CN101794638B - Circuit connecting material, connecting structure for circuit parts and connecting method for circuit parts - Google Patents

Abstract

The invention relates to a circuit connecting material, a connecting structure for circuit parts and a connecting method for circuit parts. The circuit connecting material contains an optical or thermal cured adhesive composite and an organic compound with urethano and ester group and is used for connecting circuit parts provided with base plates and circuit electrodes formed on the main surfaces of the base plates. The weight-average molecular weight of the organic compound is 5,000 to 100,000. When the circuit connecting material and the connecting method of the invention are used for connecting the circuit parts, the connecting structure of the circuit parts which have high adhesion strength and good durability at high temperature and humidity can be obtained.

Description

The syndeton of circuit connection material, circuit block and circuit member connecting method

The application is to be on July 21st, 2006 applying date; National applications number is 200680055407.8; International application no is PCT/JP2006/314475, and denomination of invention is divided an application for the application of " syndeton of circuit connection material, circuit block and circuit member connecting method ".

Technical field

The present invention relates to be used for syndeton and circuit member connecting method with the circuit connection material connected to one another of the circuit block with circuit electrode, circuit block.

Background technology

In recent years, in the precision electronic device field, because the densification of circuit constantly develops, electrode width, electrode gap become minimum, and therefore coming off, peel off or offset of distribution take place easily.In order to address this problem, developing excellent and the electric and electronic with sufficiently long up time of low temperature rapidly-curable with circuit connection material (for example, patent documentation 1,2).

Patent documentation 1: No. 98/44067 brochure of International Publication

Patent documentation 2: No. 01/015505 brochure of International Publication

Summary of the invention

But according to the kind of the material that constitutes the circuit block that is connected, can there be the sufficient inadequately problem of adhesive strength in above-mentioned circuit connection material in the past.Particularly the substrate of support circuit electrode is when the substrate that is formed by PETG, polyimide resin, polyether sulfone, acrylic resin or glass or the surface of circuit block is formed with when layer that is made up of organic siliconresin, polyimide resin, acrylic resin etc., can exist adhesive strength significantly to reduce such problem.

Therefore; The objective of the invention is to; A kind of such circuit connection material is provided; That is, even connect circuit block with the substrate that forms by PETG, polyimide resin, polyether sulfone, acrylic resin or glass or surface be formed with by organic siliconresin, polyimide resin, acrylic resin etc. constitute layer circuit block the time, also can obtain enough adhesive strengths.

Circuit connection material of the present invention contains the adhesive composite through light or hot curing and has urethano and the organic compound of ester group, is used for being connected to each other with the circuit block that is formed at the circuit electrode on its interarea having substrate.

Circuit connection material of the present invention; Through and with adhesive composite and have urethano and the organic compound of ester group; Become the circuit connection material that is described below: though connection have the substrate that forms by PETG, polyimide resin, polyether sulfone, acrylic resin or glass circuit block or the surface be formed with by organic siliconresin, polyimide resin, acrylic resin etc. constitute the layer circuit block the time, also can obtain enough adhesive strengths.

Above-mentioned adhesive composite preferably contains free-radical polymerised compound and passes through heating or the radical initiator of light generation free radical.At this moment, consider that more preferably free-radical polymerised compound comprises and has acrylate-based or methacrylate based phosphate compound from the angle of the adhesive strength on inorganic matters such as further raising and metal surfaces.

The vitrification point of above-mentioned organic compound is preferably more than 50 ℃.It is more than 50 ℃ that organic compound has urethano and ester group and vitrification point simultaneously, thereby can further improve the adhesive strength behind the high temperature and humidity test especially.When organic compound only had any in urethano and the ester group, if vitrification point is more than 50 ℃, although then can suppress the reduction of the adhesive strength under the hot and humid environment, it is insufficient that the adhesive strength at initial stage can become.Relative therewith, if use the circuit connection material of the organic compound that has urethano and ester group simultaneously, then when keeping fully high initial stage adhesive strength, can further suppress the reduction of the adhesive strength under the hot and humid environment.

In addition, have the above-mentioned organic compound of urethano and ester group, preferably have aromatic group and/or cyclic aliphatic group, weight average molecular weight is preferably 5000～100000.

Circuit connection material of the present invention preferably contains electroconductive particle.Thereby, not only can keep the circuit electrode state of insulation each other on the same substrate, and can circuit block more stably be electrically connected each other.

The syndeton of circuit block of the present invention does; Have first substrate and be formed at first circuit block of first circuit electrode on its interarea and have second substrate and the second circuit parts that are formed at the second circuit electrode on its interarea; The circuit connecting section part that constitutes through the solidfied material by the invention described above circuit connection material, be arranged between said first and second circuit blocks connects, and makes the relative and electrical connection of first circuit electrode and second circuit electrode.

In addition; Circuit member connecting method of the present invention does; According to the layer that has first substrate and first circuit block that is formed at first circuit electrode on its interarea, constitutes by the circuit connection material of the invention described above and have second substrate and be formed at the order of the second circuit parts of the second circuit electrode on its interarea; So that first circuit electrode and second circuit electrode relatively to mode carry out range upon range of; Form duplexer with this, through this duplexer is heated and pressurization, according to making said first circuit electrode and said second circuit electrode electricity connect said first circuit block and said second circuit parts.

The syndeton of circuit block of the present invention, because circuit block connects through circuit connection material of the present invention each other, so circuit block adhesive strength each other is high, hot and humid durability down is excellence also.In addition; Utilize circuit member connecting method of the present invention; Because circuit block connects through circuit connection material of the present invention each other, therefore can access the also syndeton of the circuit block of excellence of high, the hot and humid durability down of circuit block adhesive strength each other.

In the syndeton and circuit member connecting method of foregoing circuit parts, the surface of at least one in preferred first and second circuit electrodes is made up of the material that comprises at least a material of from the group that gold, silver, tin, platinum group metal and indium-tin-oxide are formed, selecting.

In the syndeton and circuit member connecting method of foregoing circuit parts, the substrate that at least one in preferred first and second substrates is made up of the material that comprises at least a material of from the group that PETG, polyether sulfone, epoxy resin, acrylic resin, polyimide resin and glass are formed, selecting.In addition, between at least one in preferred first and second circuit blocks and the circuit connecting section part, be formed with the layer that comprises at least a material of from the group that organic siliconresin, acrylic resin and polyimide resin are formed, selecting.The circuit connection material of these the invention described above, when solidifying to form the circuit connecting section part, and the layer that constitutes of these specific materials between the high adhesive strength of performance.

According to the present invention; Even can provide when being formed with the circuit block of the layer that constitutes by organic siliconresin, polyimide resin, acrylic resin etc., also can obtain the circuit connection material of enough strong adhesive strength on circuit block or surface that connection has a substrate that is formed by PETG, polyimide resin, polyether sulfone, acrylic resin or glass.In addition, according to the present invention, take into account adhesive strength and demand characteristics (being connected resistance, insulating properties etc.) in addition easily.In addition, according to the present invention, it is also relatively wider that the material that is used to obtain above-mentioned effect is formed the scope of selecting.

Description of drawings

Fig. 1 is the sectional view of an execution mode of the circuit connection material of expression film like of the present invention.

Fig. 2 is the sectional view of an execution mode of the syndeton of expression circuit block of the present invention.

Fig. 3 is the sectional view of other execution modes of the syndeton of expression circuit block of the present invention.

Symbol description

1...... the circuit connection material of film like

1a...... circuit connecting section part

5...... electroconductive particle

10...... first circuit block

11...... first substrate

12...... bond layer

13...... first circuit electrode

20...... second circuit parts

21...... second substrate

23...... second circuit electrode

101...... the syndeton of circuit block

102...... the syndeton of circuit block

Embodiment

Below, according to circumstances present invention will be described in detail with reference to the accompanying preferred embodiment.But the invention is not restricted to following execution mode.

Circuit connection material of the present invention contains the adhesive composite through light or hot curing.This adhesive composite preferably contains free-radical polymerised compound and passes through heating or the radical initiator of light generation free radical.

Free-radical polymerised compound has the functional group that carries out polymerization through living radical.For example, suitable acrylate compounds, methacrylate compound, the maleimide compound of using.As the optical free radical polymerizable compound, polymer monomer and polyreactive oligomers etc. are arranged.Because polyreactive oligomers is normally full-bodied, when therefore using polyreactive oligomers, preferably through also adjusting viscosity with polymerizable monomers such as low viscous polymerism polyfunctional acrylic ester monomers.

As acrylate compounds or methacrylate compound; Can use polyreactive oligomerses such as epoxy (methyl) acrylate oligomer, ammonia ester (methyl) acrylate oligomer, polyethers (methyl) acrylate oligomer, polyester (methyl) acrylate oligomer, or polymerizable monomers such as acrylic acid ester, methacrylate.

As acrylic acid ester, can enumerate simple function or polyfunctional acrylate monomers such as trimethylolpropane triacrylate, polyethyleneglycol diacrylate, PAG diacrylate, pentaerythritol acrylate, 2-cyano ethyl acrylic acid ester, cyclohexyl acrylic acid ester, dicyclopentenyl acrylic acid ester, two cyclopentene oxygen base ethyl propylene acid esters, 2-(2-ethoxy ethoxy) ethyl propylene acid esters, 2-ethoxyethyl group acrylic acid ester, 2-ethylhexyl acrylate, n-hexyl acrylic acid ester, 2-hydroxyethylmethacry,ate, hydroxypropyl acrylic acid ester, iso-bornyl acrylate, isodecyl acrylic acid ester, isooctyl acrylate, dodecyl acrylic acid ester, 2-methoxy ethyl acrylic acid ester, 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylic acid ester, neopentylglycol diacrylate, dipentaerythritol acrylate, allyl acrylate.

As methacrylate, can use the acryloyl group of aforesaid propylene acid esters to replace with compound of methacryl etc.Specifically, can enumerate simple function or polyfunctional methacrylate monomer such as tert-butyl group amino-ethyl methacrylate, cyclohexyl methyl acrylic acid ester, two cyclopentene oxygen base ethyl-methyl acrylic acid ester, 2-hydroxyethyl methacrylate, isobornyl methacrylate, isodecyl methacrylate, dodecyl acrylic acid ester, stearyl methacrylate, tridecyl methacrylate, GMA, allyl methacrylate.

As acrylic acid ester or methacrylate, except that above-mentioned, can also suitably use to have acrylate-based or methacrylate based and phosphate-based phosphate compound.As this phosphate compound, the compound of preferred formula (1) expression.In the formula (1), n representes 1～3 integer, and R representes hydrogen atom or methyl.As the object lesson of the phosphate compound of formula (1) expression, can enumerate list (2-methacryloxyethyl) phosphate ester acid, two (2-methacryloxyethyl) phosphate ester acid.As those skilled in the art institute was accessible, this phosphate compound for example can synthesize through the reaction of phosphoric anhydride and 2-hydroxyethylmethacry,ate.

As maleimide compound, preferably has the compound of the dimaleoyl imino more than 2 at least.As maleimide compound, for example can enumerate 1-methyl-2,4-BMI benzene, N with the dimaleoyl imino more than 2; N '-meta-phenylene bismaleimide, N, N '-TOPOT 2,2 maleimide, N, a N '-toluylene BMI, N, N '-4; 4-biphenylene BMI, N, N '-4,4-(3,3 '-dimethyl biphenylene) BMI, N; N '-4,4-(3,3 '-dimethyl diphenylmethane) BMI, N, N '-4; 4-(3,3 '-diethyl diphenyl methane) BMI, N, N '-4; 4-diphenyl methane BMI, N, N '-4,4-diphenyl propane BMI, N; N '-4,4-diphenyl ether BMI, N, N '-3; 3 '-diphenyl sulfone BMI, 2, two (4-(4-maleimide phenoxyl) phenyl) propane, 2 of 2-, two (3-sec-butyl-4-8 (4-maleimide phenoxyl) phenyl) propane, 1 of 2-; Two (4-(4-maleimide phenoxyl) phenyl) decane, 4 of 1-, 4 '-cyclohexylene-two (1-(4 maleimide phenoxyl)-2-cyclohexyl benzene, 2, two (4-(4-maleimide phenoxyl) phenyl) HFC-236fas of 2-etc.These compounds can use separately or multiple combination is used.

As free-radical polymerised compound, can as required above-claimed cpd be used separately or multiple combination use.From the cure shrinkage that can suppress circuit connection material or give solidfied material flexibility angle and consider, preferred especially ammonia ester acrylate oligomer is more preferably with this ammonia ester acrylic acid ester and polymerizable monomer more than a kind and usefulness.

As the radical initiator that produces free radical through heating or light, can use organic peroxide, azo based compound, light trigger such pass through in heating and the rayed compound that the processing of any at least produces living radical.

Organic peroxide and azo based compound mainly produce living radical through heating.When using these compounds, from organic peroxide and/or azo based compound, select more than a kind or 2 kinds according to connection temperature, connect hours, the pot life of purpose waiting aptly as radical initiator.

Organic peroxide; From taking into account high response and enough aspect considerations pot lives two; The temperature of preferred 10 hours half-life is more than 40 ℃ and the temperature of 1 minute half-life is below 180 ℃, and more preferably the temperature of 10 hours half-life is more than 60 ℃ and the temperature of 1 minute half-life is below 170 ℃.In addition, for the corrosion of the circuit electrode (splicing ear) that prevents circuit block, in the organic peroxide, preferred chloride ion or organic acid content are below the 5000ppm, and then, the material that the organic acid that more preferably produces after the heating and decomposition is few.

As organic peroxide, specifically, suitable diacyl peroxide, dialkyl peroxide, peroxy dicarbonate, peroxyester, ketal peroxide, hydroperoxides, the silicyl peroxide etc. of using.

As diacyl peroxide; Can enumerate isobutyl peroxide, 2; 4-dichloro-benzoyl base peroxide, 3; 5,5-trimethyl acetyl base peroxide, sim peroxides, lauroyl peroxide, stearyl peroxide, succinyl group peroxide, benzoyl peroxidating toluene, benzoyl peroxide etc.

As dialkyl peroxide, can enumerate α, α ' two (tert-butyl hydroperoxide) diisopropyl benzene, dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, tert-butyl group cumyl peroxide etc.

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

As peroxyester; Can enumerate cumyl new decanoate ester peroxide, 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, tert-butyl hydroperoxide trimethylace tonitric 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, uncle's hexyl peroxidating-2 ethyl hexanoic acid ester, tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, tert-butyl hydroperoxide isobutyrate, 1; Two (tert-butyl hydroperoxide) cyclohexanes of 1-, uncle's hexyl peroxidating isopropyl monocarbonate, tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester, tert-butyl hydroperoxide laurate, 2; 5-dimethyl-2,5-two (a benzoyl peroxidating) hexane, tert-butyl hydroperoxide isopropyl monocarbonate, tert-butyl hydroperoxide-2-ethylhexyl monocarbonate, uncle's hexyl peroxide benzoate, tert-butyl hydroperoxide acetic acid esters, two (tert-butyl hydroperoxide) six hydrogen terephthalate etc.

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

As hydroperoxides, can enumerate diisopropyl benzene hydrogen peroxide, cumene hydroperoxide etc.

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 etc.

These organic peroxides and azo based compound can use separately or multiple mixing is used.In addition, also can be also with decomposition accelerating agent, inhibitor etc.And then, be lining such as macromolecular compound and the material of microencapsulation with these compounds with polyurethane series, polyester, owing to can obtain the long up time, thereby preferred.

As light trigger; For example, suitable ketone such as benzil ketals such as benzoin ether, benzil, hydroxycyclohexylphenylketone, benzophenone, acetophenones such as benzoin ethylether, isopropyl benzoin ether and derivative thereof, thioxanthene ketone, the diimidazole class etc. used.

When using light trigger,, select the righttest light trigger according to the wavelength of the light source that uses or the curing characteristics of expectation etc.In addition, light trigger, as required, also can be according to arbitrary proportion and with sensitizers such as amine, sulfide, phosphides.

As sensitizer; Aliphatic amine, aromatic amine, cyclic amine such as piperidines, o-tolyl thiocarbamide, diethyldithioposphoric acid sodium, the soluble-salt of aromatic series sulfinic acid, N with nitrogenous circulus; N '-dimethyl-p-aminophenyl formonitrile HCN, N; N '-diethyl-p-aminophenyl formonitrile HCN, N, N '-two (beta-cyano ethyl)-p-aminophenyl formonitrile HCN, N, N '-two (β-chloroethyl)-p-aminophenyl formonitrile HCN, tri-n-butyl phosphine etc.

Perhaps; Can use propiophenone, acetophenone, xanthene ketone, 4-methyl acetophenone, benzophenone, fluorenes, benzophenanthrene, biphenyl, thioxanthones, anthraquinone, 4; 4 '-two (dimethylamino) benzophenone, 4; 4 '-two (diethylamino) benzophenone, phenanthrene, naphthalene, 4-phenyl acetophenone, 4-phenyl benzophenone, 1-iodonaphthalene, 2-iodonaphthalene, acenaphthene, 2-naphthonitrile, 1-naphthonitrile,

benzil, fluoranthene, pyrene, 1; Non-pigmenteds such as 2-benzanthracene, acridine, En 、 perylene, aphthacene, 2-methoxynaphthalene are sensitizer, thionine, methylenum careuleum, lumiflavin, riboflavin, photopigment, cumarin, psoralen, 8-methoxypsoralen, 6-Methylcoumarin, 5-MOP, 5-hydroxyl psoralen, coumaric acyl pyrones (Network マ リ Le ピ ロ Application), acridine orange, acridine yellow, proflavin, fluorescein, eosin W or W S, eosin B, erythrosine sodium salt, rose-red isochrome prime system sensitizer.

As radical initiator, also can aforesaid light trigger and organic peroxide, azo based compound etc. be produced the compound of free radical through heat and use.

Adhesive composite also can be the composition that contains epoxy resin and curing agent thereof.As epoxy resin, can with various epoxy compoundss that have 2 above glycidyls in 1 molecule etc. separately or mix 2 kinds with on use.Specifically; Can enumerate the bisphenol-type epoxy resin of deriving, epoxy radicals novolac resin of deriving by chloropropylene oxide and phenol novolaks or cresols novolaks or naphthalene type epoxy resin, glycidyl amine type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin etc. with naphthalene-ring containing skeleton by chloropropylene oxide and bisphenol-A, F, AD etc.Epoxy resin is with foreign ion (Na ⁺, Cl ^-Deng) or water-disintegrable alkali etc. be reduced to the high purity product below the 300ppm owing to prevent electromigration, thereby preferred.

As curing agent for epoxy resin, in order to obtain fully long pot life, preferred potentiality curing agent.As the potentiality curing agent, imidazoles system, hydrazides system, boron trifluoride-amine complex, sulfonium salt, amine acid imide, the salt of polyamines, dicyandiamide are arranged.Also can be to be that these curing agent of lining such as macromolecular compound carry out the material that microencapsulation obtains with polyurethane series, polyester.These curing agent can use separately also can mix use, can also and use with decomposition accelerating agent, inhibitor etc.

Circuit connection material of the present invention is with aforesaid adhesive composite and has urethano and material that the organic compound of ester group (below be sometimes referred to as " ester urethane compound ") combination obtains.The ester urethane compound preferably has urethano and ester group in its main chain.

This ester urethane compound for example can obtain through the reaction of the pure and mild vulcabond of polyester polyols.Ester urethane compound through this reaction obtains is called as the poly ester urethane resin usually sometimes.

As vulcabond; Suitable use 2; 4-inferior cresyl vulcabond (TDI), 4,4 '-methyl diphenylene diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), IPDI aromatic series, alicyclic or aliphatic vulcabond such as (IPDI).

PEPA is the polymer with a plurality of ester groups and a plurality of hydroxyls.PEPA for example can obtain through the reaction of dicarboxylic acids and glycol.As dicarboxylic acids, aromatic series or aliphatic dicarboxylic acids such as preferred terephthalic acid (TPA), M-phthalic acid, adipic acid, decanedioic acid.As glycol, preferred ethylene glycol, propane diols, 1,4-butanediol, hexylene glycol, neopentyl glycol, diethylene glycol (DEG), the such glycols of triethylene glycol.

The vitrification point of ester urethane compound is preferably more than 50 ℃.The ester urethane compound, the kind through suitable adjustment PEPA, vulcabond or molecular weight etc. can make its vitrification point reach more than 50 ℃.

The ester urethane compound preferably has anionic property.Thereby adhesive strength further improves.Ester urethane compound with anionic property, through when the pure and mild di-isocyanate reaction of polyester polyols, make have sulfonic group, the glycol of carboxyl or two amine combined polymerizations obtain in side chain.That is, the ester urethane compound preferably has sulfonic group or carboxyl.

The ester urethane compound preferably has the aromatic group that contains phenyl ring etc., the cyclic aliphatic group that contains cyclohexane ring etc.

The ester urethane compound can mix use more than 2 kinds.The material that material that for example, can the reaction through aromatic polyester polyol and aliphatic diisocyanate be obtained and the reaction through aliphatic polyester polyols and aromatic diisocyanate obtain makes up.

The weight average molecular weight of ester urethane compound is preferably 5000～100000.If weight average molecular weight, then has the tendency of the film formation property reduction when being shaped to film like less than 5000; If weight average molecular weight surpasses 100000, the dissolubility or the intermiscibility that then have in solvent reduce, and are difficult to prepare the tendency of the coating fluid that is used to be shaped to film like.

The ester urethane compound preferably comprises and has free-radical polymerised unsaturated double-bond and at least one in the epoxy radicals.Thus, when curing circuit connected material, with epoxy resin or free-radical polymerised compound reaction in the adhesive composite, the modulus of elasticity of the solidfied material of circuit connection material, thermal endurance improved.

Circuit connection material except that the composition of above explanation, can also contain hydroxy-containing resin.As hydroxy-containing resin, can use polyvinyl butyral resin, polyvinyl formal, polyamide, polyester, phenol resin, epoxy resin, phenoxy resin, polyurethane resins such as (not comprising above-mentioned ester urethane compound).Wherein, preferred especially phenoxy resin.Through using these hydroxy-containing resins, the stress retentivity during curing is excellent, because the hydroxyl cementability further improves.

The weight average molecular weight of hydroxy-containing resin is preferably more than 10000, and more preferably 10000～1000000.If the weight average molecular weight of hydroxy-containing resin surpasses 1000000, then have and be difficult to the tendency of mixing with other compositions.In addition, the vitrification point of hydroxy-containing resin is preferably more than-50 ℃.

In order further to improve thermal endurance, hydroxy-containing resin preferably has free-radical polymerised functional group.Hydroxy-containing resin with free-radical polymerised functional group is as above-mentioned free-radical polymerised compound.Hydroxy-containing resin also can be through containing the carboxyl elastomer, containing modifications such as epoxy radicals elastomer.

Circuit connection material in order to become at material excellent aspect the stress mitigation, preferably contains acrylic rubber.As ACM, can use polymer or copolymer that at least a acrylic monomer polymerization in acrylic acid, acrylic acid ester, methacrylate and the acrylonitrile is obtained.Acrylic rubber also can be the copolymer of above-mentioned monomer and glycidyl acrylate or GMA.Consider that from the cohesive force aspect that improves circuit connection material the weight average molecular weight of acrylic rubber (weight average) is preferably more than 200,000.

Circuit connection material also can contain styrene resin.Styrene resin can be the resin that the polymerizing styrene monomer obtains, and also can be the copolymer that at least one copolymerization in styrene and maleic anhydride compound, the maleimide compound is obtained.Consider that from the cohesive force aspect that improves circuit connection material the weight average molecular weight of styrene resin (weight average) is preferably more than 100,000.

Circuit connection material can also further contain filler, softening agent, promoter, age resister, colouring agent, fire retardant, thixotropic agent, coupling agent and phenol resin, melamine resin, isocyanates etc.

When containing filler, connection reliability etc. can be improved, thereby preferred.The maximum gauge of filler is preferably the particle diameter less than electroconductive particle, and its amount is preferably in the scope of 5～60 parts by volume (with respect to adhesive composite 100 parts by volume).If surpass 60 parts by volume, then the effect of reliability raising can be saturated, if less than 5 parts by volume, the effect of then adding is little.As coupling agent, consider from the aspect that cementability improves, preferably contain vinyl, acryloyl group, amino, epoxy radicals, and the material of NCO.

Circuit connection material preferably contains electroconductive particle.Even though do not contain electroconductive particle, also can the connecting circuit parts through circuit electrode direct contact each other, through containing conducting particles, can more stably connect.

As electroconductive particle, can enumerate metallics such as Au, Ag, Ni, Cu, scolder or carbon particle etc.In order fully to prolong pot life, electroconductive particle preferably comprises Au, Ag, platinum group metal, more preferably comprises Au.

Electroconductive particle is preferably, and the particle that forms with transition metal such as Ni or dielectric glass, pottery, plastics etc. is as nuclear, the particle that its surface uses the coating lining that is made up of noble metals such as Au to obtain.Electroconductive particle like this with noble metal coating, distortion with circuit connection material heating and pressurization the time, thus increasing with the contact area of circuit electrode, reliability further improves.In order to obtain good connection resistance, the thickness of the coating of noble metal is preferably more than 100 dusts.And then when examining the particle into transition metal such as Ni, the thickness of coating is more preferably more than 300 dusts.The thickness of coating is during less than 300 dusts, when being scattered in electroconductive particle in the resin etc. under the situation, during coating a part of damaged, because redox produces free free radical, has the tendency that the storage stability of circuit connection material reduces.

The amount of electroconductive particle with respect to adhesive composite 100 parts by volume, is preferably 0.1～30 parts by volume.In order to prevent that superfluous electroconductive particle from causing the short circuit of adjacent circuit etc., more preferably 0.1～10 parts by volume.

Fig. 1 is the sectional view of an execution mode of the circuit connection material of film like of the present invention.The circuit connection material 1 of film like is that a plurality of electroconductive particles 5 are scattered in the circuit connection material that obtains in the resin combination layer 3 that contains adhesive composite and ester urethane compound etc. and are shaped to the material that film like obtains.The circuit connection material 1 of film like for example can be made through with specific thickness circuit connection material being coated on the support film.As support film, surface treatment has been carried out in suitable use so that it has PET film of release property etc.

The circuit connection material 1 of film like, being clipped in that relative 1 pair of circuit block state each other is heated and when pressurizeing, melt-flow after relative circuit electrode is electrically connected to each other, is solidified, and shows adhesive strength.So the flowability of the circuit connection material 1 of film like is important.Specifically; In that (thick 35 μ m, 5mm * 5mm) are clipped in 2 glass sheets (under the state between the thick 0.7mm, 15mm * 15mm) with the circuit connection material 1 of film like; Carry out 150 ℃, 2MPa, heating and when pressurization of 10 seconds; Value with the index (B)/(A) of the flowability of the initial stage area (A) of circuit connection material 1 and the expression of the area (B) after the heating and pressurizing is preferably 1.3～3.0, and more preferably 1.5～2.5.If value (B)/(A) less than 1.3, then has illiquidity, can't obtain the tendency of good connection; If surpass 3.0, then can produce bubble, the tendency that has reliability to reduce.

The circuit connection material 1 of film like only has 1 layer, but circuit connection material of the present invention also can replace this 1 layer, and uses to be shaped to the state with a plurality of layers different film of composition.Particularly circuit connection material contains adhesive composite in electroconductive particle, the circuit connection material and contains when producing the radical initiator of free radical through heating or light, circuit connection material is become separately have to contain layer and the plural layers of the layer that contains electroconductive particle that produce the radical initiator of free radical through heating or light.Like this, can obtain the longer up time.

The circuit connection material 1 of film like for example can be used for such circuit blocks such as chip part, printed base plate such as semiconductor chip, resistance chip, capacitor chip are connected to each other.

Fig. 2 is the sectional view of an execution mode of the syndeton of expression circuit block of the present invention.The syndeton 101 of circuit block shown in Figure 2 is following syndeton: has first substrate 11 and is formed at first circuit block 10 of first circuit electrode 13 on its interarea and has second substrate 21 and the second circuit parts 20 that are formed at the second circuit electrode 23 on its interarea through bond layer 12, and that solidfied material that material cured obtains constitutes through connecting, be formed at the structure that first and second circuit blocks 10, the circuit connecting section part 1a between 20 are formed by connecting foregoing circuit.In the syndeton 101 of circuit block, first circuit electrode 13 and second circuit electrode 23 are relatively and be electrically connected.

Circuit connecting section part 1a is made up of with the electroconductive particle 5 that is scattered in wherein the solidfied material 3a of the resin combination that contains adhesive composite and ester urethane compound etc.First circuit electrode 13 and second circuit electrode 23 is electrically connected through electroconductive particle 5.40 ℃ the modulus of elasticity of circuit connecting section part 1a is preferably 100～3000MPa, more preferably 500～2000MPa.

First substrate 11 is the resin films that contain at least a kind of resin from the group that PETG, polyether sulfone, epoxy resin, acrylic resin and polyimide resin are formed, selecting.

Circuit electrode 13 forms by having the material (being preferably from the group that the metal and the indium-tin-oxide of gold, silver, tin, platinum family are formed, select at least a) that can bring into play as the conductivity of the function degree of electrode.A plurality of circuit electrodes 13 are bonded on the interarea of first substrate 11 through bond layer 12.Bond layer 12 is formed by normally used bonding agent in the circuit block etc.

Second substrate 21 is glass substrates, is formed with a plurality of second circuit electrodes 23 on the interarea of second substrate 21.

The syndeton 101 of circuit block; For example can obtain: according to first circuit block 10, the circuit connection material 1 of above-mentioned film like and the order of second circuit parts 20 through following method; So that first circuit electrode 13 and second circuit electrode 23 relatively to mode carry out range upon range of; Form duplexer with this,, be connected first circuit block 10 and second circuit parts 20 according to first circuit electrode 13 and second circuit electrode 23 being electrically connected fetching through to this duplexer heating and pressurization.

In this method; At first; The circuit connection material that is formed at the film like on the support film 1 is heated under the state that is pasted on the second circuit parts 20 and pressurizes, thus circuit connection material 1 is bonding in advance, peel off support film after; The position of alignment circuit electrode is placed first circuit block 10 on one side on one side, can prepare duplexer.

The condition of above-mentioned heating and pressurization duplexer is suitably adjusted according to the curable of the adhesive composite in the circuit connection material etc., so that circuit connection material solidifies and can obtain sufficient adhesion strength.

Fig. 3 is the sectional view of other execution modes of the syndeton of expression circuit block of the present invention.The syndeton 102 of circuit block shown in Figure 3, first circuit electrode 13 directly was formed on the interarea of first substrate 11 in first circuit block 10, all the other were identical with the syndeton 101 of circuit block.

As the syndeton 102 of circuit block; Under circuit connecting section part 1a and the situation with the such structure of the direct driving fit of substrate of materials such as PETG, polyether sulfone, epoxy resin, acrylic resin, polyimide resin and glass formation, circuit connection material in the past is difficult to obtain sufficient adhesion strength.Relative therewith, in the syndeton 102 of circuit block, circuit connecting section part 1a is the solidfied material of the circuit connection material of the invention described above, even thereby under hot and humid environment, also can keep sufficient adhesion strength.Such effect is even also can obtain under the situation that is formed with the layer that contains polyimide resin, acrylic resin, organic siliconresin etc. between circuit connecting section part and the circuit block.

Embodiment

Below, enumerate embodiment and comparative example, the present invention more specifically is described.But, the invention is not restricted to following embodiment.

(preparation method of poly ester urethane resin)

The PEPA that will obtain through the reaction of dicarboxylic acids and glycol is dissolved in and obtains solution in the methyl ethyl ketone, this solution input is possessed in the stainless steel autoclave of band heater of mixer, thermometer, condenser and vacuum generating device and nitrogen ingress pipe.Then, drop into the isocyanates of ormal weight, dropping into respect to PEPA 100 weight portions is the dibutyl tin laurate as catalyst of 0.02 weight portion, after 10 hours, is cooled to 40 ℃ 75 ℃ of reactions.And then, through adding after piperidines makes its reaction carry out chain elongation in 30 minutes, neutralize with triethylamine.

Above-mentioned reacted solution is added drop-wise in the pure water, and not only solvent and catalyst dissolution and are separated out as the poly ester urethane resin of ester urethane compound in water.With the poly ester urethane resin drying of separating out, obtain the poly ester urethane resin with vacuum drier.

Embodiment 1

(synthesizing of poly ester urethane Resin A)

Will be as the terephthalic acid (TPA) of dicarboxylic acids, as the propane diols of glycol, as 4 of isocyanates; 4 '-methyl diphenylene diisocyanate; With terephthalic acid (TPA)/propane diols/4; The mol ratio of 4 '-methyl diphenylene diisocyanate is that the amount of 1.0/1.3/0.25 is used, and obtains the poly ester urethane Resin A according to above-mentioned steps.The weight average molecular weight of poly ester urethane Resin A when using gel permeation chromatography, is 27000.

The poly ester urethane Resin A is dissolved in reaches 20 weight % in the methyl ethyl ketone; Form methyl ethyl ketone solution; With apparatus for coating this solution coat has been carried out through 70 ℃, 10 minutes heated-air drying, forming the film of thick 35 μ m on the surface-treated PET film (thick 80 μ m) at single face.For this film, use wide area Measurement of Dynamic Viscoelasticity device, under the condition of stretching loading 5gf, frequency 10Hz, measure the temperature dependency of modulus of elasticity.In the modulus of elasticity-temperature curve that obtains; With on the y direction with the glass transition zone before and after the equidistant straight line of straight line behind separately the base line extension; The temperature (intermediate point vitrification point) of intersection point of curve that changes part with glass transition zone stepped is as the vitrification point of poly ester urethane Resin A, and trying to achieve the result is 105 ℃.

(circuit connection material)

On one side with polycaprolactone glycol 400 weight portions of weight average molecular weight 800,2-hydroxypropyl acrylic acid ester 131 weight portions, be heated to 50 ℃ as dibutyltin dilaurate 0.5 weight portion of catalyst with as hydroquinone monomethyl ether 1.0 weight portions of polymerization inhibitor, Yi Bian mix.Then, drip IPDI 222 weight portions, and then, be warming up to 80 ℃ while stir, carry out the ammonia esterification.The reactivity of confirming NCO be 99% or more after, the reduction temperature obtains the ammonia ester acrylic acid ester as free-radical polymerised compound.

On the surface that with the polystyrene is the particle of nuclear, form the nickel dam of thick 0.2 μ m and the gold layer of thick 0.04 μ m in order, process the electroconductive particle of average grain diameter 10 μ m.

In solid constituent weight; According to poly ester urethane Resin A 50g, ammonia ester acrylate 49g, phosphate type acrylic acid ester 1g, mix each composition as uncle's hexyl peroxidating 2 ethyl hexanoic acid ester 5g of radical initiator; And then; Add electroconductive particle and make its amount, make its even dispersion, obtain being coated with the dispersion liquid of usefulness for 3 whole volume %.During the modulation dispersion liquid; Under the state of poly ester urethane Resin A for the solution that is dissolved in methyl ethyl ketone with the concentration of 20 quality %; At uncle's hexyl peroxidating 2 ethyl hexanoic acid ester is that (NOF Corp makes 50 weight %DOP solution; Trade name " cross can (パ one キ ュ ァ) HO ") under the state, mixes with other compositions.With apparatus for coating the dispersion liquid that obtains being coated on single face has carried out through 70 ℃, 10 minutes heated-air drying, obtaining the circuit connection material of the film like of thick 20 μ m on the surface-treated PET film (thick 80 μ m).

Embodiment 2

Will be as M-phthalic acid, terephthalic acid (TPA) and the adipic acid of dicarboxylic acids, as ethylene glycol, the neopentyl glycol and 1 of glycol, 6-hexylene glycol; As 4 of vulcabond; 4 '-methyl diphenylene diisocyanate, with M-phthalic acid/terephthalic acid (TPA)/adipic acid/ethylene glycol/neopentyl glycol/1,6-hexylene glycol/4; The mol ratio of 4 '-methyl diphenylene diisocyanate is that the amount of 0.21/0.21/0.58/0.19/0.55/0.46/0.3 is used, according to above-mentioned steps synthesizing polyester ammonia ester resin B.The weight average molecular weight of poly ester urethane resin B when using gel permeation chromatography, is 60000.In addition, likewise measure the vitrification point of poly ester urethane resin B with embodiment 1, the result is-3 ℃.

Except using the poly ester urethane resin B to replace likewise operating with embodiment 1 the poly ester urethane Resin A, process the circuit connection material of film like.

Embodiment 3

In addition, likewise operate except the 20g among the poly ester urethane resin B 50g being replaced to phenoxy resin (Union Carbide Corporation makes, trade name " PKHC ", weight average molecular weight 45000), process the circuit connection material of film like with embodiment 2.

Comparative example 1

Used PEPA (85 ℃ of vitrification points) replaces likewise operating with embodiment 1 the poly ester urethane Resin A when the synthesizing polyester ammonia ester Resin A except using, and processes the circuit connection material of film like.

Comparative example 2

Except using PEPA used when the synthesizing polyester ammonia ester resin B (vitrification point-5 ℃) to replace likewise operating with embodiment 2 the poly ester urethane resin B, process the circuit connection material of film like.

Comparative example 3

Except using PEPA used when the synthesizing polyester ammonia ester resin B (vitrification point-5 ℃) to replace likewise operating with embodiment 3 the poly ester urethane resin B, process the circuit connection material of film like.

Comparative example 4

Do not have polyurethane resin (the DIC Bayer Polymer manufactured of ester group except using; Trade name " Pan's Otto Dix T-8175 (パ Application デ ッ Network ス T-8175) ") (vitrification point-30 ℃) replaces beyond the poly ester urethane Resin A; Likewise operate with embodiment 1, process the circuit connection material of film like.

(making of the syndeton of circuit block)

Preparation is formed with the circuit block of 500 chromium circuit as circuit electrode (live width 50 μ m, spacing 100 μ m, thick 0.4 μ m) on glass substrate (CORNING manufactured, trade name " #1737 ").On this circuit block, paste the circuit connection material of the film like that embodiment 1 makes, heating and pressurizing is 5 seconds under 70 ℃, the condition of 0.5MPa, and it is bonding in advance.

Then; Peel off the PET film; Will be in polyimide film (Ube Industries, Ltd's manufacturing; Trade name " UPILEX ", thick 75 μ m) go up the flexible circuit parts (FPC1) that are bonded with the 3-tier architecture that 500 copper circuits (live width 50 μ m, spacing 100 μ m, thick 18 μ m) form across bond layer and be placed on the circuit connection material of film like, heating and pressurizing is 10 seconds under 160 ℃, the condition of 3MPa.Thereby the circuit block that will have glass substrate is connected through the width of 2mm with FPC1.

In addition; (Ube Industries, Ltd makes at polyimide film in use; Trade name " UPILEX25S "; Thick 25 μ m) flexible electric circuit board (FPC2) of 2 layers of structure that directly is formed with the copper circuit of 500 live widths, 50 μ m, spacing 100 μ m, thick 8 μ m replaces FPC1, and with above-mentioned operation likewise, the circuit block that will have glass substrate is connected with the width that FPC2 passes through 2mm.

Use the circuit connection material of the film like of embodiment 2～3, comparative example 1～4 making,, FPC1 is connected with the circuit block with glass substrate respectively with FPC2 with above-mentioned operation likewise.

(connection resistance)

For the syndeton of the circuit block of making, use the resistance value (connection resistance) between the relative circuit electrode of multitester measuring.Mensuration is in the early stage, in 85 ℃, the hot and humid groove of 85%RH, keeps carrying out after 500 hours the hot and humid processing.The mean value that resistance value shown in the table 1 is 150 (x+3 σ) is as connecting resistance.

(adhesive strength)

For the syndeton of the circuit block of making, the adhesive strength when peeling off with 90 ° of peeling rate 50mm/min mensuration.Mensuration is in the early stage, carries out after the hot and humid processing same as described above.

Table 1

The syndeton of the circuit block that the circuit connection material of use embodiment 1～3 connects, the connection resistance at initial stage is fully low, and also almost finds to connect the rising of resistance after the hot and humid processing, demonstrates high durability.Wherein, in the situation of the embodiment 1 of the poly ester urethane resin of use vitrification point more than 50 ℃, durability is excellent especially.In addition, use in the situation of vitrification point less than the embodiment 2 of 50 ℃ poly ester urethane resin, although the connection after the hot and humid processing fluffs a little, it is big that the rising that connects resistance and embodiment 1 compare relative change, in the practicality in permissible range.And then, and in the situation with the embodiment 3 of poly ester urethane resin and the phenoxy resin of vitrification point more than 50 ℃, the almost inhibition of equal extent of the rising acquisition of the connection resistance that hot and humid processing causes and embodiment 1.

Embodiment 1～3, under arbitrary situation of FPC1 and FPC2, all maintains more than the 6N/cm after initial stage and the hot and humid processing.Under the situation of this test, usually, if being more than the 6N/cm, adhesive strength thinks in the practicality it is sufficient.Embodiment 2 and embodiment 3 compare, the more embodiment 2 of poly ester urethane resin content, and the adhesive strength after the hot and humid processing is more excellent than embodiment 3.

Relative therewith, use not have ester bond and the low comparative example 4 that reaches-30 ℃ polyurethane resin of vitrification point, after the hot and humid processing, connect resistance and raise greatly.And, comparative example 4, although in the syndeton of using FPC1, demonstrate reasonable adhesive strength, in the syndeton of using FPC2, after the hot and humid processing, adhesive strength reduces greatly.Comparative example 1～3, adhesive strength are below about 6N/cm, aspect adhesive strength, in practicality, do not demonstrate sufficient characteristic at least.

Claims (16)

1. A film-like circuit connection material, characterized in that it contains an adhesive composition cured by light or heat and an organic compound with a urethane group and an ester group, and is used to have a substrate and a substrate formed on its main surface. The circuit components of the circuit electrodes are connected to each other, and the weight-average molecular weight of the organic compound is 27000-60000, and the organic compound is obtained through the reaction of polyester polyol and diisocyanate. 2. A film-like circuit connection material, characterized in that it contains an adhesive composition cured by light or heat and an organic compound with a urethane group and an ester group, and is used to form a substrate having a substrate and an organic compound formed on its main surface. The circuit components of the circuit electrodes are connected to each other, the weight average molecular weight of the organic compound is 5,000 to 100,000, wherein the glass transition temperature of the organic compound is above 50°C, and the organic compound is obtained by the reaction of polyester polyol and diisocyanate . 3. The film-form circuit connecting material according to claim 1 or 2, wherein the adhesive composition contains a radical polymerizable compound and a radical generator for generating radicals by heating or light. 4. The film-form circuit connection material according to claim 3, wherein the radically polymerizable compound contains a phosphoric acid ester compound having an acrylate group or a methacrylate group. 5. The film-form circuit connection material according to claim 1 or 2, wherein the organic compound has at least one of an aromatic group and a cyclic aliphatic group. 6. The film-form circuit connection material according to claim 2, wherein the organic compound has a weight average molecular weight of 5,000 to 60,000. The film-form circuit connection material of Claim 2 whose weight average molecular weight of the said organic compound is 27000-60000. 8. The film-form circuit connection material according to claim 1 or 2, containing electroconductive particles. 9. The connection structure of circuit components is characterized in that, the first circuit component with the first substrate and the first circuit electrode formed on its main surface and the second circuit electrode with the second substrate and formed on its main surface The second circuit part is connected through a circuit connection part arranged between the first and second circuit parts, so that the first circuit electrode and the second circuit electrode are opposite and electrically connected, wherein the circuit The connection member is formed from the hardened|cured material of the film-form circuit connection material as described in any one of Claims 1-8. 10. The connection structure of circuit components according to claim 9, wherein the surface of at least one of the first and second circuit electrodes is composed of gold, silver, tin, platinum group metals and indium-tin oxide. The material composition of at least one substance selected from the group. 11. The connection structure of circuit components according to claim 9, wherein at least one of the first and second substrates is made of polyethylene terephthalate, polyether sulfone, epoxy resin, A substrate formed of at least one material selected from the group consisting of acrylic resin, polyimide resin, and glass. 12. The connection structure of circuit components according to claim 9, wherein at least one of said first and second circuit components and said circuit connection component is formed between a silicone resin, acrylic resin and polyamide A layer of at least one substance selected from the group consisting of imide resins. 13. A method for connecting circuit components, characterized in that, according to a first circuit component having a first substrate and a first circuit electrode formed on its principal surface, the film-shaped substrate according to any one of claims 1 to 8 A layer composed of a circuit connection material, and a second circuit component having a second substrate and a second circuit electrode formed on its main surface, so that the first circuit electrode and the second circuit electrode face each other. Laminated in a manner to form a laminated body, by heating and pressing the laminated body, the first circuit part and the second circuit part are connected so that the first circuit electrode and the second circuit electrode The electrodes are electrically connected. 14. The method for connecting circuit components according to claim 13, wherein the surface of at least one of the first and second circuit electrodes is composed of gold, silver, tin, platinum group metals and indium-tin oxide. The material composition of at least one substance selected from the group. 15. The method for connecting circuit components according to claim 13, wherein at least one of the first and second substrates is made of polyethylene terephthalate, polyethersulfone, epoxy resin, A substrate formed of at least one material selected from the group consisting of acrylic resin, polyimide resin, and glass. 16. The method for connecting circuit components according to claim 13, wherein a layer comprising silicone resin, acrylic resin, A layer of at least one substance selected from the group consisting of resin and polyimide resin.

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