,
The circuit connection material that connects with the state of described first and second circuit electrode subtend,
Wherein, contain binder composition, and the coated particle that forms of being insulated property of the part surface micropartical of conducting particles lining,
The quality of described insulating fine particles be described conducting particles quality 2/1000～26/1000.
2. circuit connection material, be used to make first circuit member that on the interarea of first circuit substrate, is formed with a plurality of first circuit electrodes,
With the second circuit member that on the interarea of second circuit substrate, is formed with a plurality of second circuit electrodes,
The circuit connection material that connects with the state of described first and second circuit electrode subtend,
Wherein, contain binder composition, and the coated particle that forms of being insulated property of the part surface micropartical of conducting particles lining,
Described conducting particles has the nucleome that is made of macromolecular compound,
The quality of described insulating fine particles is 7/1000～86/1000 of a described nucleome quality.
3. circuit connection material, be used to make first circuit member that on the interarea of first circuit substrate, is formed with a plurality of first circuit electrodes,
With the second circuit member that on the interarea of second circuit substrate, is formed with a plurality of second circuit electrodes,
The circuit connection material that connects with the state of described first and second circuit electrode subtend,
Wherein, contain binder composition, and the coated particle that forms of being insulated property of the part surface micropartical of conducting particles lining,
The proportion of described coated particle be described conducting particles proportion 97/100～99/100.
4. circuit connection material as claimed in claim 3, wherein, in described coated particle, the surface of described conducting particles 5～60% by the lining of described insulating fine particles.
5. as each described circuit connection material in the claim 1 to 4, wherein, the median size of described insulating fine particles be described conducting particles median size 1/40～1/10.
6. as each described circuit connection material in the claim 1 to 5, wherein, described insulating fine particles is that the polymkeric substance by free-radical polymerised material constitutes.
7. as each described circuit connection material in the claim 1 to 6, wherein, the solidifying agent that described binder composition contains free-radical polymerised material and produced free free radical by heating.
8. as each described circuit connection material in the claim 1 to 7, wherein, also contain the film that constitutes by phenoxy resin and form material.
9. circuit connection material as claimed in claim 8, wherein, described phenoxy resin contains the molecular configuration that is derived from polycyclc aromatic compound at intramolecularly.
10. circuit connection material as claimed in claim 9, wherein, described polycyclc aromatic compound is a fluorenes.
11. a film-shaped circuit connection material wherein, makes in the claim 1 to 10 each described circuit connection material form film like and forms.
12. the connection of circuit member structure possesses: on the interarea of first circuit substrate, be formed with first circuit member of a plurality of first circuit electrodes,
On the interarea of second circuit substrate, be formed with the second circuit member of a plurality of second circuit electrodes, and
Between the described interarea that is arranged at described first circuit substrate and the described interarea of described second circuit substrate and be at described first and second circuit electrode under the state of mutual subtend and be connected the mutual circuit transom of described first and second circuit member,
Wherein, described circuit transom is made of the cured article of each described circuit connection material in the claim 1 to 10,
Described first circuit electrode is electrically connected via described coated particle with described second circuit electrode.
13. the connection of circuit member as claimed in claim 12 structure, wherein, when applying the volts DS of 50V between adjacent described circuit electrode, the resistance value between adjacent described circuit electrode is 10 9More than the Ω.
14. as the connection structure of claim 12 or 13 described circuit members, wherein, at least one is the IC chip in described first and second circuit member.
15. as the connection of each described circuit member in the claim 12 to 14 structure, wherein, described first circuit electrode is below 1 Ω with the resistance that is connected between the described second circuit electrode.
16. connection structure as each described circuit member in the claim 12 to 15, wherein, at least one has by at least a electrode surface layer that constitutes in metal that is selected from gold and silver, tin, platinum family and the indium tin oxide in described first and second circuit electrode.
17. connection structure as each described circuit member in the claim 12 to 16, wherein, at least one has by at least a substrate surface layer that constitutes that is selected from silicon nitride, silicon oxide compound and the polyimide resin in described first and second circuit member.
18. the manufacture method of the connection of circuit member structure wherein, possesses:
At first circuit member that is formed with a plurality of first circuit electrodes on the interarea of first circuit substrate and between the second circuit member that is formed with a plurality of second circuit electrodes on the interarea of second circuit substrate, described first circuit electrode and described second circuit electrode pair to state under, the operation of each described circuit connection material in the claim 1 to 10 is set; And
Make described circuit connection material solidified operation by heating and pressurization.
CNA200580001944XA 2004-01-07 2005-01-06 Circuit connection material, film-shaped circuit connection material using the same, circuit member connection structure, and manufacturing method thereof Pending CN1906265A (en)

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Application publication date: 20070131