CN101682988A

CN101682988A - Circuit connecting material and connecting structure for circuit member

Info

Publication number: CN101682988A
Application number: CN200880020091A
Authority: CN
Inventors: 小岛和良; 小林宏治; 有福征宏; 望月日臣
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Showa Denko Materials Co ltd
Priority date: 2007-10-31
Filing date: 2008-10-29
Publication date: 2010-03-24
Also published as: TWI456852B; TW200939583A; KR101180571B1; TW201334327A; CN105778815B; JP5051221B2; WO2009057612A1; JPWO2009057612A1; CN105778815A; KR20100008372A

Abstract

Disclosed is a circuit connecting material for electrically connecting two circuit members each with a circuit electrode formed thereon in such a state that the circuit electrodes are disposed to faceeach other. The circuit connecting material contains an adhesive agent composition and electroconductive particles. The electroconductive particle comprises a nucleus formed of an organic polymer compound and a metal layer covering the nucleus. The metal layer has protrusions protruded toward the outside of the electroconductive particle. The metal layer is formed of nickel or a nickel alloy. Upon the application of a pressure to the electroconductive particle, the metal layer located on the inner part of the protrusion sinks in the nucleus.

Description

The syndeton of circuit connection material and circuit block

Technical field

The present invention relates to the syndeton of a kind of circuit connection material and circuit block.

Background technology

Carry being connected of encapsulation (hereinafter referred to as " TCP "), flexible circuit board (hereinafter referred to as " FPC ") and being connected of TCP or being connected in the connection each other of such circuit block of FPC and printing distributing board at display panels and band, be dispersed with the circuit connection material (for example anisotropic conductive bonding agent) of conducting particles in the use bonding agent.

And, the situation of semiconductor silicon chips is installed on substrate recently, for the connecting circuit parts each other, do not use the lead-in wire bonding and the semiconductor silicon chips face down be directly installed on the substrate, carry out so-called flip-chip and install.In this flip-chip is installed, use circuit connection materials (with reference to patent documentation 1～5) such as anisotropically conducting adhesive in the circuit block connection each other.

Patent documentation 1: Japanese kokai publication sho 59-120436 communique

Patent documentation 2: Japanese kokai publication sho 60-191228 communique

Patent documentation 3: Japanese kokai publication hei 1-251787 communique

Patent documentation 4: Japanese kokai publication hei 7-90237 communique

Patent documentation 5: TOHKEMY 2001-189171 communique

Patent documentation 6: TOHKEMY 2005-166438 communique

Summary of the invention

The problem that invention will solve

, in recent years, be accompanied by miniaturization, the slimming of electronic equipment, the densification that is formed at the circuit on the circuit block is developed, the tendency that the interval of the electrode of existence and adjacency or the amplitude of electrode become very narrow.The formation of circuit electrode is by forming the metal as the basis of circuit on whole base plate, and at the part painting erosion resistant agent that should form circuit electrode and solidify, part is in addition carried out with the operation of acid or alkaline etching.But, above-mentioned by the situation of the circuit of densification, if it is the metal that forms on whole base plate is concavo-convex big, then different with etching period on the protuberance at recess, so can not carry out accurate etching, the problem that exists in abutting connection with short circuit between circuit or take place to break.Therefore, wish on the electrode surface of high-density circuit concavo-convex for a short time, promptly electrode surface is smooth.

But, use above-mentioned circuit connection material in the past to connect under so opposed smooth circuit electrode situation each other, will residual adhesive resin between contained conducting particles and the smooth electrode in circuit connection material, exist and can not guarantee between opposed circuit electrode to be electrically connected fully and the problem of long-term reliability.

Therefore, to address the above problem is purpose, the circuit connection material that has proposed to contain conducting particles as described below is used for the technology of opposed circuit electrode connection each other, and the outermost layer that the face side of this conducting particles has a plurality of projections and metal level is gold (Au) (with reference to patent documentation 6).

Though the circuit connection structure that uses this circuit connection material to connect can be guaranteed to be electrically connected fully and long-term reliability between opposed circuit electrode, but require when realizing the better to each other electrical connection of opposed circuit electrode, further to improve the long-term reliability of the electrical characteristics between circuit electrode.

The present invention In view of the foregoing carries out, when purpose provides a kind of good electrical connection that can realize between opposed circuit electrode, can fully improve the circuit connection material of the long-term reliability of the electrical characteristics between circuit electrode, and syndeton and the circuit member connecting method of having used the circuit block of this circuit connection material.

The means of dealing with problems

With regard to be used in the past circuit connection material, the surface has with regard to the conducting particles of projection, the outermost layer that constitutes the metal level of conducting particles is made of Au.Because Au is softer metal, so being applied in the words projection of pressure when connecting, circuit will be out of shape, be difficult to obtain long-term connectivity for circuit electrode.Therefore, the result that the inventor furthers investigate repeatedly is conceived to constitute the material of the metal level (metal level is to be outermost layer under the situation of multilayer) of conducting particles, considers and is replaced by the metal harder than Au.So, the metal level of inventor's discovery inside part that take place, jut when circuit connects is to the electrical connection that can influence between opposed circuit electrode that is absorbed in of nucleome, and it is because the hardness of the metal level of conducting particles causes with the repulsion that derives from the plastics of the nucleome that is formed by organic high molecular compound.Promptly, in the connection of the circuit block that has used circuit connection material of the present invention, pressure when relying on circuit to connect, when the jut on conducting particles surface is absorbed in the circuit electrode side, the metal level of the inside part of jut also is absorbed in the nucleome side, be crushed on the circuit electrode side by this projection of repulsion that relies on plastics, and formed the circuit connecting section that further is absorbed in circuit electrode.Its result, circuit connection material of the present invention can be brought into play the good connection between opposed circuit electrode, and can improve the long-term reliability of the electrical characteristics between circuit electrode.

The invention provides for 2 circuit blocks that will be formed with circuit electrode are electrically connected and be connected into the opposed circuit connection material of circuit electrode, circuit connection material contains adhesive composite and conducting particles, conducting particles possesses the metal level of the nucleome that is formed by organic high molecular compound and this nucleome that is covered, metal level has towards the jut of the outside projection of conducting particles, metal level is made of nickel or nickel alloy, under the situation of exerting pressure to conducting particles, the metal level of the inside part of jut can be absorbed in nucleome.

The present invention also provides for 2 circuit blocks that will be formed with circuit electrode are electrically connected and is connected into the opposed circuit connection material of circuit electrode, circuit connection material contains adhesive composite and conducting particles, conducting particles possesses a plurality of metal levels of the nucleome that is formed by organic high molecular compound and this nucleome that is covered, metal level has towards the jut of the outside projection of conducting particles, the outermost layer of metal level is made of nickel or nickel alloy, under the situation of exerting pressure to described conducting particles, the metal level of the inside part of jut can be absorbed in nucleome.

Such circuit connection material can fully improve the long-term reliability of the electrical characteristics between circuit electrode in the good electrical connection that realizes between opposed circuit path electrode.

In circuit connection material of the present invention, the outermost Vickers hardness of preferred above-mentioned metal level or metal level is 400～1000.Thus, further make the electrical connection between opposed circuit electrode good, can improve the long-term reliability of the electrical characteristics between circuit electrode more.

And, the invention provides a kind of syndeton of circuit block, the circuit connecting section part that it possesses 2 circuit blocks being formed with the configuration of circuit electrode and circuit electrode subtend, be electrically connected between circuit block and by heating and pressurizing and with circuit electrode, the circuit connecting section part is the solidfied material of circuit connection material of the present invention, at the inside part of the jut of the conducting particles that circuit connection material contained, metal level has been absorbed in nucleome.

The syndeton of this circuit block owing to use foregoing circuit to connect material, can access the good electrical connection between circuit electrode.So, clipping the good status of electrically connecting between the opposed circuit electrode of conducting particles, the long-term maintenance, can fully be improved the long-term reliability of electrical characteristics thus by the solidfied material of circuit connection material.

In the syndeton of foregoing circuit parts, the surface of at least one side's of the circuit electrode of preferred 2 circuit blocks circuit electrode is formed by indium tin oxide (hereinafter referred to as " ITO ") or indium-zinc oxide (hereinafter referred to as " IZO ").Surface by circuit electrode is formed by ITO or IZO like this, compares with the electrode that metal, Al or Cr by Au, Ag, Sn, Pt family forms, and has the advantage that can prevent the underlying metal oxidation.

Further, the invention provides a kind of circuit member connecting method, it is characterized in that, make foregoing circuit connect material between 2 circuit blocks that are formed with the configuration of circuit electrode and circuit electrode subtend, heating and pressurizing and circuit electrode is electrically connected, the metal level of the inside part of the jut of the conducting particles that makes circuit connection material thus and contained is absorbed in nucleome.Can make the syndeton of the very excellent circuit block of the long-term reliability of the electrical characteristics between circuit electrode thus.

The invention effect

Connect material in a circuit according to the invention, can realize the good electrical connection between opposed circuit electrode, can fully improve the long-term reliability of the electrical characteristics between circuit electrode simultaneously.And, syndeton of the very excellent circuit block of the long-term reliability of the electrical characteristics between circuit electrode and attaching method thereof can be provided according to the present invention.

Description of drawings

Fig. 1 is the sectional view of an execution mode of the syndeton of expression circuit block of the present invention.

Fig. 2 is the sectional view of the various forms of the expression conducting particles that constitutes circuit connection material of the present invention.

Fig. 3 is the sectional view of an execution mode of expression membranaceous circuit connection material of the present invention.

Fig. 4 is the section S EM photo of connecting portion in the syndeton of the circuit block made among the embodiment 2.

Symbol description

The 1st, the syndeton of circuit block; The 10th, the circuit connecting section part; The 11st, the insulating properties material; The 12nd, conducting particles; The 14th, projection (jut); The 21st, nucleome (particle); 21a is center portion (nucleome); 21b is a jut; The 22nd, metal level; 30 is first circuit blocks; The 31st, circuit substrate (first circuit substrate); 31a is an interarea; The 32nd, circuit electrode (first circuit electrode); The 40th, the second circuit parts; The 41st, circuit substrate (second circuit substrate); 41a is an interarea; The 42nd, circuit electrode (second circuit electrode); The 50th, membranaceous circuit connection material; The 51st, adhesive composite; H is the rising height of conducting particles; S is the distance between the projection of adjacency.

Embodiment

Below, as required with reference to accompanying drawing, suitable execution mode of the present invention is elaborated.In addition, in the accompanying drawing, same element annotation prosign omits repeat specification.And the position relation that waits up and down is as long as not explanation in advance just is based on the position relation shown in the drawing.Further, the dimension scale of accompanying drawing is not limited to illustrated ratio.

The syndeton of circuit block

Fig. 1 is the schematic cross-section of an example of the syndeton of expression circuit block of the present invention.The syndeton 1 of circuit block possesses opposed the 1st circuit block 30 and the 2nd circuit block 40 mutually, is provided with the circuit connecting section part 10 that connects them between the 1st circuit block 30 and the 2nd circuit block 40.Circuit connecting section part 10 obtains the circuit connection material cured that contains the conducting particles 12 that possesses a plurality of projections 14 on adhesive composite and the surface.Thereby circuit connecting section part 10 contains insulating properties material 11 and conducting particles 12.Here, insulating properties material 11 is made of the solidfied material of adhesive composite.

The circuit electrode (the 1st circuit electrode) 32 that the 1st circuit block 30 possesses circuit substrate (the 1st circuit substrate) 31 and forms on the interarea 31a of circuit substrate 31.The circuit electrode (the 2nd circuit electrode) 42 that the 2nd circuit block 40 possesses circuit substrate 41 and forms on the interarea 41a of circuit substrate 41.

In

circuit substrate

31,41, the surface of

circuit electrode

32,42 is smooth." having an even surface of circuit electrode " is meant surface concavo-convex below 20nm of circuit electrode in addition, in the present invention.

More than the preferred 50nm of thickness of circuit electrode 32,42.Under the situation of the not enough 50nm of the thickness of

circuit electrode

32,42, the jut 14 that has a face side of the conducting particles 12 in the circuit connection material runs through

circuit electrode

32,42 and the possibility that contacts with

circuit substrate

31,41 when crimping.In this case, there is the contact area minimizing of

circuit electrode

32,42 and conducting particles 12 and is connected the tendency that resistance rises.And the thickness of

circuit electrode

32,42 is considered from the angle of manufacturing cost etc., below the preferred 1000nm, is more preferably below the 500nm.

As the material of

circuit electrode

32,42, can enumerate the metal of Au, Ag, Sn, Pt family or ITO, IZO, Al, Cr.Especially the material of

circuit electrode

32,42 is under the situation of ITO or IZO, is electrically connected to become good significantly, has brought into play effect of the present invention.And

circuit electrode

32,42 can all be made of above-mentioned substance, and also only surface (outermost layer) is made of above-mentioned substance.

Though the material of

circuit substrate

31,41 is not done special restriction, is generally organic insulation material, glass or silicon.

As the object lesson of the 1st circuit block 30 and the 2nd circuit block 40, can enumerate chip parts such as semiconductor chip, resistance chip, capacitor chip, substrates such as printed base plate.These

circuit blocks

30,40 are typically provided with a plurality of (according to circumstances can be single) circuit electrode (circuit terminal) 32,42.And,, also have the form of the mutual syndeton of syndeton, the electric circuit of IC chip and chip mounted board as the form of the syndeton of circuit block.

And, in the 1st circuit block 30, also can between the 1st circuit electrode 32 and circuit substrate 31, insulating barrier be set further; In the 2nd circuit block 40, also can between the 2nd circuit electrode 42 and circuit substrate 41, insulating barrier be set further.Insulating barrier is as long as be made of insulating material and just do not do special restriction, but is made of organic insulation material, silicon dioxide or silicon nitride usually.

And in the syndeton 1 of this circuit block, opposed circuit electrode 32 and circuit electrode 42 are electrically connected by conducting particles 12.That is, conducting particles 12 directly contacts with the both sides of circuit electrode 32,42.Concrete, the projection of conducting particles 12 (being called " jut " again) 14 runs through insulating properties material 11 and contacts with the 1st circuit electrode the 32, the 2nd circuit electrode 42.

Therefore, the connection resistance that circuit electrode is 32,42 fully reduces, and makes the good electrical connection of 32,42 of circuit electrodes become possibility.Thereby, can make electric current mobile unimpeded of 32,42 of circuit electrodes, and can give full play to the function that circuit has.

A part of projection in a plurality of projections 14 of conducting particles 12 preferably is absorbed in circuit electrode 32 or the circuit electrode 42.At this moment, the contact area of the projection 14 of conducting particles 12 and

circuit electrode

32,42 further increases, and can further reduce connection resistance.

In the syndeton 1 of circuit block, at least one side's of preferred the 1st circuit electrode the 32, the 2nd circuit electrode 42 surface area is at 15000 μ m ²Below, simultaneously, be in average conducting particles number between the 1st circuit electrode 32 and the 2nd circuit electrode 42 more than 1.Here, average conducting particles number is meant the mean value of the conducting particles number of average every circuit electrode.At this moment, the connection resistance of 32,42 of opposed circuit electrodes can more fully reduce.

And average conducting particles number can further be realized good connection resistance under the situation more than 3.This is because the connection resistance of 32,42 of opposed circuit electrodes fully reduces.And, connect resistance and become too high under the situation below 1 at the average conducting particles number of 32,42 of circuit electrodes, electronic circuit is cisco unity malfunction sometimes.

Below, circuit connecting section part 10 is elaborated.Circuit connecting section part 10 is membranaceous, as mentioned above, is cured to handle and obtains containing circuit connection material that face side has the conducting particles 12 of jut 14 and adhesive composite.

Circuit connecting section part 10 contains insulating properties material 11 and conducting particles 12.Conducting particles 12, in the back narration, still shown in the (a) and (b) of Fig. 2, its face side has a plurality of juts 14 to its detailed content.And in the syndeton 1 of this circuit block, opposed circuit electrode 32 and circuit electrode 42 are electrically connected by conducting particles 12.That is, conducting particles 12 directly contacts with

circuit electrode

32,42 both sides.Particularly, the jut 14 of conducting particles 12 runs through insulating properties material 11, contacts with the 1st circuit electrode the 32, the 2nd circuit electrode 42.And the metal level 22 of the inside part of the jut 14 of conducting particles 12 is absorbed in nucleome 21a side, and at this moment, the repulsion jut 14 of the plastics by nucleome 21a is pressed to

circuit electrode

32,42 sides, and jut 14 becomes the state that is absorbed in circuit electrode more.

Therefore, the contact area of conducting particles 12 and

circuit electrode

32,42 increases, and the connection resistance that circuit electrode is 32,42 is fully reduced, and makes the good electrical connection of 32,42 of circuit electrodes become possibility.Thereby, the mobile of electric current of 32,42 of circuit electrodes can be become unimpeded, and can give full play to the function that circuit has.

Circuit connection material

Conducting particles

Conducting particles 12 is made of the particle with conductivity (body) and a plurality of juts of forming on the surface of this particle 14.Here, a plurality of juts 14 are made of the metal with conductivity.Fig. 2 is the sectional view of the various forms of the conducting particles that contains in the expression circuit connection material related to the present invention.

The conducting particles 12 of Fig. 2 (a) expression is made of nucleome 21 and the metal level 22 that forms on the surface of nucleome 21, and described nucleome 21 is formed by organic high molecular compound.Nucleome 21 is made of 21a of center portion and the jut 21b that forms on the surface of the 21a of center portion.Metal level 22 has a plurality of juts 14 in its face side.Metal level 22 is covered with nucleome 21, and in the outside projection of location guide electrochondria corresponding with jut 21b, the part that its projection becomes jut 14.

Nucleome 21 is compared with the nucleome that is formed by metal, and cost is low, and the change in size regime of elastic deformation during for thermal expansion or crimping joint is wide, and is therefore as circuit connection material, more suitable.

Organic high molecular compound as the 21a of center portion that constitutes nucleome 21, for example can enumerate acrylic resin, styrene resin, benzene guanamine resin, organic siliconresin, polybutadiene or these copolymer, also can use the material that these are crosslinked.

Preferred 1～4 μ m of the average grain diameter of the 21a of center portion of nucleome 21, more preferably 2～4 μ m, further preferred 2.5～3.5 μ m.If the secondary aggegation of particle will take place in average grain diameter less than 1 μ m, the inadequate tendency of insulating properties of the circuit of existence and adjacency.On the other hand, if average grain diameter surpasses 4 μ m, the area of getting rid of adhesive composite when connecting owing to circuit becomes big, so there is the inadequate tendency of the eliminating of adhesive composite.In addition, the average grain diameter of the nucleome 21 in this specification is meant the average grain diameter of the 21a of center portion, can perhaps measure by the cross section of electron microscope observation conducting particles by using particle size distribution device.

Organic high molecular compound as the jut 21b that constitutes nucleome 21, for example can enumerate acrylic resin, styrene resin, benzene guanamine resin, organic siliconresin, polybutadiene or these copolymer, also can use the material that these are crosslinked.The organic high molecular compound that constitutes jut 21b can be identical or different with the organic high molecular compound that constitutes the center 21a of portion.In addition, the preferred 50～500nm of the average grain diameter of jut 21b.

Nucleome 21 can be by forming at a plurality of jut 21b with diameter littler than the 21a of center portion of the surface adsorption of the 21a of center portion.As method, for example can enumerate the method that both sides or a side's particle is adhered to both mixing after with the dilute solution treatment surface of various coupling agents such as silane, aluminium, titanium and bonding agent at the surface adsorption jut 21b of the 21a of center portion.

Can enumerate Cu, Ni or Ni alloy, Ag or Ag alloy as the material of metal level 22, preferred Ni or Ni alloy.And, under the situation that metal level 22 is made of a plurality of metal levels, the preferred Ni of outermost material or the Ni alloy of metal level 22.For example can enumerate Ni-B, Ni-W, Ni-B, Ni-W-Co, Ni-Fe and Ni-Cr as nickel alloy.

As the hardness of metal level 22, preferred Vickers hardness is 400～1000, is more preferably 500～800.And under the situation that metal level 22 is made of a plurality of metal levels, the outermost Vickers hardness of metal level 22 is 400～1000, is more preferably 500～800.Under the situation of the Vickers hardness less than 400 of metal level, the metal level of projection will be out of shape during the circuit electrode contact, will die down to being absorbed in of circuit electrode, exists contact area to reduce and connects the tendency that resistance uprises.And,,, become the cut state of circuit electrode conduction path each other and exist and connect the tendency that resistance increases because the particle distortion when connecting causes metal level to produce slight crack if the Vickers hardness of metal level surpasses 1000.

Metal level 22 can form these metals of nucleome 21 plating by using electroless plating method.Electroless plating method roughly is divided into batch mode and continuous dropping mode, makes in any way and can both form metal level 22.

Preferred 65～the 125nm of the thickness of metal level 22 (thickness of coating) is more preferably 75～100nm, further preferred 80～90nm.Thickness by making metal level 22 can make the connection resistance of 32,42 of circuit electrodes better in such scope.Here, the thickness of the metal level 22 of the conducting particles in this specification refers to not comprise the metal level thickness partly of jut 14, can pass through determination of electron microscopy.

If the not enough 65nm of the thickness of metal level 22 because the thin thickness of coating exists to make to connect the big tendency of resistance change, if surpass 125nm, condenses during plating, exist in the tendency that is short-circuited easily between the circuit electrode of adjacency between conducting particles.

And, in conducting particles 12, the incorporation rate of the particle that metal level 22 has been peeled off from the nucleome 21 fully, preferably in 250,000 middle less thaies 5% of particle, more preferably less than 1.0%, further preferred less than 0.1%.Incorporation rate by making the particle that metal level 22 peeled off from the nucleome 21 fully can make the conduction of 32,42 of circuit electrodes definite in such scope.If the incorporation rate of the particle that metal level 22 has been peeled off from the nucleome 21 fully is more than 5%, owing to be present on the electrode, exist to connect resistance and become big tendency with the irrelevant particle of conduction.

The situation that conducting particles 12 among the present invention also has nucleome 21 parts ground to expose.Consider from the angle of connection reliability, preferred more than 70% to the lining rate of the metal level 22 of the surface area of nucleome 21, be more preferably 80～100%.Lining rate by making metal level 22 can make the connection resistance of 32,42 of circuit electrodes better in such scope.If the lining rate less than 70% of metal level 22, so, the conduction surface on conducting particles surface connects the big tendency of resistance change because can diminishing to exist.

The height H of the projection 14 of conducting particles 12, preferred 65～500nm is more preferably 100～300nm.And, 14 of the projections of adjacency apart from S, below the preferred 1000nm, be more preferably 500nm.

And, about 14 of the projections of adjacency apart from S, do not enter between conducting particles 12 and the

circuit electrode

32,42 in order to make adhesive composite, and conducting particles 12 fully contacted with

circuit electrode

32,42, preferably at least more than 50nm.Here, 14 of the projections of the height H of the projection 14 of conducting particles 12 and adjacency can pass through determination of electron microscopy apart from S.

In addition, conducting particles 12 is shown in Fig. 2 (b), and nucleome 21 can only be made of the 21a of center portion.In other words, in the conducting particles 12 shown in Fig. 2 (a), also can not be provided with jut 21b.Conducting particles 12 shown in Fig. 2 (b) can be by at the coating surface metal of nucleome 21a, forms metal level 22 and obtain on the surface of nucleome 21a.

Here, to describing for the coating method that forms projection 14.For example, make the bath concentration heterogeneity form projection 14 by the plating bath that in the way of plating reaction, appends than the plating bath high concentration of initial use.And, can be by regulating the pH value of plating bath, the pH that for example makes nickel plating bath is 6 and can access the knurl shape metal level of dashing forward, the metal level 22 (full moon etc., sufacing, Vol.48, No.4,429～432 pages, 1997) that promptly has projection 14.And, as stable contributive complexing agent to plating bath, with to access level and smooth metal level (epithelium) under the situation of using glycine relative, use and can access the epithelium of the prominent shape of knurl under the situation of tartaric acid or DL-malic acid, (reed is former etc. promptly to have the metal level 22 of projection 14, noncrystalline plating (non-Jing Quality メ Star キ), Vol.36, the 35th～37 page, 1994; Obtain formerly etc., circuit is installed the will (Hui Lu of association real dress Hui Chi), Vol.10, No.3,148～152 pages, 1995).

Metal level 22 can be made of the layer of single metal, also can be made of the layer of a plurality of metals.

Adhesive composite

As adhesive composite, composition, (2) that preferred (1) contains the potentiality curing agent of epoxy resin and epoxy resin are contained free-radical polymerised material and are produced the composition of curing agent of free free radical or the blend compositions of (1) and (2) by heating.

At first, the composition that (1) is contained the potentiality curing agent of epoxy resin and epoxy resin describes.Can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, bisphenol F phenolic varnish type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glycolylurea type epoxy resin, isocyanuric acid ester type epoxy resin, chain aliphatic epoxy resin as above-mentioned epoxy resin.These epoxy resin can by halogenation, also can be by hydrogenation.These epoxy resin also can will also be used more than 2 kinds.

As the potentiality curing agent so long as can make the just passable of epoxy resin cure.Can enumerate the catalyst type curing agent of anionic polymerization, the catalyst type curing agent of cationically polymerizable, the curing agent of polyaddition type as such potentiality curing agent.These can use separately or as the mixture more than 2 kinds.This wherein, from the rapidly-curable excellence, do not need to consider that stoichiometric angle considers the catalyst type curing agent of preferred anionic or cationically polymerizable.

Catalyst type curing agent as anion or cationically polymerizable, imidazoles system, hydrazides system, boron trifluoride-amine complex, sulfosalt, amine acid imide, diaminomaleonitrile, melamine and derivative thereof, the salt of polyamine, dicyandiamide can be enumerated, these modifier can also be used.Curing agent as polyaddition type can be enumerated polyamine class, polymercaptan, polyphenol, acid anhydrides.

Under the situation that has cooperated tertiary amines or imidazoles, epoxy resin solidifies by heating degree of several 10 seconds～a few hours in the middle temperature of 160 ℃～200 ℃ of degree as the catalyst type curing agent of anionic polymerization type.Therefore, up duration (pot life) becomes long, so preferred.

As the catalyst type curing agent of cationic polymerization type, the photonasty salt (with aromatic series diazol, aromatic series sulfosalt etc. is main use) of preference as make epoxy resin cure by the energy-ray irradiation.

And, as except the energy-ray irradiation by heating activate and making the material of epoxy resin cure, the aliphat sulfosalt is arranged.This curing agent is preferred because have the feature that is called rapidly-curable.

With these potentiality curing agent with polymer substances such as polyurethane series, polyester systems, inorganic matter lining such as metallic film such as nickel, copper and calcium silicates and the curing agent of microencapsulation is preferred because can prolong up duration.

Then, (2) are contained free-radical polymerised material and describe by the composition that heating produces the curing agent of free free radical.

Free-radical polymerised material is to have the material that carries out the functional group of polymerization by free radical.As so free-radical polymerised material, can enumerate acrylate and (also comprise corresponding methacrylate.Below identical) compound, acryloyl-oxy (comprise corresponding methacryloxypropyl.Below identical) compound, maleimide compound, citraconimide resin, Na Dike imide resin.Free-radical polymerised material can use with the state of monomer or oligomer, also can and use monomer and oligomer.

Object lesson as the aforesaid propylene acid compounds can be enumerated methyl acrylate, ethyl acrylate, the acrylic acid isopropyl ester, isobutyl acrylate, glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, the tetramethylol methane tetraacrylate, 2-hydroxyl-1,3-two propylene acyloxy propane, 2, two [4-(acryloyl-oxy ylmethoxy) phenyl] propane of 2-, 2, two [4-(acryloxy polyethoxy) phenyl] propane of 2-, the acrylic acid dicyclopentenyloxyethyl methacrylate, acrylic acid three ring esters in the last of the ten Heavenly stems, three (acrylyl oxy-ethyl) chlorinated isocyanurates, ammonia ester acrylate etc.These can use separately or with mixing more than 2 kinds.

And, can suitably use polymerization inhibitors such as hydroquinones, hydroquinones methyl ethers as required.Further, consider that the preferred acrylate compound has at least a kind the substituting group that is selected from the group who is made up of double cyclopentenyl, three ring decyls and triazine ring from improving stable on heating angle.

Above-mentioned maleimide compound is the compound that contains 2 above dimaleoyl iminos in molecule at least.As this type of maleimide compound, for example can enumerate 1-methyl-2,4-dimaleoyl imino benzene, N, a N '-penylene bismaleimides, N, N '-to the penylene bismaleimides, N, a N '-toluene support bismaleimides, N, N '-4,4-biphenylene bismaleimides, N, N '-4,4-(3, the support of 3 '-dimethyl diphenyl) bismaleimides, N, N '-4,4-(3,3 '-dimethyl diphenylmethane) bismaleimides, N, N '-4,4-(3,3 '-diethyl diphenyl methane) bismaleimides, N, N '-4,4-diphenyl methane bismaleimides, N, N '-4,4-diphenyl propane bismaleimides, N, N '-3,3 '-diphenyl sulphone (DPS) bismaleimides, N, N '-4,4-diphenyl ether bismaleimides, 2, two (4-(4-maleimide phenoxyl) phenyl) propane of 2-, 2, two (3-sec-butyl-4,8-(4-maleimide phenoxyl) phenyl) propane of 2-, 1, two (4-(4-maleimide phenoxyl) phenyl) decane of 1-, 4,4 '-cyclohexylidene-two (1-(4-maleimide phenoxyl) phenoxy group)-2-cyclohexyl benzene, 2, two (4-(4-maleimide phenoxyl) phenyl) HFC-236fa of 2-.These can use separately or with mixing more than 2 kinds.

Above-mentioned citraconimide resin is the material that the citraconimide compound that will have 1 citraconimide base at least in molecule is polymerized.As the citraconimide compound, for example can enumerate the phenyl citraconimide, 1-methyl-2,4-dual-citraconic imide base benzene, N, a N '-phenyl dual-citraconic imide, N, N '-to the phenyl dual-citraconic imide, N, N '-4,4-biphenylene dual-citraconic imide, N, N '-4,4-(3, the support of 3-dimethyl diphenyl) dual-citraconic imide, N, N '-4,4-(3, the 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-diphenyl ether dual-citraconic imide, N, N '-4,4-diphenyl sulphone (DPS) dual-citraconic imide, 2, two (4-(the 4-citraconimide phenoxyl) phenyl) propane of 2-, 2, two (the 3-sec-butyls-3 of 2-, 4-(4-citraconimide phenoxyl) phenyl) propane, 1, two (4-(the 4-citraconimide phenoxyl) phenyl) decane of 1-, 4,4 '-cyclohexylidene-two (1-(4-citraconimide phenoxyl) phenoxy group)-2-cyclohexyl benzene, 2, two (4-(the 4-citraconimide phenoxyl) phenyl) HFC-236fa of 2-.These can separately or mix more than 2 kinds and use.

Above-mentioned Na Dike imide resin is the material that the Na Dike imide compound that will have 1 Na Dike imide at least in molecule is polymerized.As the Na Dike imide compound, for example can enumerate phenyl Na Dike acid imide, 1-methyl-2, the two Na Dike imide benzene of 4-, N, the two Na Dike acid imides of a N '-phenyl, N, N '-to the two Na Dike acid imides of phenyl, N, N '-4, the two Na Dike acid imides of 4-biphenylene, N, N '-4,4-(3, the support of 3-dimethyl diphenyl) two Na Dike acid imides, N, N '-4,4-(3, the 3-dimethyl diphenylmethane) two Na Dike acid imides, N, N '-4,4-(3,3-diethyl diphenyl methane) two Na Dike acid imides, N, N '-4, the two Na Dike acid imides of 4-diphenyl methane, N, N '-4, the two Na Dike acid imides of 4-diphenyl propane, N, N '-4, the two Na Dike acid imides of 4-diphenyl ether, N, N '-4, the two Na Dike acid imides of 4-diphenyl sulphone (DPS), 2, two (4-(the 4-Na Dike imide phenoxy group) phenyl) propane of 2-, 2, two (the 3-sec-butyls-3 of 2-, 4-(4-Na Dike imide phenoxy group) phenyl) propane, 1, two (4-(the 4-Na Dike imide phenoxy group) phenyl) decane of 1-, 4,4 '-cyclohexylidene-two (1-(4-Na Dike imide phenoxy group) phenoxy group)-2-cyclohexyl benzene, 2, two (4-(the 4-Na Dike imide phenoxy group) phenyl) HFC-236fa of 2-.These can use separately or with mixing more than 2 kinds.

And, preferred and with above-mentioned free-radical polymerised thing and the free-radical polymerised material represented by following chemical formula (I) with phosphate ester structure.In this case, owing to improve adhesive strength, be suitable for each other bonding of circuit electrode to inorganic matter surfaces such as metals.

[changing 1]

In the formula, n represents 1～3 integer.

Above-mentioned free-radical polymerised material with phosphate ester structure can obtain by phosphoric anhydride and (methyl) acrylic acid 2-hydroxy methacrylate are reacted.As the free-radical polymerised material with phosphate ester structure, concrete have one (2-methacryloxyethyl) phosphate ester acid, two (2-methacryloxyethyl) phosphate ester acid.These can use separately or with mixing more than 2 kinds.

Above-mentioned use level with free-radical polymerised material of the phosphate ester structure of representing by chemical formula (I), with respect to free-radical polymerised material with total 100 mass parts of the film formation material that cooperates as required, preferred 0.01～50 mass parts is more preferably 0.5～5 mass parts.

Above-mentioned free-radical polymerised material can and be used with the pi-allyl acrylate.In this case, the use level of pi-allyl acrylate, with respect to free-radical polymerised material with total 100 mass parts of the film formation material that cooperates as required, preferred 0.1～10 mass parts is more preferably 0.5～5 mass parts.

The curing agent that produces free free radical by heating is the curing agent that produces free free radical by heating and decomposition.Can enumerate peroxide compound, azo based compound as such curing agent.Such curing agent can connect according to target suitably to be selected temperature, connect hours, pot life etc.From high response and the viewpoint that improves pot life, the temperature of preferred 10 hours half-life more than 40 ℃ and the temperature of 1 minute half-life at the organic peroxide below 180 ℃, the temperature of preferred 10 hours half-life more than 60 ℃ and the temperature of 1 minute half-life at the organic peroxide below 170 ℃.

The use level of above-mentioned curing agent, under the connect hours is situation below 25 seconds, in order to obtain enough reactivities, with respect to total 100 mass parts of free-radical polymerised material and the film formation material that cooperates as required, preferred 2～10 mass parts degree are more preferably 4～8 mass parts.In addition, the use level of the curing agent under the situation that does not limit the connect hours, with respect to free-radical polymerised material with total 100 mass parts of the film formation material that cooperates as required, preferred 0.05～20 mass parts, more preferably 0.1～10 mass parts.

As the curing agent that produces free free radical by heating, more specifically can enumerate diacyl peroxide, peroxy dicarbonate, peroxyester ketal peroxide, dialkyl peroxide, hydroperoxides, silicyl peroxide.

And from the viewpoint of the corrosion that can suppress

circuit electrode

32,42, chloride ion that contains in the agent of curing agent preferred consolidation or organic acid concentration further, are more preferably the few curing agent of organic acid that produces after the heating and decomposition below 5000ppm.

As such curing agent, can enumerate peroxyester, dialkyl peroxide, hydroperoxides, silicyl peroxide particularly, be more preferably from the peroxyester that can obtain high response selected.In addition, above-mentioned curing agent can suitably mix use.

As peroxyester; can enumerate peroxidating neodecanoic acid isopropylbenzene ester; 1; 1; 3; 3-tetramethyl butyl new decanoate ester peroxide; 1-cyclohexyl-1-Methylethyl new decanoate ester peroxide; uncle's hexyl new decanoate ester peroxide; the peroxidating trimethylace tonitric tert-butyl ester; 1; 1; 3; 3-tetramethyl butyl peroxidating-2 ethyl hexanoic acid ester; 2; 5-dimethyl-2; 5-two (peroxidating of 2-ethyl hexanoyl base) hexane; 1-cyclohexyl-1-Methylethyl peroxidating-2 ethyl hexanoic acid ester; peroxidating-own the ester of 2 ethyl hexanoic acid uncle; peroxide-2-ethyl hexanoic acid tert-butyl; the peroxidating tert-butyl isobutyrate; 1; two (tert-butyl hydroperoxide) cyclohexanes of 1-; the own ester of peroxidating isopropyl one carbonic acid uncle; peroxidating-3; 5; the 5-tri-methyl hexanoic acid tert-butyl ester; the peroxidating laurate tert-butyl ester; 2; 5-dimethyl-2,5-two (peroxidating of toluoyl base) hexane; the peroxidating isopropyl one carbonic acid tert-butyl ester; peroxidating-2-ethylhexyl one carbonic acid the tert-butyl ester; the own ester of peroxidating benzoic acid uncle; peroxide acetic acid butyl ester.

As dialkyl peroxide, can enumerate α, α '-two (tert-butyl hydroperoxide) diisopropyl benzene, diisopropylbenzyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, tert butyl isopropyl benzene peroxide.

As hydroperoxides, can enumerate diisopropyl benzene hydrogen peroxide, isopropyl benzene hydroperoxide.

As diacyl peroxide; can enumerate isobutyl peroxide, 2; 4-dichloro-benzoyl peroxide, 3; 5,5-trimethyl acetyl peroxide, decoyl peroxide, lauroyl peroxide, hard ester acyl peroxide, succinyl peroxide, benzoyl peroxidating toluene, benzoyl peroxide.

As peroxy dicarbonate, can enumerate peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, two (4-tert-butylcyclohexyl) peroxy dicarbonate, two-2-ethyoxyl methoxy base peroxy dicarbonate, two (peroxidating of 2-ethylhexyl), two carbonic esters, peroxy dicarbonate dimethoxy butyl ester, two (3-methyl-3-methoxyl group butyl peroxyization) two carbonic esters.

As ketal peroxide, can use 1, two (peroxidating of uncle's hexyl)-3,3 of 1-, 5-trimethyl-cyclohexane, 1, two (peroxidating of the uncle's hexyl) cyclohexanes, 1 of 1-, two (tert-butyl hydroperoxide)-3,3 of 1-, 5-trimethyl-cyclohexane, 1,1-(tert-butyl hydroperoxide) cyclododecane, 2, two (tert-butyl hydroperoxide) decane of 2-.

As the silicyl peroxide, can enumerate tert-butyl group trimethyl silyl peroxide, two (tert-butyl group) dimetylsilyl peroxide, tert-butyl group trivinyl silicyl peroxide, two (tert-butyl group) divinyl silicyl peroxide, three (tert-butyl group) vinyl silicyl peroxide, tert-butyl group triallyl silicyl peroxide, two (tert-butyl group) diallyl silicyl peroxide, three (tert-butyl group) pi-allyl silicyl peroxide.

These curing agent can use separately or with mixing more than 2 kinds, decomposition accelerating agent, inhibitor etc. can also be mixed and use.And, also can with these curing agent with lining such as the polymer substance of polyurethane series, polyester system microencapsulation.Microencapsulation curing agent preferred because up duration is extended.

Adhesive composite can add film formation material as required to be used.Film formation material has following effect: with the liquid solidification and will constitute composition and make the film shape time, can make the operation of this film become easy, give that this film is difficult for splitting, broken, the mechanical property that is clamminess etc., can operate as film down at common state (normal temperature and pressure).

Can enumerate phenoxy resin, vinyl-formal resin, polystyrene resin, polyvinyl butyral resin, mylar, polyamide, xylene resin, polyurethane resin etc. as film formation material.This wherein considers preferred phenoxy resin from the angle of cementability, intermiscibility, thermal endurance, mechanical strength excellence.

Phenoxy resin be by can phenols with 2 officials and epoxyhalopropane react to producing high-molecular, perhaps can epoxy resin with 2 officials and 2 officials can phenols carry out addition polymerization and the resin that obtains.Phenoxy resin for example can by make 2 officials can phenols 0.985～1.015 mole of 1 mole and epoxyhalopropane, in the presence of catalyst such as alkali metal hydroxide, in non-reactive solvent, under 40～120 ℃ temperature, react and obtain.

And, as phenoxy resin, from the mechanical property of resin or the viewpoint of thermal characteristics, especially preferably the cooperation equivalent proportion with 2 officials energy epoxy resin and 2 officials energy phenols is made as epoxy radicals/phenolic hydroxyl group=1/0.9～1/1.1, in the presence of catalyst such as alkali metal compound, organophosphor based compound, cyclic amine based compound, in organic solvents such as the acid amides system of boiling point more than 120 ℃, ether system, ketone system, lactone system, alcohol system, be heated to 50～200 ℃ and carry out sudden reaction and obtain to react the condition of solid constituent below 50 quality %.

As above-mentioned 2 officials energy epoxy resin, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D type epoxy resin, bisphenol-s epoxy resin, biphenyldiglycid ether, methyl substituted biphenyldiglycid ether.

2 officials can phenols be the materials with 2 phenol hydroxyls.Can for example can enumerate bisphenols such as hydroquinones, bisphenol-A, Bisphenol F, bisphenol-A D, bisphenol S, bisphenol fluorene, methyl substituted bisphenol fluorene, dihydroxybiphenyl, methyl substituted dihydroxybiphenyl by phenols as 2 officials.

Phenoxy resin can be by free-radical polymerised functional group or other reactive compounds modification (for example epoxide modified).Phenoxy resin can use separately or with mixing more than 2 kinds a kind.

Adhesive composite can further contain at least a polymer or copolymer as monomer component in acrylic acid, acrylate, methacrylate and the acrylonitrile.Here, relax excellent angle from stress and consider, preferred also with containing the glycidyl acrylate of glycidyl ether or the copolymerization system acrylic rubber of glycidyl methacrylate.The weight average molecular weight of these acrylic rubbers is considered preferred more than 200,000 from the angle of the cohesiveness that improves bonding agent.

The use level of conducting particles 12 is 0.1～30 parts by volume with respect to adhesive composite 100 parts by volume preferably, and its use level can specifically be used according to purposes.Because the viewpoint of the short circuit of the circuit electrode that causes of excessive conducting particles 12 etc., the use level of conducting particles 12 is 0.1～10 parts by volume more preferably from preventing.

Also can further contain rubber particle, filler, softening agent, promoter, age resister, colouring agent, fire retardant, thixotropic agent, coupling agent, phenol resin, melmac, isocyanates in the circuit connection material.

Rubber particle is so long as have the average grain diameter below 2 times of the average grain diameter of the conducting particles 12 that is cooperated, and has the getting final product of the storage elastic modulus below 1/2 of conducting particles 12 and adhesive composite storage elastic modulus at room temperature.Especially the material of rubber particle is that the particulate of organosilicon, acrylic compounds emulsion, SBR, NBR, polybutadiene rubber is fit to separately or will mixes more than 2 kinds and use.These crosslinked rubber particles of 3 dimensions, the solvent resistance excellence is dispersed in the adhesive composite easily.

Connection reliability etc. contain in the circuit connection material under the situation of filler, so because can improve preferred.Filler is as long as its maximum gauge is just the using 1/2 below of particle diameter of conducting particles 12.As long as its maximum gauge is just the using 1/2 below of particle diameter of conducting particles.And, also to use under the situation of the particle that does not have conductivity, filler is as long as just can use below the diameter of the particle that does not have conductivity.

The use level of filler is with respect to adhesive composite 100 parts by volume, preferred 5～60 parts by volume.If surpassing 60 parts by volume, use level will exist connection reliability to improve the saturated tendency of effect, if the inadequate tendency of effect that less than 5 parts by volume will exist filler to add.

As above-mentioned coupling agent, contain the compound of vinyl, acryloyl group, epoxy radicals or NCO, so because cementability improves preferred.

Circuit member connecting method

Next, the manufacture method to the syndeton of foregoing circuit parts describes.

At first, prepare to have the 1st above-mentioned circuit electrode 32 the 1st circuit block 30, have the 2nd circuit block 40, the circuit connection material of the 2nd circuit electrode 42.Prepare for example to be configured as membranaceous circuit connection material (below, be called membranaceous circuit connection material) 50 as circuit connection material.

Fig. 3 is the sectional view of an execution mode of the membranaceous circuit connection material that the present invention relates to of expression.Membranaceous circuit connection material 50 is that foregoing circuit is connected material forming is membranaceous circuit connection material, and circuit connection material contains conducting particles 12 and the adhesive composite 51 that has projection 14 in face side usually.Generally, the adhesive composite that contains in the circuit connection material has cementability, by the cured of the 1st and the

2nd circuit electrode

30,40 is solidified.Preferred 10～50 μ m of the thickness of membranaceous circuit connection material 50.

Then, on the 1st circuit block 30, place membranaceous circuit connection material 50.Then, the 2nd circuit block 40 is placed on the membranaceous circuit connection material 50, makes the 1st circuit electrode 32 mutually opposed with the 2nd circuit electrode 42.Thus, can make membranaceous circuit road connect material 50 between the 1st circuit block 30 and the 2nd circuit block 40.At this moment, membranaceous circuit connection material 50 is membranaceous, easily operation.Therefore, according to this membranaceous circuit connection material 50, when connecting the 1st circuit block 30 and the 2nd circuit block 40, can the operation that be connected of the 1st circuit block 30 and the 2nd circuit block 40 be carried out easily easily between between them.

Then, cured is implemented in pressurization in the time of by the membranaceous circuit connection material of the 1st circuit block 30 and the heating of the 2nd circuit block 40 50, forms circuit connecting section part 10 between the

circuit block

30,40 the 1st and the 2nd.Cured can be undertaken by general method, and the method can suitably be selected by adhesive composite.

At this moment, the jut 14 of the conducting particles 12 in the circuit connecting section part 10 runs through insulating properties material 11 and contacts with the 1st circuit electrode the 32, the 2nd circuit electrode 42.And the metal level 22 of the inboard of the jut 14 of conducting particles 12 is absorbed in nucleome 21 sides.At this moment, because the repulsion of the plastics (organic polymer) of nucleome 21 makes jut 14 be pressed towards circuit electrode 32,42 sides, jut 14 is in the state that further also is absorbed in circuit electrode.And, the metal level of the conducting particles 12 in the circuit connection material or outermost layer are under the situation of Ni or Ni alloy, because it is harder than Au, so with in the past outermost layer is that the conducting particles of Au is compared, jut 14 is absorbed in darker for the 1st or the 2nd circuit electrode 32,42, the contact area of conducting particles 12 and circuit electrode 32,42 increases, and connects resistance stabilization.And the metal level by making conducting particles 12 or its outermost Vickers hardness are in 400～1000 scope, and jut 14 will become big for being absorbed in of circuit electrode 32,42.Then, be cured by circuit connection material and handle adhesive composite 51 and be cured, realize high-adhesive-strength, keep conducting particles 12 and the 1st and the 2nd circuit electrode 32,42 firm state of contact for a long time the 1st circuit block 30 and the 2nd circuit block 40.The state of such syndeton can be confirmed by the cross section with the syndeton of electron microscope observation circuit block.And, use as circuit substrate under the situation of transparent glass substrate, can confirm by the surface that glass substrate is observed circuit connecting section.

Thereby, let loose on the surface of the 1st and/or the

2nd circuit electrode

32,42, no concave-convex being arranged, can fully reduce the opposed the 1st with the resistance that is connected of 32,42 of the 2nd circuit electrodes, and can in the good electrical connection of reaching the 1st circuit electrode 32 and the 2nd circuit electrode 42, fully improve the long-term reliability of the electrical characteristics of 32,42 of the 1st and the 2nd circuit electrodes.

In addition, in the above-described embodiment, use membranaceous circuit connection material 50 to make the syndeton of circuit block, but also can replace membranaceous circuit connection material 50, use circuit connection material described later.In this case, circuit connection material is dissolved in the solvent, again with either party and the drying of this solution coat at the 1st circuit block 30 or the 2nd circuit block 40, just can be between the 1st and the

2nd circuit block

30,40.

In addition, membranaceous circuit connection material 50 can be put (not expression among the figure) coating foregoing circuit connection material by going up at support (PETG film etc.) with being coated with frock, and makes by the heated-air drying of preset time.

More than, suitable execution mode of the present invention is illustrated, but the present invention is not limited by this.

Embodiment

Below, specify the present invention based on embodiment, but the present invention is not limited by this.

The making of conducting particles

The making of nucleome

Change the mixing ratio of tetramethylol methane tetraacrylate, divinylbenzene and the rare monomer of benzene second, use benzoyl peroxide to hang turbid polymerization as polymerization initiator.Then, the nucleome of the average grain diameter by the classification of gained condensate having been obtained have about 3 μ m.

The making of conducting particles No.1

Electroless plating Ni is implemented on the surface of above-mentioned nucleome handle, made the conducting particles No.1 of Ni layer (metal level) with homogeneous thickness 100nm.

The making of conducting particles No.2

By on conducting particles No.1 Au being replaced plating with the thickness of 25nm, formation has the Au layer of homogeneous thickness, and has made conducting particles No.2.

The making of conducting particles No.3

Specially permit No. 3696429 etc. based on Japan, input amount, treatment temperature and the time of the plating bath when handling by adjusting plating Ni is also changed the thickness of coating, forms the projection of plating Ni on the surface of above-mentioned nucleome.Thus, made the conducting particles No.3 that the target thickness that also contains projection and Ni layer is 180～210nm.

The making of conducting particles No.4

By on conducting particles No.3 Au being replaced plating with the thickness of 25nm, formation has the Au layer of a plurality of projections, and has made conducting particles No.4.

For conducting particles No.1～4 that make as mentioned above, use electron microscope (Hitachi makes, trade name " S-800 ") to observe, calculate the distance between the projection of the height of having measured projection and adjacency.The height and the distance between projection of the metal level material of each conducting particles, Vickers hardness, projection are as shown in table 1.

Table 1

The making of circuit connection material

The modulation of phenoxy resin solution

50g is dissolved in the mixed solvent of toluene/ethyl acetate=50/50 (mass ratio) with phenoxy resin (weight average molecular weight 45000, U.S. combinating carbide company makes, trade name " PKHC "), has modulated the phenoxy resin solution of solid constituent 40 quality %.

Synthesizing of ammonia ester acrylate

Stir polycaprolactone glycol (weight average molecular weight: 800) 400 mass parts, 2-hydroxypropyl acrylate 131 mass parts, be heated to 50 ℃ as dibutyltin dilaurate 0.5 mass parts of catalyst with as monomethyl ether of hydroquinone 1.0 mass parts of polymerization inhibitor the time and mix.Then,, drip IPDI 222 mass parts, be warmed up to 80 ℃ when further stirring and carry out the ammonia esterification to this mixed liquor.After the reactivity of affirmation NCO reaches more than 99%, reduce reaction temperature and obtained ammonia ester acrylate.

The making of circuit connection material A

(solid component content: 50g) 125g, above-mentioned ammonia ester acrylate 49g, phosphate type acrylate 1g and conduct have obtained adhesive composite by the own ester 5g of peroxidating-2 ethyl hexanoic acid uncle that heating produces the curing agent of free free radical to mix above-mentioned phenoxy resin solution.With respect to gained adhesive composite 100 mass parts, disperse 2.3 mass parts to modulate circuit connection material conducting particles No.3.

Then, use to be coated with frock and to put this circuit connection material is coated on single face is carried out on the PET film that surface-treated thickness is 50 μ m, by 70 ℃ of heated-air dryings of 3 minutes, having formed thickness on the PET film is the membranaceous circuit connection material A of 18 μ m.

The making of circuit connection material B

Replace conducting particles No.3 to use the conducting particles No.1 of 2.3 mass parts to carry out equally with circuit connection material A in addition, having made thickness is the membranaceous circuit connection material B of 18 μ m.

The making of circuit connection material C

Replace conducting particles No.3 to use the conducting particles No.2 of 2.1 mass parts to carry out equally with circuit connection material A in addition, having made thickness is the membranaceous circuit connection material C of 18 μ m.

The making of circuit connection material D

Replace conducting particles No.3 to use the conducting particles No.4 of 2.1 mass parts to carry out equally with circuit connection material A in addition, having made thickness is the membranaceous circuit connection material D of 18 μ m.

Embodiment 1

The flexible electric circuit board (hereinafter referred to as FPC) that preparation has 2 layers of structure being made up of polyimide film (thickness 38 μ m) and zinc-plated Copper Foil (thickness 8 μ m) as the 1st circuit block.For the circuit of this FPC, be set at live width 18 μ m and spacing 50 μ m.

Then, as the glass substrate (thickness 1.1mm) that possesses ITO circuit substrate (thickness 50nm, sheet resistance＜20 Ω) on the 2nd circuit block preparation surface.For the circuit of this 2nd circuit block, be set at live width 25 μ m and spacing 50 μ m.

Then, on the 2nd circuit block, stick and be cut into given size (1.5 * 30mm) circuit connection material A, heating is 3 seconds under 70 ℃, the condition of 1.0MPa, and pressurizes interim the connection.Then, peel off the PET film after, configuration FPC makes FPC and the 2nd circuit material clip circuit connection material A, makes the aligned in position of the circuit of the circuit of FPC and the 2nd circuit block.Then, with 170 ℃, 3MPa, 10 seconds condition heat from FPC top, pressurizeing formally is connected FPC with the 2nd circuit block.Made the syndeton of circuit block like this.

Embodiment 2

As the 1st circuit block, prepare FPC similarly to Example 1.Then, as the glass substrate (thickness 1.1mm) of the circuit electrode (sheet resistance＜20 Ω) of the 3-tier architecture that possesses IZO (outermost layer, thickness are 50nm)/Cr (thickness 20nm)/Al (thickness 100nm) on the 2nd circuit block preparation surface.For the circuit of this 2nd circuit block, be set at live width 25 μ m and spacing 50 μ m.Then, use circuit connection material A similarly to Example 1, made the syndeton of circuit block.

Embodiment 3

As the 1st circuit block, prepare FPC similarly to Example 1.Then, as the glass substrate (thickness 1.1mm) of the circuit electrode (sheet resistance＜20 Ω) of 2 layers of structure that possess ITO (outermost layer, thickness are 50nm)/Cr (thickness 200nm) on the 2nd circuit block preparation surface.For the circuit of this 2nd circuit block, be set at live width 25 μ m and spacing 50 μ m.Then, use circuit connection material A similarly to Example 1, made the syndeton of circuit block.

Embodiment 4

As the 1st circuit block, prepare FPC similarly to Example 1.Then, glass substrate (thickness 1.1mm) as the circuit electrode (sheet resistance＜20 Ω) of 4 layers of structure that possess ITO (outermost layer, thickness are 50nm)/Ti (thickness 100nm)/Al (thickness 200nm)/Ti (thickness 100nm) on the 2nd circuit block preparation surface.For the circuit of this 2nd circuit block, be set at live width 25 μ m and spacing 50 μ m.Then, use circuit connection material A similarly to Example 1, made the syndeton of circuit block.

Embodiment 5

As the 1st circuit block, prepare FPC similarly to Example 1.Then, as the glass substrate (thickness 1.1mm) that possesses Al circuit electrode (thickness 200nm, sheet resistance＜5 Ω) on the 2nd circuit block preparation surface.For the circuit of this 2nd circuit block, be set at live width 25 μ m and spacing 50 μ m.Then, use circuit connection material A similarly to Example 1, made the syndeton of circuit block.

Comparative example 1

Other carry out according to embodiment 1 in addition to replace circuit connection material A to use circuit connection material B, have made the syndeton of circuit block.

Comparative example 2

Other carry out according to embodiment 2 in addition to replace circuit connection material A to use circuit connection material B, have made the syndeton of circuit block.

Comparative example 3

Other carry out according to embodiment 3 in addition to replace circuit connection material A to use circuit connection material B, have made the syndeton of circuit block.

Comparative example 4

Other carry out according to embodiment 4 in addition to replace circuit connection material A to use circuit connection material B, have made the syndeton of circuit block.

Comparative example 5

Other carry out according to embodiment 5 in addition to replace circuit connection material A to use circuit connection material B, have made the syndeton of circuit block.

Comparative example 6

Other carry out according to embodiment 1 in addition to replace circuit connection material A to use circuit connection material C, have made the syndeton of circuit block.

Comparative example 7

Other carry out according to embodiment 2 in addition to replace circuit connection material A to use circuit connection material C, have made the syndeton of circuit block.

Comparative example 8

Other carry out according to embodiment 3 in addition to replace circuit connection material A to use circuit connection material C, have made the syndeton of circuit block.

Comparative example 9

Other carry out according to embodiment 4 in addition to replace circuit connection material A to use circuit connection material C, have made the syndeton of circuit block.

Comparative example 10

Other carry out according to embodiment 5 in addition to replace circuit connection material A to use circuit connection material C, have made the syndeton of circuit block.

Comparative example 11

Other carry out according to embodiment 1 in addition to replace circuit connection material A to use circuit connection material D, have made the syndeton of circuit block.

Comparative example 12

Other carry out according to embodiment 2 in addition to replace circuit connection material A to use circuit connection material D, have made the syndeton of circuit block.

Comparative example 13

Other carry out according to embodiment 3 in addition to replace circuit connection material A to use circuit connection material D, have made the syndeton of circuit block.

Comparative example 14

Other carry out according to embodiment 4 in addition to replace circuit connection material A to use circuit connection material D, have made the syndeton of circuit block.

Comparative example 15

Other carry out according to embodiment 5 in addition to replace circuit connection material A to use circuit connection material D, have made the syndeton of circuit block.

The mensuration that connects resistance

To the syndeton of foregoing circuit parts, use the resistance value that is connected between universal instrument (ADC Co., Ltd. makes, trade name " digital multimeter the 7461A ") circuit electrode of mensuration the 1st circuit block (FPC) and the circuit electrode of the 2nd circuit block.Connect resistance value and be in the early stage in the constant temperature and humidity cabinet of (after the connection immediately) and 80 ℃, 95%RH and keep 500 hours (hot and humid processing) back mensuration.The result is as shown in table 2.

In table 2, connect resistance value with the mean value of 37 of the resistance between the adjacency circuit and 3 times standard deviation value sum (x+3 σ) expression.And the resistance increment rate is to represent with percentage to the hot and humid recruitment of handling the back resistance value from the initial stage resistance value, specifically calculates according to following formula:

Resistance increment rate (%)=[(handling back resistance value-initial stage resistance value)/initial stage resistance value] * 100

As the judgement that improves effect of connection reliability, resistance increment rate less than 10% has been designated as improved effect, with more than 10% and less than 20% be designated as product level in the past, do not improve effect (NG) with being designated as more than 20%.

The conducting particles number that exists on the circuit electrode

Use differential interference microscope, the conducting particles number that will exist on each circuit electrode in the syndeton of foregoing circuit parts is counted (n=38) by eyes.Its result, the average conducting particles number on the circuit electrode of embodiment 1～15 and comparative example 1～25 does not have to find the extreme increase and decrease of the conducting particles number that the difference by circuit connection material or circuit block causes in 32～45 scope.

Table 2

As shown in table 2, under the situation of whole or the 2nd circuit block that the surface is made of ITO or IZO that uses circuit electrode, in the syndeton of the circuit block of embodiment 1～4, obtained resistance increment rate less than 7.5% so very little result.Relative therewith, the resistance increment rate of the syndeton of comparative example 1～4 is about 27～39%, and the resistance increment rate of the syndeton of comparative example 6～9 is about 20～25%, and the resistance increment rate of the syndeton of comparative example 11～14 is about 14～18%.

Hence one can see that, the whole or surperficial circuit electrode that constitutes by ITO or IZO for circuit electrode, by containing the outermost layer with projection and metal level or metal level is that the circuit connection material of the conducting particles of Ni is used for connecting, and can see the improvement of connection reliability.

And, possessing in use under the situation of the 2nd circuit block of Al circuit electrode, in the embodiment 5 that connects with the circuit connection material that contains the conducting particles with projection, the comparative example 15, the result is about 3.5% for the resistance increment rate, and is less.This result, being considered to may be that the projection on conducting particles surface owing to connecting punctures the reason that it is contacted with circuit electrode to the oxide-film on Al circuit electrode surface.To this, in the comparative example 5,10 that connects with the circuit connection material that contains the conducting particles that does not have projection, the resistance increment rate of comparative example 10 is about 34%, and the resistance increment rate of comparative example 15 is about 15%.

In addition, use and have projection and metal level embodiment 5 as the conducting particles of Ni, have projection and outermost layer and be same degree with using as the resistance increment rate of the comparative example 15 of the conducting particles of Au, therefore, for the circuit block that circuit electrode is made of Al, there are the effect of improving connection reliability and the inapparent tendency that cause by the outermost different metal kind of conducting particles.

And, observe the result in cross section of the syndeton of the circuit block of in embodiment 1～5, making with scanning electron microscopy (SEM), the metal level of inside part of jut of having confirmed to constitute the metal level of conducting particles is absorbed in nucleome.As its example, the section S EM photo of connecting portion is shown in Fig. 4 in the syndeton of the circuit block that will make in embodiment 2.

According to more than, confirmed the syndeton of parts in a circuit according to the invention, can be in the good electrical connection of reaching between opposed circuit electrode, under hot and humid environment or in the thermal shock test etc., also can fully improve stable connection reliability.

Utilize possibility on the industry

Connecting material in a circuit according to the invention can be in good being electrically connected of reaching between opposed circuit electrode When connecing, can fully improve the long-term reliability of the electrical characteristics between circuit electrode. And, according to this Bright, the johning knot of the very excellent circuit block of the long-term reliability of the electrical characteristics between circuit electrode can be provided Structure and attaching method thereof.

Claims

1. a circuit connection material is characterized in that, is used to be electrically connected 2 circuit blocks that are formed with circuit electrode, so that described circuit electrode is opposed,

Described circuit connection material contains adhesive composite and conducting particles,

Described conducting particles possesses the metal level of the nucleome that is formed by organic high molecular compound and this nucleome that is covered,

Described metal level has towards the jut of the outside projection of conducting particles, and described metal level is made of nickel or nickel alloy,

When described conducting particles was applied in pressure, the metal level of the inside part of described jut was absorbed in described nucleome.

2. circuit connection material according to claim 1 is characterized in that, the Vickers hardness of described metal level is 400～1000.

3. a circuit connection material is characterized in that, is used to be electrically connected 2 circuit blocks that are formed with circuit electrode, so that described circuit electrode is opposed,

Described conducting particles possesses a plurality of metal levels of the nucleome that is formed by organic high molecular compound and this nucleome that is covered,

Described metal level has towards the jut of the outside projection of conducting particles, and the outermost layer of described metal level is made of nickel or nickel alloy,

4. circuit connection material according to claim 3 is characterized in that, the outermost Vickers hardness of described metal level is 400～1000.

5. the syndeton of a circuit block is characterized in that, possess 2 circuit blocks being formed with circuit electrode and described circuit electrode and being disposed relatively,

Between described circuit block, the circuit connecting section part that described circuit electrode is electrically connected by heating and pressurizing,

Described circuit connecting section part is the solidfied material of each described circuit connection material of claim 1～4, and at the inside part of the jut of the conducting particles that described circuit connection material contained, metal level is absorbed in nucleome.

6. the syndeton of circuit block according to claim 5 is characterized in that, the surface of at least one side's of the circuit electrode of described 2 circuit blocks circuit electrode is formed by indium tin oxide.

7. according to the syndeton of claim 5 or 6 described circuit blocks, it is characterized in that the surface of at least one side's of the circuit electrode of described 2 circuit blocks circuit electrode is formed by indium-zinc oxide.

8. circuit member connecting method, it is characterized in that, be formed with between 2 circuit blocks that circuit electrode and described circuit electrode disposed relatively, each described circuit connection material of claim 1～4 is set, by heating and pressurizing described circuit electrode is electrically connected, the metal level of the inside part of the jut of the conducting particles that makes described circuit connection material thus and contained is absorbed in nucleome.