CN107254264B - The connection structure and its manufacturing method of circuit connection material, circuit block - Google Patents

The connection structure and its manufacturing method of circuit connection material, circuit block Download PDF

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Publication number
CN107254264B
CN107254264B CN201710459575.3A CN201710459575A CN107254264B CN 107254264 B CN107254264 B CN 107254264B CN 201710459575 A CN201710459575 A CN 201710459575A CN 107254264 B CN107254264 B CN 107254264B
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circuit
application according
resin
conducting particles
connection material
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CN107254264A (en
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中泽孝
藤绳贡
竹村贤三
饭岛由佑
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/14—Structural association of two or more printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0218—Composite particles, i.e. first metal coated with second metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
    • H05K2201/10621—Components characterised by their electrical contacts
    • H05K2201/10681—Tape Carrier Package [TCP]; Flexible sheet connector

Abstract

The present invention relates to the connection structures and its manufacturing method of circuit connection material, circuit block.Circuit connection material of the invention is for opposite circuit electrode to be electrically connected to each other, the circuit connection material includes adhesive composite and conducting particles, the conducting particles is the outermost layer formed with the nucleome and the noble metal by being coated the nucleome formed by the metal or nickel of Vickers hardness 300~1000 and 5~20 μm of average grain diameter of blocky particle, is formed with bumps on the surface of conducting particles.

Description

The connection structure and its manufacturing method of circuit connection material, circuit block
It is on April 10th, 2012 that the application, which is the applying date of original application, and application No. is 201280023903.0 (international applications Number PCT/JP2012/059804), entitled " circuit connection material, the connection structure of circuit block and circuit block The manufacturing method of connection structure " Chinese patent application divisional application.
Technical field
The present invention relates to the manufactures of the connection structure of circuit connection material, the connection structure of circuit block and circuit block Method.
Background technique
As semiconductor element, bonding agent used for liquid crystal display element, using excellent in adhesion and show highly reliable The thermosetting resins (referring for example to patent document 1) such as the epoxy resin of property.It is usually used as the constituent of above-mentioned bonding agent Epoxy resin, with the curing agent such as the reactive phenolic resin of epoxy resin, promote reacting for epoxy resin and curing agent Hot potentiality catalyst.Hot potentiality catalyst becomes an important factor for solidification temperature and curing rate for determining bonding agent, Various compounds are used always from the viewpoint of storage-stable at room temperature and curing rate when heating.
In addition, recently, by the free-radical polymerised compounds such as acrylate derivative, methacrylate derivative and work The radical-curable bonding agent constituted for the peroxide of radical polymerization initiator attracts attention.Radical-curable bonding Agent can solidify (referring for example to patent document 2~4) at low temperature and in the short time.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 1-113480 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2002-203427 bulletin
Patent document 3: No. 98/044067 pamphlet of international publication
Patent document 4: Japanese Unexamined Patent Publication 2005-314696 bulletin
Summary of the invention
Problems to be solved by the invention
These bonding agents mainly the flat-panel monitors such as liquid crystal display panel (Flat Panel Display, hereinafter referred to as " FPD ") field is universal, and begins to use that (Printed Wiring Board, is known as below according to situation in printed circuit board " PWB ") with carrier tape package (Tape Carrier Package, hereinafter referred to as " TCP ") or flip chip (Chip On Flex, Hereinafter referred to as " COF ") connection.The field FPD flexible print wiring board (Flexible Printed Circuits, below According to circumstances be known as " FPC ") and the connection of PWB in using circuit connection material, gold-plated processing usually is implemented to circuit.Another party Face, for wanting the PWB of the components such as chip, capacitor, it is mainstream that installation is carried out by welding.It is good in order to obtain Suitable weldering attempt the processing for be formed the resin coating of imidazo-containing compounds as the surface treatment of circuit.In addition, In large-scale mother board etc., due to can reduce cost without using gold, usually by with organic tree such as imidazo-containing compounds The solution of rouge, which is handled and (is known as " OSP processing " below according to situation), forms organic envelope (hereinafter, being according to circumstances known as " OSP film ").Also studying making for foregoing circuit connecting material always in the installation of the processed circuit substrate of such OSP With.
In addition, the mainstream of circuit board structure is multilayered structure, when in order to release connection due to the trend of high-density installation Heat, via hole, through-hole etc. are equipped near interconnecting piece.Therefore, heat is assigned to interconnecting piece and need time enough, still From the viewpoint of improving production efficiency, it is desirable that the connection of short time.
Rapidly-curable radically curing system bonding agent can be short used in the connection of the FPC and PWB in the field FPD Solidification in time, but in the case where being used for substrate processed through OSP, and for through phase the case where gold-plated processed substrate Than there is connection resistance and be easy the tendency risen.
In addition, the use for not needing rapid curing connection on the way, the anionic curing system of previous general epoxy resin Bonding agent shows good bonding force to OSP processing substrate, but in order to weld and by existing on connection resistance after reflow ovens The tendency risen.
Here, the purpose of the present invention is to provide can solidify in a short time and be used for through the processed substrate of OSP In the case where assign sufficiently high connection reliability circuit connection material, using its circuit block connection structure and electricity The manufacturing method of the connection structure of circuit unit.
The means solved the problems, such as
The inventors of the present invention are concentrated on studies in response to the above problems, and it is aftermentioned to complete as a result to have obtained opinion below Invention: it is non-that the main reason for being the rising of the connection resistance in the case where bonding agent using above-mentioned solidification, which is OSP film itself, Electric conductivity, and cause the OSP film of circuit substrate to be hardened by reflow ovens to weld.
That is, the present invention provides a kind of circuit connection material, it is the electricity for opposite circuit electrode to be electrically connected to each other Road connecting material, containing adhesive composite and conducting particles, conducting particles is with the metal by Vickers hardness 300~1000 The bulk that the nucleome of formation and the outermost layer formed by the noble metal on the surface for being coated the nucleome and average grain diameter are 5~20 μm Particle is formed with bumps on the surface of conducting particles.
In addition, the present invention provides a kind of circuit connection material, it is for opposite circuit electrode to be electrically connected to each other Circuit connection material, containing adhesive composite and conducting particles, conducting particles is with the nucleome formed by nickel and by being coated The blocky particle that the outermost layer and average grain diameter that the noble metal on the surface of the nucleome is formed are 5~20 μm, in the table of conducting particles Face is formed with bumps.
Circuit connection material of the invention passes through contains conducting particles as described above and adhesive composite simultaneously, thus It can solidify in a short time, and for can also show good connection reliability through the processed substrate of OSP.
For the conducting particles in circuit connection material of the invention, the difference in height at bumps is preferably 70nm~2 μm. As long as the difference in height at bumps is above range, it is easy the OSP film of perforation circuit electrode, is easy to inhibit the upper of connection resistance It rises.
From the viewpoint of it can solidify in a shorter time, in circuit connection material of the invention, bonding agent combination Object preferably comprises free-radical polymerised substance and generates the curing agent of free free radical by heating.
In addition, the adhesive composite in circuit connection material of the invention contains epoxy resin and potentiality curing agent In the case of, the connection reliability of the connection structure of circuit block can be further increased.
In addition, in circuit connection material of the invention, it is preferable that at least one party in opposite circuit electrode, which has, contains miaow The envelope of azole compounds.Circuit connection material of the invention containing conducting particles as described above and bonding agent by combining simultaneously Object can also obtain good connectivity even if circuit electrode has the envelope of imidazo-containing compounds within the short Connection Time.
The present invention provides a kind of connection structure of circuit block, comprising: is formed with the 1st on the interarea of the 1st circuit substrate 1st circuit block of circuit electrode, be formed on the interarea of the 2nd circuit substrate the 2nd circuit electrode and the 2nd circuit electrode with With the 2nd circuit block that configures of mode of the 1st circuit electrode relative configuration, be set to the 1st circuit substrate and the 2nd circuit substrate it Between and connect the circuit connection that the 1st circuit block and the 2nd circuit block are electrically connected the 1st circuit electrode and the 2nd circuit electrode Portion；Circuit connecting section is the solidfied material of the film-like circuit connecting material of aforementioned present invention.
In the connection structure of circuit block of the invention, in preferably the 1st circuit electrode and the 2nd circuit electrode extremely A few side has the envelope of imidazo-containing compounds.
For the connection structure for using the circuit block of circuit connection material of previous short time curing type, in electricity In the case that path electrode has OSP film, the connection of short time, which exists, is difficult to improve internuncial tendency.On the other hand, just originally For the connection structure of the circuit block of invention, circuit connecting section is the solidfied material of the circuit connection material of aforementioned present invention, by This, can obtain good connectivity the shorter Connection Time.In addition, just circuit block of the invention connection structure and Speech, forms circuit electrode surface by the envelope that the material of imidazo-containing compounds is formed, therefore circuit electrode can be protected from oxygen Change, obtains good suitable weldering.Further, connection structure of the invention using the circuit connection material of aforementioned present invention due to being made It obtains circuit block to be connected to each other, to have sufficiently high adhesive strength and connection reliability.
The present invention provides a kind of manufacturing method of the connection structure of circuit block, including following process: will be in the 1st circuit base It is formed with the 1st circuit block of the 1st circuit electrode on the interarea of plate and is formed with the 2nd circuit on the interarea of the 2nd circuit substrate 2nd circuit block of electrode is configured in the 1st circuit electrode mode opposite with the 2nd circuit electrode, in the 1st electricity of relative configuration It is situated between in the state of having above-mentioned film-like circuit connecting material between path electrode and the 2nd circuit electrode and is heated and pressurizeed to whole, It connects the 1st circuit block and the 2nd circuit block is electrically connected the 1st circuit electrode and the 2nd circuit electrode.With regard to circuit of the invention For the manufacturing method of the connection structure of component, by making the circuit connection material of aforementioned present invention between the 1st circuit electrode and It between 2nd circuit electrode and is heated and pressurizeed, can obtain that there is good connection in the shorter Connection Time The connection structure of circuit block.
The present invention relates to a kind of bonding agents as the circuit connection material for opposite circuit electrode to be electrically connected to each other Application, the bonding agent contains adhesive composite and conducting particles, and conducting particles is that have by Vickers hardness 300~1000 The metal nucleome formed and the outermost layer and average grain diameter that are formed by the noble metal on the surface for being coated the nucleome be 5~20 μm Blocky particle, be formed with bumps on the surface of conducting particles.
Moreover, it relates to which a kind of bonding agent is as the circuit connection for opposite circuit electrode to be electrically connected to each other The application of material, the bonding agent contain adhesive composite and conducting particles, and conducting particles is with the nucleome formed by nickel The blocky particle that the outermost layer and average grain diameter formed with the noble metal by the surface for being coated the nucleome is 5~20 μm, in conduction The surface of particle is formed with bumps.
The present invention relates to a kind of bonding agents in the circuit connection material for opposite circuit electrode to be electrically connected to each other Application in manufacture, the bonding agent contain adhesive composite and conducting particles, and conducting particles is that have by Vickers hardness 300 The nucleome of~1000 metal formation and the outermost layer and average grain diameter formed by the noble metal on the surface for being coated the nucleome are 5 ~20 μm of blocky particle is formed with bumps on the surface of conducting particles.
Moreover, it relates to which a kind of bonding agent is in the circuit connection material for opposite circuit electrode to be electrically connected to each other Application in the manufacture of material, the bonding agent contain adhesive composite and conducting particles, and conducting particles is that have to be formed by nickel Nucleome and the outermost layer and average grain diameter that are formed by the noble metal on the surface for being coated the nucleome be 5~20 μm blocky particle, Bumps are formed on the surface of conducting particles.
Invention effect
Using the present invention, it is capable of providing a kind of can solidify in a short time and for the feelings through the processed substrate of OSP The connection structure of the circuit connection material of high connecting reliability, the connection structure of circuit block and circuit block is assigned under condition Manufacturing method.
Detailed description of the invention
Fig. 1 is the cross-sectional view of an embodiment of indication circuit connecting material.
Fig. 2 is the SEM image for indicating an example of appearance for conducting particles.
Fig. 3 is the SEM image for indicating an example on the surface of amplification for conducting particles.
Fig. 4 is the cross-sectional view for indicating an embodiment of connection structure.
Fig. 5 is the cross-sectional view for indicating an embodiment of connection structure.
Specific embodiment
Hereinafter, as needed referring to attached drawing, the embodiment that the present invention will be described in detail is suitable for.But the present invention does not limit In the following embodiments and the accompanying drawings.Here, identical element is paid with identical appended drawing reference in attached drawing, the repetitive description thereof will be omitted.Separately Outside, unless otherwise specified, positional relationship equal up and down is on the basis of positional relationship shown in the accompanying drawings.Further, The dimensional ratios of attached drawing are not limited to the ratio of diagram.
Circuit connection material of the present embodiment is the bonding agent for circuit electrode to be electrically connected to each other.Fig. 1 is The cross-sectional view of one embodiment of indication circuit connecting material.As shown in Figure 1, circuit connection material 1 is by resin layer 3 and dispersion It is constituted in multiple conducting particles 8 in resin layer 3, there is membranaceous shape.
Hereinafter, each constituent material to circuit connection material 1 is illustrated.
(conducting particles)
Conducting particles 8 is with the nucleome formed by the metal of Vickers hardness 300~1000 and by being coated the expensive of the nucleome Metal formed outermost layer and be formed with the blocky particle of multiple bumps on the surface of conducting particles.In addition, conducting particles 8 is It the outermost layer that is formed with the nucleome formed by nickel and the noble metal by being coated the nucleome and is formed on the surface of conducting particles The blocky particle of multiple bumps.Here, the bumps on conducting particles surface are produced by the bumps as aftermentioned core surface.
Fig. 2 is the SEM image for indicating an example of appearance for conducting particles, and Fig. 3 is the amplification for indicating conducting particles The SEM image of one example on surface.As shown in Figures 2 and 3, the conducting particles of present embodiment is not spherical but blocky grain Son has been formed on its surface bumps.Such conducting particles 8 is easy the dielectric OSP envelope of perforation circuit electrode, is easy Inhibit the rising of connection resistance.Therefore, using the circuit connection material 1 for containing above-mentioned conducting particles 8, it is reliable that connection can be made The connection structure of the excellent circuit block of property.
The nucleome of conducting particles 8 preferably by from nickel, chromium, molybdenum, manganese, cobalt, iron, vanadium, titanium, platinum, iridium, osmium, tungsten, tantalum, niobium, zirconium, At least one metal selected in the transition metal such as palladium is constituted, and is more preferably made of nickel.
The Vickers hardness for constituting the metal of nucleome is 300~1000, more preferably 400~800, further preferably 500 ~700.If the Vickers hardness of nucleome, less than 300, there are conducting particles 8 to be easily deformed, the removing property of OSP film on electrode drop Low tendency, if conducting particles 8 is difficult to deform more than 1000, it is difficult to ensure enough contacts area are to assign good company Connect reliability.
Nucleome has bumps on its surface.There are bumps on surface by nucleome, so as on the surface of conducting particles It is formed concave-convex.Concave-convex method is formed in core surface to be not particularly limited, such as in the case where nucleome is nickel, passes through carbonyl Method reacts nickel ores at normal temperature with carbon monoxide, carbonyl nickel complex is formed, further by making in 100 DEG C or more heating Carbon monoxide is detached from, and can obtain forming indent and convex nickel on surface.
Difference in height at the bumps that the surface of conducting particles 8 is formed is preferably 70nm~2 μm, and more preferably 90nm~ 1.5 μm, further preferably 120nm~1 μm.If the difference in height at bumps is 70nm or more, for the circuit with OSP film Electrode is easy insertion, and there are the tendencies that the connection resistance after reliability test is suppressed.In addition, if the difference in height at bumps is Within 2 μm, then the protrusion foundation position at bumps is not easy to remain adhesive composite, and there is also the connections after reliability test The tendency that resistance is suppressed.
The average grain diameter of conducting particles 8 is 5~20 μm, preferably 8~20 μm, more preferably 8~15 μm.If average grain diameter Less than 5 μm, then the solidification of resin layer 3 occurs before conducting particles 8 and electrode contact, if more than 20 μm, due to conductive particle The radius of curvature of son 8 is big, therefore the removing property of the OSP film on electrode reduces, and conducts all be difficult to realize under any circumstance.This In, the average grain diameter of conducting particles specified in the application is the survey obtained by SEM image observation conducting particles (n number 50) Definite value, such as can be by being calculated to longest particle size fraction with most short particle size fraction averaging and.
The outermost layer of conducting particles 8 is formed by noble metal, preferably by from noble metals such as Au Ag Pt Pd, rhodium, iridium, ruthenium, osmiums In at least one metal for selecting constitute, be more preferably made of gold or platinum, be further preferably made of gold.By by these metals The outermost layer for constituting conducting particles 8, can make the working life long enough of circuit connection material 1.
The outermost thickness of conducting particles 8 is preferably 0.03~0.4 μm, and more preferably 0.08~0.2 μm.If outermost layer With a thickness of 0.03 μm or more, then the electric conductivity that there is conducting particles 8 is maintained, inhibits to connect the tendency of resistance, if 0.4 Within μm, then there is the cost when nucleome forms outermost layer and be able to inhibition, cheapness excellent tendency.Here, it is preferred that nucleome The outermost layer covering that is formed by noble metal of entire surface, but in the range of not departing from effect of the present invention, a part of nucleome, Such as the bumps of core surface can be exposed from outermost layer.
Use level of the conducting particles 8 in circuit connection material 1 is suitable for depending on the application setting, in general, relative to bonding Agent composition (part of the resin layer 3 i.e. in circuit connection material 1 other than conducting particles 8) 100 parts by volume are 0.1~30 volume In the range of part.Further, conductive from preventing from the viewpoint of circuit electrode adjacent on same circuit substrate is electrically short-circuited to each other The use level of particle 8 is more preferably 0.1~10 parts by volume.
(adhesive composite)
The adhesive composite of resin layer 3 is formed containing the curing agent and free-radical polymerised object for generating free free radical Matter.In other words, circuit connection material 1 can contain adhesive composite and conducting particles 8, and the adhesive composite contains generation The curing agent and free-radical polymerised substance of free free radical.When circuit connection material 1 is heated, due to free-radical polymerised The polymerization of substance forms cross-linked structure in adhesive composite, forms the solidfied material of circuit connection material 1.In this case, electric Road connecting material 1 plays a role as radical-curable bonding agent.
The curing agent of the free free radical of generation used in circuit connection material 1 is peroxide compound, azo system chemical combination Object etc. decomposes by heating and generates the substance of free free radical, according to as a purpose connection temperature, the Connection Time, be applicable in Phase etc. is suitable for selected.Use level is on the basis of the total quality of circuit connection material 1, and preferably 0.05~10 mass % is more excellent Be selected as 0.1~5 mass % (with the total quality of circuit connection material 1 be 100 mass parts, preferably 0.05~10 mass parts, more Preferably 0.1~5 mass parts).The curing agent for generating free free radical specifically can be from diacyl peroxide, peroxidating two It is selected in carbonic ester, peroxyester, ketal peroxide, dialkyl peroxide, hydroperoxides etc..In addition, in order to inhibit electricity The corrosion of the connection terminal of circuit unit is preferably selected from peroxyester, dialkyl peroxide, hydroperoxides, more preferably From can obtain selecting in the peroxyester of high response.
As diacyl peroxide class, it can be cited for example that 2,4- dichlorobenzoyl peroxides, 3,5,5 ,-trimethyl Hexanoyl peroxidating, decoyl peroxide, lauroyl peroxide, peroxidating stearic acid, succinic acid peroxide (ス Network シ ニ ッ Network パ ー オ キ サ イ De), benzoyl peroxide toluene, benzoyl peroxide.
As peroxy dicarbonates, it can be cited for example that diη-propyl peroxy dicarbonate, diisopropyl peroxide Change two carbonic esters, bis- (4- tert-butylcyclohexyl) peroxy dicarbonates, two -2- ethoxymethyl) epoxide peroxy dicarbonates, Two (peroxidating of 2- ethylhexyl) two carbonic esters, dimethoxybutyl peroxy dicarbonate and two (3- methyl -3- methoxyl groups Butyl peroxy) two carbonic esters.
As peroxyesters, it can be cited for example that 1,1,3,3 ,-tetramethyl butyl new decanoate ester peroxide, 1- hexamethylene Base -1- Methylethyl new decanoate ester peroxide, tert-hexyl peroxide neodecanoic acid ester, t-butylperoxy pivarate, 1,1,3, 3,-tetramethyl butyl peroxidating -2 ethyl hexanoic acid ester, 2,5- dimethyl -2,5- two (2- ethylhexanoyl-peroxy) hexane, 1- Cyclohexyl -1- Methylethyl peroxidating 2 ethyl hexanoic acid ester, tert-hexyl peroxide -2 ethyl hexanoic acid ester, tert-butyl hydroperoxide -2- Bis- (tert-butyl hydroperoxide) hexamethylenes of ethylhexoate, tert-butyl hydroperoxide isobutyrate, 1,1-, tert-hexyl peroxide isopropyl Monocarbonate, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, tert-butyl hydroperoxide laurate, 2,5- dimethyl -2,5- Two (toluoyl peroxidating) hexanes, t-butylperoxyisopropyl monocarbonate, tert-butyl hydroperoxide -2- ethylhexyl single carbon Acid esters, tert-hexyl peroxide benzoic ether and tert-butyl hydroperoxide acetic acid esters.
As ketal peroxide class, it can be cited for example that 1,1- bis- (tert-hexyl peroxide) -3,3,5- trimethyl-cyclohexanes, Bis- (tert-hexyl peroxide) hexamethylenes of 1,1-, bis- (the tert-butyl hydroperoxide) -3,3,5- trimethyl-cyclohexanes of 1,1-, 1,1- (tertiary fourth Base peroxidating) cyclododecane and 2,2- it is bis--(tert-butyl hydroperoxide) decane.
As dialkyl peroxide class, it can be cited for example that α, α ' bis- (tert-butyl hydroperoxide) diisopropyl benzenes, peroxide Change diisopropylbenzene (DIPB), two (tert-butyl hydroperoxide) hexane of 2,5- dimethyl -2,5- and t-butylcumylperoxide.
As hydroperoxide type, it can be cited for example that hydroperoxidation diisopropylbenzene (DIPB) and cumene hydroperoxide.
These curing agent for generating free free radical can be used alone or as a mixture, can also be with decomposition accelerating agent, inhibitor Etc. being used in mixed way.In addition, these curing agent polyurethane series, Polyester polymer substance etc. is coating to after microencapsulation It is thus preferred to extend the up time for substance.
Free-radical polymerised substance used in circuit connection material 1 refers to the functional group using free radical polymerization It is sub- can to enumerate acrylate, methacrylate, maleimide compound, citraconimide resin, nadik acyl for substance Amine (Na ジ イ ミ De) resin etc..The use level of free-radical polymerised substance is with the total quality of circuit connection material 1 for 100 matter Measure part, preferably 20~50 mass parts, more preferably 30~40 mass parts.Free-radical polymerised substance can be in monomer and low It uses, monomer and oligomer can also be used in combination under any state of polymers.
As above-mentioned acrylate (further including corresponding methacrylate, similarly hereinafter), it can be cited for example that metering system Acid esters, ethyl propylene acid esters, isopropylacrylic acid ester, isobutyl acrylate, glycol diacrylate, diethylene glycol dipropyl Olefin(e) acid ester, trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, two acryloxy of 2- hydroxyl -1,3- Bis- [4- (acryloyl-oxy ylmethoxy) phenyl] propane of propane, 2,2-, 2,2- bis- [4- (acryloxy polyethoxy) phenyl] Propane, dicyclopentenyl acrylate, tricyclic decenyl acrylate, three (acryloyl-oxyethyl) isocyanuric acid esters and poly- Urethane acrylate.They can be used singly or two or more kinds in combination, and also can according to need is suitable for using quinhydrones, quinhydrones first The polymerization inhibitors such as base ethers.In addition, with dicyclopentenyl and/or in the case where tricyclic decenyl and/or triazine ring, heat resistance Improve thus it is preferred.
It is the compound containing the above dimaleoyl imino of at least two in molecule as above-mentioned maleimide compound, It can be cited for example that 1- methyl -2,4- bismaleimide benzene, N, N '-meta-phenylene bismaleimide, N, N '-is to phenylene Bismaleimide, N, N '-talan bismaleimide, N, N ' -4,4- biphenylene bismaleimide, N, N ' - 4,4- (3,3 '-dimethyl biphenylene) bismaleimide, N, N ' -4,4- (3,3 '-dimethyl diphenylmethane) span come Acid imide, N, N ' -4,4- (3,3 '-diethyl diphenyl methane) bismaleimide, N, N ' -4,4- diphenyl methane span come Acid imide, N, N ' -4,4- diphenyl propane bismaleimide, N, N ' -3,3 '-diphenyl sulfone bismaleimide, N, N ' -4, Bis- (4- (4- maleimidephenoxy) phenyl) propane of 4- diphenyl ether bismaleimide, 2,2-, bis- (the tertiary fourths of 3- of 2,2- Base -4,8- (4- maleimidephenoxy) phenyl) propane, bis- (4- (4- maleimidephenoxy) phenyl) decane of 1,1-, 4,4 '-cyclohexylidenes-bis- (1- (4- maleimidephenoxy) -2- cyclohexyl benzene and bis- (4- (the 4- maleimides of 2,2- Phenoxy group) phenyl) hexafluoropropane.They can be used alone or two or more is applied in combination.
Above-mentioned citraconimide resin is the citraconimide instigated in molecule at least one citraconimide base The resin that polymerize of object is closed, as citraconimide compound, it can be cited for example that phenyl citraconimide, methyl -2 1-, 4- dual-citraconic imide benzene, N, N '-metaphenylene dual-citraconic imide, N, N '-TOPOT 2,2′ p phenylenebis citraconimide, N, N ' -4, 4- biphenylene dual-citraconic imide, N, N ' -4,4- (3,3- dimethyl biphenylene) dual-citraconic imide, N, N ' -4,4- (3, 3- dimethyl diphenylmethane) dual-citraconic imide, N, N ' -4,4- (3,3- diethyl diphenyl methane) dual-citraconic imide, N, N ' -4,4- diphenyl methane dual-citraconic imide, N, N ' -4,4- diphenyl propane dual-citraconic imide, N, N ' -4,4- hexichol Base ether dual-citraconic imide, N, bis- (4- (the 4- citraconimide phenoxy group) benzene of N ' -4,4- diphenyl sulphone (DPS) dual-citraconic imide, 2,2- Base) propane, 2,2- bis- (3- tert-butyl -3,4- (4- citraconimide phenoxy group) phenyl) propane, bis- (4- (the 4- citraconoyls of 1,1- Imines phenoxy group) phenyl) decane, 4,4 '-cyclohexylidenes-bis- (1- (4- citraconimide phenoxy group) phenoxy group) -2- cyclohexyl Benzene and bis- (4- (the 4- citraconimide phenoxy group) phenyl) hexafluoropropane of 2,2-.They can be used alone or two or more group It closes and uses.
Above-mentioned nadikimide resin is the nadik acyl instigated in molecule at least one nadikimide base The resin that group with imine moiety polymerize, as nadikimide compound, it can be cited for example that phenyl nadikimide, The double nadikimide benzene of 1- methyl -2,4-, N, N '-metaphenylene double nadikimides, N, N '-TOPOT 2,2′ p phenylenebis nadik Acid imide, N, N ' -4,4- biphenylene double nadikimides, N, N ' -4,4- (3,3- dimethyl biphenylene) double nadiks Acid imide, N, the double nadikimides of N ' -4,4- (3,3- dimethyl diphenylmethane), N, N ' -4,4- (3,3- diethyl hexichol Methylmethane) double nadikimides, N, N ' -4,4- diphenyl methane double nadikimides, N, N ' -4,4- diphenyl propane is double Nadikimide, N, N ' -4,4- diphenyl ether double nadikimides, N, N ' -4,4- diphenyl sulphone (DPS) double nadikimides, 2, Bis- (4- (the 4- nadikimide phenoxy group) phenyl) propane of 2-, bis- (3- tert-butyl -3,4- (the 4- nadikimide benzene of 2,2- Oxygroup) phenyl) propane, 1,1- bis- (4- (4- nadikimide phenoxy group) phenyl) decane, 4,4 '-cyclohexylidenes-bis- (1- (4- nadikimide phenoxy group) phenoxy group) -2- cyclohexyl benzene and bis- (4- (the 4- nadikimide phenoxy group) benzene of 2,2- Base) hexafluoropropane.They can be used alone or two or more is applied in combination.
Circuit connection material 1 may be used also other than generating the curing agent and free-radical polymerised substance of free free radical Contain other compositions.Such as thermoplastic resin and thermosetting resin can be contained.
As thermoplastic resin, polyvinyl resin, polyimide resin, Corvic, polyphenylene oxide tree can be used Rouge, polyvinyl butyral resin, vinyl-formal resin, polyamide, polyester resin, phenoxy resin, polyphenyl second Olefine resin, xylene resin, polyurethane resin etc..
As thermoplastic resin can be 40 DEG C or more and molecular weight 10000 it is preferable to use Tg (glass transition temperature) with On hydroxy-containing resin, such as phenoxy resin can be properly used.Phenoxy resin can pass through two trifunctional phenol classes and table halogen Alcohol reaction is until reach high molecular weight to obtain, or by making two functional epoxy resins and two trifunctional phenol classes carry out addition polymerization conjunction Reaction obtains.
As thermosetting resin, urea resin, melamine resin, phenolic resin, xylene resin, epoxy can be enumerated Resin, polyisocyanate resin etc..
Contain above-mentioned thermoplastic resin in the case where, due to process performance is good, solidify when stress mitigation it is excellent, thus It is preferred that.In addition, in the case where above-mentioned thermoplastic resin and thermosetting resin have the functional groups such as hydroxyl, since cementability mentions Height, thus more preferably, can also be used the elastomer containing epoxy group, free-radical polymerised functional group and be modified.Utilize freedom The substance that the functional group modification of base polymerism obtains, heat resistance improve thus it is preferred.
From the point of view of the viewpoints such as film formation property, the weight average molecular weight of above-mentioned thermoplastic resin is preferably 10000 or more, but if 1000000 or more, then there is the tendency of Combination variation.Here, weight average molecular weight specified in the application refers to according to following Condition uses the weight average molecular weight of the calibrating curve determining according to standard polystyren using gel permeation chromatography (GPC).
<GPC condition>
Use machine: Hitachi's L-6000 type (Hitachi (strain) system)
Chromatographic column: Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440 (meter 3) (Hitachi At industrial (strain) system)
Eluent: tetrahydrofuran
Measuring temperature: 40 DEG C
Flow: 1.75mL/ minutes
Detector: L-3300RI (Hitachi (strain) system)
In addition, adhesive composite (resin layer 3) can also contain epoxy resin and potentiality curing agent, trip is generated to substitute From the curing agent of free radical and free-radical polymerised substance.That is, circuit connection material 1 can be containing containing epoxy resin and potentiality The adhesive composite and conducting particles 8 of curing agent.When circuit connection material 1 is heated due to the solidification of epoxy resin from And cross-linked structure is formed in adhesive composite, form the solidfied material of circuit connection material 1.In this case, circuit connection Material 1 plays a role as the bonding agent of curable epoxide type.
As epoxy resin, glycidol ether, that is, bisphenol-type epoxy resin of the bis-phenols such as bisphenol-A, F, AD and by phenol phenol Epoxy-Novolak resin derived from Novolac or cresol novolak is representative epoxy resin.As other examples, may be used To enumerate naphthalene type epoxy resin with naphthalene skeleton, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, alicyclic ring Formula epoxy resin and hetero ring type epoxy resin.They can be used alone or two or more are used in mixed way.
In above-mentioned epoxy resin, the grade different from broadly available molecular weight can arbitrarily set cementability, reactivity etc. The case where consider, preferred bisphenol-type epoxy resin.In bisphenol-type epoxy resin, particularly preferred bisphenol f type epoxy resin.Bis-phenol The viscosity of F type epoxy resin is low, by being applied in combination with phenoxy resin, can easily set the mobility of circuit connection material 1 It is set to wide scope.In addition, bisphenol f type epoxy resin also has the advantages that be easy to assign good adhesion to circuit connection material 1.
Electromigration is, it is preferable to use foreign ion (Na in order to prevent+、Cl-Deng) concentration or water-disintegrable chlorine is that 300ppm is below Epoxy resin.
As potentiality curing agent, as long as epoxy resin cure can be made.In addition, potentiality curing agent can be It is reacted with epoxy resin and is introduced into the compound in cross-linked structure, be also possible to promote the catalysis of the curing reaction of epoxy resin Dosage form curing agent.The two can also be used in combination.
As catalyst type curing agent, it can be cited for example that promoting the anionically polymerized of the anionic polymerisation of epoxy resin The cationic polymerization type potentiality curing agent of the cationic polymerization of potentiality curing agent and promotion epoxy resin.
As anionically polymerized potentiality curing agent, it can be cited for example that imidazoles system, hydrazides system, trifluoro boron-amine complexing Object, aminimide, the salt of polyamines, dicyandiamide and their modifier.The anionically polymerized potentiality of imidazoles system solidifies Agent is, for example, to add in epoxy resin imidazoles or derivatives thereof and formed.
As cationic polymerization type potentiality curing agent, preferably for example make epoxy resin cure using energy-ray irradiation Photonasty salt (mainly using aromatic diazonium salt, aromatic series sulfonium salt etc.).In addition, leading to as other than irradiation energy ray Heating is crossed to activate and make the substance of epoxy resin cure, there is aliphatic sulfonium salt.This curing agent is due to rapid curing The feature of property and it is preferred that.
By polymer substances such as these potentiality curing agent polyurethane series, Polyesters, the metallic films such as nickel, copper and silicon The inorganic matters such as sour calcium are coating, and to microencapsulation, this is able to extend the up time, thus preferably.
The use level of potentiality curing agent relative to 100 mass parts of epoxy resin be preferably 30~60 mass parts, more preferably For 40~55 mass parts.If the use level of potentiality curing agent is 30 mass parts or more, because the solidification of circuit connection material 1 is received Contracting and generate the fastening force of adherend is difficult to decrease.As a result, contact of the conducting particles 8 with circuit electrode is kept, There are the connection resistance after reliability test to be easy repressed tendency.On the other hand, if the use level of potentiality curing agent is Within 60 mass parts, then fastening force is not become too strong, thus the internal stress in the solidfied material of circuit connection material 1 is difficult to become Greatly, there is the tendency for being easy that adhesive strength is inhibited to reduce.
When circuit connection material 1 is epoxide resin adhesive, film formation material is preferably comprised.By liquid material Cure will be constituted in the case that composition does film forming shape, and film formation material is that the processing of the film is made to be easy and assign not It is easily broken, splits, the film of the mechanical property of adhesion etc., being able to carry out under common state (normal temperature and pressure) as film and locate Reason.
As film formation material, above-mentioned thermoplastic resin can be used, from cementability, intermiscibility, heat resistance and machinery , it is preferable to use phenoxy resin from the point of view of excellent strength.
Phenoxy resin is by reacting two degree of functionality phenols up to producing high-molecular with epihalohydrins or by making two functions It spends epoxy resin and two degree of functionality phenols carries out resin obtained from addition polymerization conjunction.Phenoxy resin can be for example, by making two functions 1 mole of degree phenol is with 0.985~1.015 mole of epihalohydrins in the presence of the catalyst such as alkali metal hydroxide, non-anti- In answering property solvent 40~120 DEG C at a temperature of reaction to obtaining.
In addition, as phenoxy resin, from the mechanical property, thermal characteristics of resin from the viewpoint of, particularly preferably make two functions The cooperation equivalent proportion for spending epoxy resin and two degree of functionality phenols is epoxy group/phenolic hydroxyl group=1/0.9~1/1.1, in alkali metal In the presence of closing the catalyst such as object, organophosphorus compound, cyclic annular amine compound, boiling point be 120 DEG C or more amide system, It is heated in the organic solvents such as ether system, ketone system, lactone system, alcohol system, under the conditions of reacting solid component and being 50 mass % below 50~200 DEG C of progress polyaddition reactions obtain.
As two degree of functionality epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D-ring can be used Oxygen resin, bisphenol-s epoxy resin.Two degree of functionality phenols are the substances with 2 phenolic hydroxyl group, it can be cited for example that quinhydrones The bisphenol compounds such as class, bisphenol-A, Bisphenol F, bisphenol-A D, bisphenol S.
Phenoxy resin can pass through free-radical polymerised functional group modification.Phenoxy resin can be used alone a kind or by 2 kinds with On be used in mixed way.
Further, circuit connection material 1 can also containing packing material, softener material, promotor, age resister, colorant, Fire retardant, thixotropic agent, coupling agent and isocyanates etc..In the case where containing packing material, due to can be improved connection Reliability etc. is thus preferred.It is able to use as long as the partial size that the maximum gauge of packing material is less than conducting particles 8, use level is excellent Select the range of 5~60 volume %.If 5~60 volume %, then the effect for maintaining reliability to improve is easy.As coupling agent, from From the point of view of the aspect that cementability improves, preferred vinyl contains object, acryloyl group contains object, amino contains object, epoxy group contains object And isocyanate group contains object.The polymerization inhibitors such as quinhydrones, MEHQ hydroquinone monomethyl ether class can also be properly used as needed.
The circuit connection material of present embodiment is the bonding agent for being used to for circuit electrode being electrically connected to each other as described above.
That is, the bonding agent of present embodiment is the bonding agent containing adhesive composite and conducting particles, conducting particles is It the nucleome that is formed with the metal by Vickers hardness 300~1000 and is formed by the noble metal on the surface for being coated the nucleome outermost The blocky particle that layer and average grain diameter are 5~20 μm, is formed with bumps on the surface of conducting particles.This bonding agent can be used as use It is applied in the circuit connection material that opposite circuit electrode is electrically connected to each other.In addition, can also be in order to for by opposite electricity The manufacture for the circuit connection material that path electrode is electrically connected to each other and apply.
In addition, the bonding agent of present embodiment is the bonding agent containing adhesive composite and conducting particles, conducting particles Be the outermost layer formed with the nucleome that is formed by nickel and by the noble metal on the surface for being coated the nucleome and average grain diameter for 5~ 20 μm of blocky particle is formed with bumps on the surface of conducting particles.This bonding agent can be used as by opposite circuit electrode The circuit connection material that is electrically connected to each other and apply.In addition, can also be in order to for opposite circuit electrode to be electrically connected to each other The manufacture of circuit connection material and apply.
Then, it is illustrated for the connection structure of the circuit block for the present embodiment for using circuit connection material 1.Electricity Road connecting material 1 is suitable for forming the chip parts such as semiconductor chip, resistor body chip and capacitor chip and printing The connection structure that the such circuit block with 1 or 2 or more circuit electrode (connection terminal) of circuit board is connected to each other.
Fig. 4 is the cross-sectional view of an embodiment of the connection structure of indication circuit component.Circuit block shown in Fig. 4 Connection structure 100 includes: the 1st circuit block of the 1st circuit electrode 13 formed with the 1st circuit substrate 11 and on its major face 10；The 2nd circuit electrode 23 that is formed with the 2nd circuit substrate 21 and on its major face and with the 23 and the 1st electricity of the 2nd circuit electrode The 2nd circuit block 20 that the opposite mode of path electrode 13 configures；And between the 1st circuit block 10 and the 2nd circuit block 20 it Between interconnecting piece 1a.
Interconnecting piece 1a is the solidfied material that circuit connection material 1 is formed by curing, and contains conducting particles 8.Interconnecting piece 1a is electric by the 1st Circuit unit 10 and the 2nd circuit block 20 are bonded so that the 1st opposite circuit electrode 13 and the electrical connection of the 2nd circuit electrode 23.Relatively The 1st circuit electrode 13 and the 2nd circuit electrode 23 via conducting particles 8 be electrically connected.Here, it is led even if not contained in interconnecting piece 1a In the case where charged particle 8, can also it be electrically connected via the 1, the 1st circuit electrode 13 of circuit connection material and the 2nd circuit electrode 23.
1st circuit substrate 11 is containing from polyester terephthalate, polyether sulfone, epoxy resin, acrylic resin and poly- The resin film for at least one resin selected in group composed by imide resin.1st circuit electrode 13 can be made by having For electrode play a role degree electric conductivity material (preferably composed by gold, silver, tin, platinum group metal and the indium-tin-oxide At least one selected in group) it is formed.
2nd circuit substrate 21 be by silicon, gallium, arsenic of chip type semiconductor etc., glass, ceramics, glass/epoxy composite body, The multilayer circuit board that the insulating substrates such as plastics are formed.Preferably, the 2nd circuit electrode 23 has conductor portion 23a and forms circuit electricity The bumps formed with the envelope 23b of the part to connect interconnecting piece 1a, envelope 23b on the surface of conducting particles 8 in 23 surface of pole It penetrates through and is electrically connected.For conductor portion 23a, circuit electrode 23 is played a role the material of degree electric conductivity by that can be used as electrode (at least one preferably selected from the group being made of gold, silver, tin, the metal of platinum family and indium-tin-oxide) is formed.
Envelope 23b is the envelope formed by the material containing organic resin, preferably comprises the organic resins such as imidazolium compounds. Envelope 23b is by carrying out OSP (Organic Solderability Preservative: organic weldable to the 2nd circuit substrate 21 Property protective agent) processing to be formed.Here, OSP processing refers to the substrate processing method using same of also referred to as water-soluble preflux, generally Ground, by carrying out processing to substrate with the solution of imidazo-containing compounds to form OSP film.The envelope of imidazo-containing compounds refers to The complex compound generated by imidazoles system derivative and metal is bonding to each other at the electrode surface thus the film formed.That is, containing imidazoles The envelope for closing object can be carried out OSP by the solution to the substrate imidazo-containing compounds for being formed with circuit electrode and be handled to be formed. It is suitable for using benzimidazole system derivative from the viewpoint of heat resistance as imidazolium compounds.OSP processing can be used for example Trade name タ Off エ ー ス F2, the F2 (LX) of four countries' chemical conversion (strain) system as commercially available material or (strain) three and the made De of research Mec seal CL-5824S of ー コ ー ト GVII or Enthone corporation Entek106A, 106A (X) or Mec (strain) system, CL-5018, CL-5018S are carried out.
In circuit connection material of the present embodiment, at least one party in the 1st circuit electrode and the 2nd circuit electrode can For having the connection of the circuit block of the envelope formed by the material containing organic resin.Here, expression as shown in Figure 5 electricity The cross-sectional view of one embodiment of the connection structure of circuit unit, it is preferable that be not only the 2nd circuit electrode 23, the 1st circuit electrode 13 also can have conductor portion 13a and formed in 13 surface of circuit electrode with the envelope 13b of the part to connect interconnecting piece 1a, the The envelope 13b of 1 circuit electrode 13 is also penetrated through by the bumps formed on the surface of conducting particles 8 and is electrically connected.Envelope 13b by with The same method of envelope 23b is formed.
The manufacturing method of the connection structure of the circuit block of present embodiment includes following process: will be in the 1st circuit substrate Interarea on be formed with the 1st circuit block of the 1st circuit electrode and be formed on the interarea of the 2nd circuit substrate the 2nd circuit electricity 2nd circuit block of pole is configured in the opposite mode of the 1st circuit electrode and the 2nd circuit electrode, in the 1st circuit of relative configuration Be situated between in the state of having the film-like circuit connecting material of present embodiment between electrode and the 2nd circuit electrode to it is whole heated with And pressurization, it connects the 1st circuit block and the 2nd circuit block is electrically connected the 1st circuit electrode and the 2nd circuit electrode.
The connection structure 100 of circuit block is to be manufactured by the following method to obtain, that is, to such as the 1st circuit block 10, Above-mentioned 1 and the 2nd circuit block 20 of film-like circuit connecting material is according to this sequentially with the 1st circuit electrode 13 and the 2nd circuit electrode 23 The laminated body that opposite mode is laminated is heated and is pressurizeed, so that the 1st circuit block 10 of connection and the 2nd circuit block 20 make Obtain the 1st circuit electrode 13 and the electrical connection of the 2nd circuit electrode 23.
In this manufacturing method, such as the film-like circuit connecting material 1 formed on film can will supported to fit in the 2nd circuit It is heated and is pressurizeed in the state of on component 20 so that 1 temporary bond of circuit connection material, is removed after supporting film, by the 1st Circuit block 10 is aligned and is loaded in the opposite mode of circuit electrode, to prepare laminated body.In order to prevent due to connection When heating and volatile ingredient influence caused by connection for generating, circuit block is carried out in advance preferably before connecting process Heat treatment.
The condition that above-mentioned laminated body is heated and pressurizeed is according to the curability etc. of composition in circuit connection material It carries out being suitable for adjustment, so that circuit connection material solidifies and obtains sufficient adhesive strength.In addition, according in circuit connection material Composition can also be connected by light irradiation.
Constitute connection structure circuit block possessed by substrate can be the semiconductor chips such as silicon and gallium, arsenic and Glass, ceramics, glass/insulating substrates such as epoxy composite body and plastics.
Embodiment
Hereinafter, being further elaborated with using embodiment to the contents of the present invention.However, the present invention is not limited to these Embodiment.
(1) production of circuit connection material
(1-1) constitutes the preparation of each ingredient of adhesive composite
" PERHEXA 25O ": 2,5- dimethyl -2,5- bis- (2- ethyl hexyl) hexanes (Japanese grease system, trade name)
" UN5500 ": urethane acrylate oligomer (industry system, trade name on root)
" DCP-A ": dicyclopentadiene-type diacrylate (East Asia synthesis system, trade name)
" M-215 ": cyamelide EO modified diacrylate (East Asia synthesis system, trade name)
" P-2M ": 2- methacryloxyethyl phosphate ester acid (common prosperity society chemistry system, trade name)
" HX3941HP ": epoxy resin (the imidazoles system containing 35 mass % of the curing agent of potentiality containing anionically polymerized Microcapsule-type curing agent, Asahi Chemical Industry's Chemicals system, trade name)
" UR-8200 ": polyester polyurethane (Japan's weaving system, trade name)
" EV40W ": ethylene-vinyl acetate copolymer (three well Du Pont POLYCHEMICALS systems, trade name)
" PKHC ": bisphenol A-type phenoxy resin (weight average molecular weight 45000, INCHEM CORPORATION system, trade name)
" acrylic rubber A ": 40 mass parts of butyl acrylate -30 mass parts of ethyl acrylate -30 mass parts of acrylonitrile-first The copolymer (weight average molecular weight about 850,000) of 3 mass parts of base glycidyl acrylate
" SH6040 ": silane coupling agent (γ-glycidyl ether oxypropyltrimethoxysilane, the beautiful DOW CORNING in east Organosilicon system, trade name)
The preparation of (1-2) conducting particles
As " conducting particles A ", prepare to have the nucleome formed by the Ni particle for being formed with multiple bumps on surface and The conducting particles that outermost layer and 10 μm of average grain diameter are formed by by gold that is gold-plated and being formed is implemented to the nucleome.As " conductive Particle B ", prepare to have the nucleome formed by the Ni particle for being formed with multiple bumps on surface and palladium plated to nucleome implementation and The outermost layer being made of palladium and 10 μm of average grain diameter of conducting particles formed.In addition, preparing tool as " conducting particles C " There is the nucleome formed by spherical Ni particle and implements gold-plated to the nucleome and what is formed be formed by outermost layer and flat by gold The conducting particles of equal 10 μm of partial size.As " conducting particles D ", prepare there is the nucleome formed by spherical Ni particle and to this Nucleome implements the conducting particles that outermost layer and 10 μm of average grain diameter are formed by by gold that is gold-plated and being formed.In addition, as " leading Charged particle E " prepares the conduction for only having by forming the nucleome that indent and convex Ni particle is formed and 10 μm of average grain diameter on surface Particle.As " conducting particles F ", prepare the nucleome and 10 μm of average grain diameter of conductive particle that only have as spherical Ni particle Son.It here, is to make nickel ores and carbon monoxide in 25 DEG C of rings by the nucleome that the Ni particle for being formed with multiple bumps on surface is formed Reaction forms carbonyl nickel complex under border, which is heated at 100 DEG C, carbon monoxide is made to be detached from (carbonyl process), To obtain.
(embodiment 1)
50 mass % hydrocarbon solvent solution, 8 mass parts of cooperation " PERHEXA 25O " (are scaled 4 mass with nonvolatile component Part), (changed with nonvolatile component as 60 mass parts of toluene solution of the 50 mass % of " UN5500 " of free-radical polymerised substance Calculate be 30 mass parts), " DCP-A " 8 mass parts, " M-215 " 8 mass parts, " P-2M " 2 mass parts, " UR-8200 " 30 mass % 150 mass parts of methyl ethyl ketone/toluene (=50/50) solution (45 mass parts are scaled with nonvolatile component) and 50 mass parts of toluene solution (10 mass parts are scaled with nonvolatile component) of the 20 mass % of " EV40W ", further, cooperation " conducting particles A " 10 mass parts.Mixed solution coating machine is coated on a pet film, 70 DEG C of 10 minutes hot air dryings are passed through It is dry, obtain the film-like circuit connecting material that resin layer thickness is 35 μm.
(embodiment 2)
Other than using 10 mass parts of conducting particles B as conducting particles, operate similarly with example 1 to obtain film Shape circuit connection material.
(embodiment 3)
Other than using conducting particles A20 mass parts as conducting particles, operate similarly with example 1 to obtain membranaceous Circuit connection material.
(embodiment 4)
Cooperate " HX3941HP-SS " 50 mass parts, " PKHC " 40 mass % toluene/ethyl acetate (=50/50) it is molten 37.5 mass parts of liquid (15 mass parts are scaled with nonvolatile component), " acrylic rubber A " 10 mass % toluene/acetic acid second 350 mass parts of ester (=50/50) solution (35 mass parts are scaled with nonvolatile component) and " SH6040 " 2 mass parts, into one Step cooperates " conducting particles A " 10 mass parts.By mixed solution coating machine be coated on a pet film, by 70 DEG C 10 minutes Heated-air drying obtains the membranaceous circuit connection material that resin layer thickness is 35 μm.
(embodiment 5)
Other than using 10 mass parts of conducting particles B as conducting particles, operation obtains film similarly to Example 4 Shape circuit connection material.
(embodiment 6)
Other than using conducting particles A20 mass parts as conducting particles, operation is obtained membranaceous similarly to Example 4 Circuit connection material.
(comparative example 1)
Other than using 10 mass parts of conducting particles C as conducting particles, operate similarly with example 1 to obtain film Shape circuit connection material.
(comparative example 2)
Other than using 10 mass parts of conducting particles D as conducting particles, operate similarly with example 1 to obtain film Shape circuit connection material.
(comparative example 3)
Other than using 10 mass parts of conducting particles E as conducting particles, operate similarly with example 1 to obtain film The circuit connection material of shape.
(comparative example 4)
Other than using 10 mass parts of conducting particles F as conducting particles, operate similarly with example 1 to obtain film Shape circuit connection material.
(comparative example 5)
Other than using 10 mass parts of conducting particles C as conducting particles, operation obtains film similarly to Example 4 Shape circuit connection material.
(comparative example 6)
Other than using 10 mass parts of conducting particles D as conducting particles, operation obtains film similarly to Example 4 Shape circuit connection material.
(comparative example 7)
Other than using 10 mass parts of conducting particles E as conducting particles, operation obtains film similarly to Example 4 Shape circuit connection material.
(comparative example 8)
Other than using 10 mass parts of conducting particles F as conducting particles, operation obtains film similarly to Example 4 Shape circuit connection material.
By the composition of Examples 1 to 6 and the circuit connection material of comparative example 1~8, with mass parts, (nonvolatile component is changed Calculate) shown in table 1 and table 2.
[table 1]
[table 2]
(2) production of the connection structure of circuit block
The production of (2-1) through the processed printed circuit board of OSP (PWB)
It is electric that 100 μm of line width, 400 μm of spacing, the copper circuit of 35 μm of thickness are formed on glass/epoxy multilayer board Pole (hereinafter referred to as " PWB ").Further in the copper circuit electrode surface of PWB, using benzimidazole compound, (four countries are melted into (strain) system, trade name " タ フ エ ー ス ") OSP processing is carried out, form 0.10~0.32 μm of thickness of benzimidazole system resin network Close the envelope (hereinafter referred to as " OSP-PWB ") of object.
The production of (2-2) through the processed flexible print wiring board of OSP (FPC)
Prepare to be formed directly with 100 μm of line width, 400 μm of spacing, 18 μm of thickness on 25 μm of thickness of polyimide film The flexible print wiring board (hereinafter referred to as " FPC ") of copper circuit electrode.It is operated in the same way with above-mentioned OSP-PWB and it is implemented OSP processing, form 0.10~0.32 μm of thickness of benzimidazole system resin complexation object is touched (hereinafter referred to as " OSP- FPC”)。
The connection (connection of PWB and FPC) of (2-3) circuit electrode
In the pre-connection, the heating plate as the simulation process by reflow ovens, by OSP-PWB and OSP-FPC at 250 DEG C The upper heat treatment for carrying out 30 seconds.On OSP-PWB, after the bonding plane for attaching above-mentioned membranaceous circuit connection material, 70 DEG C, 1MPa carries out heating in 2 seconds and pressurization to temporarily connect, and then, PET film is removed.Then, with the circuit electrode of OSP-FPC After mode relative to each other aligns with the circuit electrode of OSP-PWB, for Examples 1 to 3 and comparative example 1~4 160 DEG C, 4MPa carries out heating in 6 seconds and pressurization.In addition, being carried out 20 seconds for embodiment 4~6 and comparative example 5~8 in 170 DEG C, 4MPa Heating.Width between the substrate of FPC and PWB is 2mm.
(3) evaluation of the connection structure of circuit block
The measurement of (3-1) connection resistance
Using digital multimeter using four-terminal method between the circuit of the circuit connecting section of the connection structure comprising production Resistance value be measured.The measurement of connection resistance is to carry out protecting in 85 DEG C, the constant temperature and humidity cabinet of 85%RH after newly connection After holding high temperature and humidity processing in 1000 hours, and carrying out -40 DEG C~+100 DEG C of thermal shock test 1000 circulations It is measured respectively after processing.It is 100m Ω range below by the connection resistance using four-terminal method measurement after reliability test It is judged as good.As a result it is shown in table 3.
[table 3]
As shown in table 3, it is thus identified that the circuit connection material of Examples 1 to 6 is after high temperature and humidity processing and thermal shock tries The rising that resistance is connected after testing is all small, and connection reliability is all excellent.On the other hand, the circuit connection material of comparative example 1~8 is in height The connection resistance more than 100m Ω is shown after warm high humidity treatment and after thermal shock test, connection reliability is poor.
Industrial applicibility
Using the present invention, being capable of providing one kind can solidify and for the feelings through the processed substrate of OSP in the short time The connection structure of the circuit connection material of high connecting reliability, the connection structure of circuit block and circuit block is assigned under condition Manufacturing method.
Description of symbols
1- circuit connection material；1a- interconnecting piece；3- resin layer；8- conducting particles；The 1st circuit block of 10-；The 1st electricity of 11- Base board；The 1st circuit electrode of 13-；The 2nd circuit block of 20-；The 2nd circuit substrate of 21-；The 2nd circuit electrode of 23-；23a- conductor Portion；23b- envelope；The connection structure of 100- circuit block.

Claims (93)

1. a kind of circuit connection material, which is characterized in that it connects for the circuit for opposite circuit electrode to be electrically connected to each other Material is connect,
Containing adhesive composite and conducting particles,
The conducting particles be with is formed by the metal of Vickers hardness 300~1000 and surface have indent and convex nucleome with The blocky particle that the outermost layer and average grain diameter that noble metal by being coated the core surface is formed are 8~20 μm, in the conduction The surface of particle is formed with bumps.
2. circuit connection material according to claim 1, which is characterized in that the nucleome is made of transition metal.
3. circuit connection material according to claim 2, which is characterized in that the transition metal be selected from by nickel, chromium, At least one of molybdenum, manganese, cobalt, iron, vanadium, titanium, platinum, iridium, osmium, tungsten, tantalum, niobium, zirconium and palladium metal.
4. circuit connection material according to claim 1, which is characterized in that the Vickers hardness is 400~800.
5. circuit connection material according to claim 1, which is characterized in that the Vickers hardness is 500~700.
6. a kind of circuit connection material, which is characterized in that it connects for the circuit for opposite circuit electrode to be electrically connected to each other Material is connect,
Containing adhesive composite and conducting particles,
The conducting particles is that have to be formed by nickel and have indent and convex nucleome on surface and by being coated the expensive of the core surface The blocky particle that the outermost layer and average grain diameter that metal is formed are 8~20 μm, is formed with recessed on the surface of the conducting particles It is convex.
7. circuit connection material described according to claim 1~any one of 6, which is characterized in that in the conducting particles The difference in height for the bumps that surface is formed is 70nm~2 μm.
8. circuit connection material described according to claim 1~any one of 6, which is characterized in that in the conducting particles The difference in height for the bumps that surface is formed is 90nm~1.5 μm.
9. circuit connection material described according to claim 1~any one of 6, which is characterized in that in the conducting particles The difference in height for the bumps that surface is formed is 120nm~1 μm.
10. circuit connection material described according to claim 1~any one of 6, which is characterized in that the conducting particles is put down Equal partial size is 8~15 μm.
11. circuit connection material described according to claim 1~any one of 6, which is characterized in that the noble metal by from At least one metal selected in Au Ag Pt Pd, rhodium, iridium, ruthenium and osmium is constituted.
12. circuit connection material described according to claim 1~any one of 6, which is characterized in that the outermost thickness It is 0.03~0.4 μm.
13. circuit connection material described according to claim 1~any one of 6, which is characterized in that the outermost thickness It is 0.08~0.2 μm.
14. circuit connection material described according to claim 1~any one of 6, which is characterized in that the conducting particles is matched Resultant is 0.1~30 parts by volume relative to 100 parts by volume of adhesive composite.
15. circuit connection material described according to claim 1~any one of 6, which is characterized in that the conducting particles is matched Resultant is 0.1~10 parts by volume relative to 100 parts by volume of adhesive composite.
16. circuit connection material described according to claim 1~any one of 6, which is characterized in that the adhesive composite The curing agent of free free radical is generated containing free-radical polymerised substance and by heating.
17. circuit connection material according to claim 16, which is characterized in that the curing agent for generating free free radical It is peroxide compound.
18. circuit connection material according to claim 16, which is characterized in that be with the total quality of circuit connection material The use level of benchmark, the curing agent for generating free free radical is 0.05~10 mass %.
19. circuit connection material according to claim 16, which is characterized in that the free-radical polymerised substance contains third Olefin(e) acid ester or methacrylate.
20. circuit connection material according to claim 16, which is characterized in that be with the total quality of circuit connection material 100 mass parts, the use level of the free-radical polymerised substance are 20~50 mass parts.
21. circuit connection material according to claim 16, which is characterized in that the adhesive composite also contains thermoplastic Property resin.
22. circuit connection material according to claim 21, which is characterized in that the thermoplastic resin is polyethylene tree Rouge, polyimide resin, Corvic, polyphenylene oxide resin, polyvinyl butyral resin, polyvinyl formal tree Rouge, polyamide, polyester resin, phenoxy resin, polystyrene resin, xylene resin or polyurethane resin.
23. circuit connection material described according to claim 1~any one of 6, which is characterized in that the adhesive composite Contain epoxy resin and potentiality curing agent.
24. circuit connection material according to claim 23, which is characterized in that the epoxy resin includes to be selected from bisphenol type Epoxy resin, naphthalene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, ester ring type asphalt mixtures modified by epoxy resin At least one of rouge and hetero ring type epoxy resin.
25. circuit connection material according to claim 23, which is characterized in that the potentiality curing agent is that anion is poly- Mould assembly potentiality curing agent or cationic polymerization type potentiality curing agent.
26. circuit connection material according to claim 25, which is characterized in that the cationic polymerization type potentiality solidification Agent is aromatic diazonium salt or aromatic series sulfonium salt.
27. circuit connection material according to claim 23, which is characterized in that the use level phase of the potentiality curing agent It is 30~60 mass parts for 100 mass parts of epoxy resin.
28. circuit connection material according to claim 23, which is characterized in that the adhesive composite also contains film shape At material.
29. circuit connection material according to claim 28, which is characterized in that the film formation material is phenoxy resin.
30. circuit connection material described according to claim 1~any one of 6, which is characterized in that the opposite circuit electricity At least one party in extremely has the envelope of imidazo-containing compounds.
31. a kind of connection structure of circuit block comprising:
The 1st circuit block of the 1st circuit electrode is formed on the interarea of the 1st circuit substrate；
The 2nd circuit electrode and the 2nd circuit electrode are formed on the interarea of the 2nd circuit substrate with electric with the 1st circuit The 2nd circuit block that the mode of pole relative configuration configures；
Between the 1st circuit substrate and the 2nd circuit substrate and connect the 1st circuit block and the 2nd electricity The circuit connecting section that circuit unit is electrically connected the 1st circuit electrode and the 2nd circuit electrode,
The circuit connecting section is the solidfied material of circuit connection material described in any one of claims 1 to 30.
32. connection structure according to claim 31, which is characterized in that the 1st circuit electrode and the 2nd circuit electricity At least one party in extremely has the envelope of imidazo-containing compounds.
33. a kind of manufacturing method of the connection structure of circuit block, which is characterized in that including following process:
The 1st circuit block of the 1st circuit electrode will be formed on the interarea of the 1st circuit substrate and in the master of the 2nd circuit substrate The 2nd circuit block of the 2nd circuit electrode side opposite with the 1st circuit electrode and the 2nd circuit electrode is formed on face Formula configuration, has the right to require in 1~30 to be situated between the 1st circuit electrode of relative configuration and the 2nd circuit electrode The state of described in any item circuit connection materials is heated and pressurizeed to whole, connects the 1st circuit block and described 2nd circuit block is electrically connected the 1st circuit electrode and the 2nd circuit electrode.
34. a kind of application of bonding agent as the circuit connection material for opposite circuit electrode to be electrically connected to each other, special Sign is,
The bonding agent contains adhesive composite and conducting particles,
The conducting particles be with is formed by the metal of Vickers hardness 300~1000 and surface have indent and convex nucleome with The blocky particle that the outermost layer and average grain diameter that noble metal by being coated the core surface is formed are 8~20 μm, in the conduction The surface of particle is formed with bumps.
35. application according to claim 34, which is characterized in that the nucleome is made of transition metal.
36. application according to claim 35, which is characterized in that the transition metal be selected from by nickel, chromium, molybdenum, manganese, At least one of cobalt, iron, vanadium, titanium, platinum, iridium, osmium, tungsten, tantalum, niobium, zirconium and palladium metal.
37. application according to claim 34, which is characterized in that the Vickers hardness is 400~800.
38. application according to claim 34, which is characterized in that the Vickers hardness is 500~700.
39. a kind of application of bonding agent as the circuit connection material for opposite circuit electrode to be electrically connected to each other, special Sign is,
The bonding agent contains adhesive composite and conducting particles,
The conducting particles is that have to be formed by nickel and have indent and convex nucleome on surface and by being coated the expensive of the core surface The blocky particle that the outermost layer and average grain diameter that metal is formed are 8~20 μm, is formed with recessed on the surface of the conducting particles It is convex.
40. the application according to any one of claim 34~39, which is characterized in that in the surface shape of the conducting particles At the bumps difference in height be 70nm~2 μm.
41. the application according to any one of claim 34~39, which is characterized in that in the surface shape of the conducting particles At the bumps difference in height be 90nm~1.5 μm.
42. the application according to any one of claim 34~39, which is characterized in that in the surface shape of the conducting particles At the bumps difference in height be 120nm~1 μm.
43. the application according to any one of claim 34~39, which is characterized in that the average grain diameter of the conducting particles It is 8~15 μm.
44. the application according to any one of claim 34~39, which is characterized in that the noble metal by from gold, silver, At least one metal selected in platinum, palladium, rhodium, iridium, ruthenium and osmium is constituted.
45. the application according to any one of claim 34~39, which is characterized in that described outermost with a thickness of 0.03 ~0.4 μm.
46. the application according to any one of claim 34~39, which is characterized in that described outermost with a thickness of 0.08 ~0.2 μm.
47. the application according to any one of claim 34~39, which is characterized in that the use level phase of the conducting particles It is 0.1~30 parts by volume for 100 parts by volume of adhesive composite.
48. the application according to any one of claim 34~39, which is characterized in that the use level phase of the conducting particles It is 0.1~10 parts by volume for 100 parts by volume of adhesive composite.
49. the application according to any one of claim 34~39, which is characterized in that the adhesive composite contains certainly The curing agent of free free radical is generated by base polymeric agents and by heating.
50. application according to claim 49, which is characterized in that the curing agent for generating free free radical is peroxidating Compound.
51. application according to claim 49, which is characterized in that on the basis of the total quality of circuit connection material, institute Stating and generating the use level of the curing agent of free free radical is 0.05~10 mass %.
52. application according to claim 49, which is characterized in that the free-radical polymerised substance contain acrylate or Methacrylate.
53. application according to claim 49, which is characterized in that with the total quality of circuit connection material for 100 mass Part, the use level of the free-radical polymerised substance is 20~50 mass parts.
54. application according to claim 49, which is characterized in that the adhesive composite also contains thermoplastic resin.
55. application according to claim 54, which is characterized in that the thermoplastic resin is polyvinyl resin, polyamides Asia Polyimide resin, Corvic, polyphenylene oxide resin, polyvinyl butyral resin, vinyl-formal resin, polyamide resin Rouge, polyester resin, phenoxy resin, polystyrene resin, xylene resin or polyurethane resin.
56. the application according to any one of claim 34~39, which is characterized in that the adhesive composite contains ring Oxygen resin and potentiality curing agent.
57. application according to claim 56, which is characterized in that the epoxy resin includes to be selected from biphenol type epoxy tree Rouge, naphthalene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin and At least one of hetero ring type epoxy resin.
58. application according to claim 56, which is characterized in that the potentiality curing agent is that anionically polymerized is potential Property curing agent or cationic polymerization type potentiality curing agent.
59. application according to claim 58, which is characterized in that the cationic polymerization type potentiality curing agent is fragrance Race's diazonium salt or aromatic series sulfonium salt.
60. application according to claim 56, which is characterized in that the use level of the potentiality curing agent is relative to described 100 mass parts of epoxy resin are 30~60 mass parts.
61. application according to claim 56, which is characterized in that the adhesive composite also contains film formation material.
62. application according to claim 61, which is characterized in that the film formation material is phenoxy resin.
63. the application according to any one of claim 34~39, which is characterized in that in the opposite circuit electrode At least one party has the envelope of imidazo-containing compounds.
64. a kind of bonding agent answering in the manufacture of the circuit connection material for opposite circuit electrode to be electrically connected to each other With, which is characterized in that
The bonding agent contains adhesive composite and conducting particles,
The conducting particles be with is formed by the metal of Vickers hardness 300~1000 and surface have indent and convex nucleome with The blocky particle that the outermost layer and average grain diameter that noble metal by being coated the core surface is formed are 8~20 μm, in the conduction The surface of particle is formed with bumps.
65. application according to claim 64, which is characterized in that the nucleome is made of transition metal.
66. application according to claim 65, which is characterized in that the transition metal be selected from by nickel, chromium, molybdenum, manganese, At least one of cobalt, iron, vanadium, titanium, platinum, iridium, osmium, tungsten, tantalum, niobium, zirconium and palladium metal.
67. application according to claim 64, which is characterized in that the Vickers hardness is 400~800.
68. application according to claim 64, which is characterized in that the Vickers hardness is 500~700.
69. a kind of bonding agent answering in the manufacture of the circuit connection material for opposite circuit electrode to be electrically connected to each other With, which is characterized in that
The bonding agent contains adhesive composite and conducting particles,
The conducting particles is that have to be formed by nickel and have indent and convex nucleome on surface and by being coated the expensive of the core surface The blocky particle that the outermost layer and average grain diameter that metal is formed are 8~20 μm, is formed with recessed on the surface of the conducting particles It is convex.
70. the application according to any one of claim 64~69, which is characterized in that in the surface shape of the conducting particles At the bumps difference in height be 70nm~2 μm.
71. the application according to any one of claim 64~69, which is characterized in that in the surface shape of the conducting particles At the bumps difference in height be 90nm~1.5 μm.
72. the application according to any one of claim 64~69, which is characterized in that in the surface shape of the conducting particles At the bumps difference in height be 120nm~1 μm.
73. the application according to any one of claim 64~69, which is characterized in that the average grain diameter of the conducting particles It is 8~15 μm.
74. the application according to any one of claim 64~69, which is characterized in that the noble metal by from gold, silver, At least one metal selected in platinum, palladium, rhodium, iridium, ruthenium and osmium is constituted.
75. the application according to any one of claim 64~69, which is characterized in that described outermost with a thickness of 0.03 ~0.4 μm.
76. the application according to any one of claim 64~69, which is characterized in that described outermost with a thickness of 0.08 ~0.2 μm.
77. the application according to any one of claim 64~69, which is characterized in that the use level phase of the conducting particles It is 0.1~30 parts by volume for 100 parts by volume of adhesive composite.
78. the application according to any one of claim 64~69, which is characterized in that the use level phase of the conducting particles It is 0.1~10 parts by volume for 100 parts by volume of adhesive composite.
79. the application according to any one of claim 64~69, which is characterized in that the adhesive composite contains certainly The curing agent of free free radical is generated by base polymeric agents and by heating.
80. the application according to claim 79, which is characterized in that the curing agent for generating free free radical is peroxidating Compound.
81. the application according to claim 79, which is characterized in that on the basis of the total quality of circuit connection material, institute Stating and generating the use level of the curing agent of free free radical is 0.05~10 mass %.
82. the application according to claim 79, which is characterized in that the free-radical polymerised substance contain acrylate or Methacrylate.
83. the application according to claim 79, which is characterized in that with the total quality of circuit connection material for 100 mass Part, the use level of the free-radical polymerised substance is 20~50 mass parts.
84. the application according to claim 79, which is characterized in that the adhesive composite also contains thermoplastic resin.
85. the application according to claim 84, which is characterized in that the thermoplastic resin is polyvinyl resin, polyamides Asia Polyimide resin, Corvic, polyphenylene oxide resin, polyvinyl butyral resin, vinyl-formal resin, polyamide resin Rouge, polyester resin, phenoxy resin, polystyrene resin, xylene resin or polyurethane resin.
86. the application according to any one of claim 64~69, which is characterized in that the adhesive composite contains ring Oxygen resin and potentiality curing agent.
87. the application according to claim 86, which is characterized in that the epoxy resin includes to be selected from biphenol type epoxy tree Rouge, naphthalene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin and At least one of hetero ring type epoxy resin.
88. the application according to claim 86, which is characterized in that the potentiality curing agent is that anionically polymerized is potential Property curing agent or cationic polymerization type potentiality curing agent.
89. the application according to claim 88, which is characterized in that the cationic polymerization type potentiality curing agent is fragrance Race's diazonium salt or aromatic series sulfonium salt.
90. the application according to claim 86, which is characterized in that the use level of the potentiality curing agent is relative to described 100 mass parts of epoxy resin are 30~60 mass parts.
91. the application according to claim 86, which is characterized in that the adhesive composite also contains film formation material.
92. the application according to claim 91, which is characterized in that the film formation material is phenoxy resin.
93. the application according to any one of claim 64~69, which is characterized in that in the opposite circuit electrode At least one party has the envelope of imidazo-containing compounds.
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