CN100524674C - Circuit connection method - Google Patents
Circuit connection method Download PDFInfo
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- CN100524674C CN100524674C CNB2005100764482A CN200510076448A CN100524674C CN 100524674 C CN100524674 C CN 100524674C CN B2005100764482 A CNB2005100764482 A CN B2005100764482A CN 200510076448 A CN200510076448 A CN 200510076448A CN 100524674 C CN100524674 C CN 100524674C
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Abstract
There are provided an adhesive for connecting a circuit to be interposed between substrates having circuit electrodes thereon opposed to each other and to electrically connect the circuit electrodes on the substrates opposed to each other to the pressurizing direction under pressure, wherein the adhesive contains a compound having an acid equivalent of 5 to 500 KOH mg/g.
Description
The application divides an application, the application number of its female case application: 01808255.6, and the applying date: 2001.4.25, denomination of invention: adhesive for circuit connection, the circuit connecting method that uses it and circuit connection structure
Technical field
The present invention relates to a kind of adhesive for circuit connection, use the circuit connecting method and the circuit connection structure of this bonding agent.
Background technology
In the past, being connected of LCD and carrier band encapsulation (TCP) or flexible printed circuit (FPC), being connected between TCP or FPC and the printed circuit board (PCB) was to use the anisotropically conducting adhesive that is dispersed with electroconductive particle in bonding agent.And, when recently semiconductor silicon chips being installed on substrate, also without the bonding wire method, but semiconductor silicon chips directly is installed on substrate with facing down, carry out so-called flip-chip (flip chip) and install, also begin to adopt anisotropically conducting adhesive (Japan Patent spy open clear 59-120436 number, spy open clear 60-191228 number, spy open flat 1-251787 number, spy and open flat 7-90237 communique) this moment.
Yet anisotropically conducting adhesive in the past is for the bonding force deficiency of various substrates, thereby can't obtain sufficient connection reliability.Especially, can't be fully, satisfy in order to reduce when connecting the skew of the injury of substrate or position and to enhance productivity and the low temperatureization of the connection temperature that requires and the shortening of connect hours etc. reliably.
Summary of the invention
The present invention provides a kind of realized the connecting low temperatureization of temperature, the adhesive for circuit connection of the shorteningization of connect hours, reaches circuit connecting method that uses this bonding agent and the circuit connection structure that uses this method.
The present invention's 1 is between between the substrate with circuit electrode in opposite directions, to having the substrate pressurization of circuit electrode in opposite directions, and the adhesive for circuit connection that is electrically connected between the electrode of compression aspect is characterized by above-mentioned bonding agent and contains acid equivalent and count 5 to 500 compound by KOH milligram/gram.
The present invention's 2 is 1 described adhesive for circuit connection of the present invention, and it is characterized by acid equivalent, to count 5 to 500 compound by KOH milligram/gram be the compound that contains at least one carboxyl.
The present invention's 3 is 1 or 2 described adhesive for circuit connection of the present invention, it is characterized by and also contains free-radical polymerised material.
The present invention's 4 be the present invention 1 to 3 in any described adhesive for circuit connection, it is characterized by and also contain conducting particles.
The present invention's 5 is that a kind of adhesive for circuit connection that makes is between between the substrate with circuit electrode in opposite directions, to having the substrate pressurization of circuit electrode in opposite directions, make the syndeton body that is electrically connected between the electrode of compression aspect, it is characterized by 1 to 4 any described bonding agent of foregoing circuit connecting adhesive for the present invention.
The present invention's 6 is between between the substrate with circuit electrode in opposite directions, to having the substrate pressurization of circuit electrode in opposite directions, and the adhesive for circuit connection that between the electrode of compression aspect, is electrically connected, it is characterized by above-mentioned bonding agent and have first bond layer and second bond layer, and the glass transition temperature (Tg) after the pressurization of first bond layer connection is higher than the Tg after the pressurization of second bond layer connects.
The present invention's 7 is 6 described adhesive for circuit connection according to the present invention, the Tg that it is characterized by after the connection of first bond layer is 50 to 200 ℃, and the Tg after the connection of second bond layer is 40 to 100 ℃, and the Tg of the Tg of first bond layer after than the connection of second bond layer is high more than 5 ℃.
The present invention's 8 is the 7 described adhesive for circuit connection of 6 or the present invention according to the present invention, and the one deck at least that it is characterized by in first bond layer and second bond layer contains conducting particles.
The present invention's 9 is 68 any described adhesive for circuit connection to the present invention according to the present invention, and the one deck at least that it is characterized by in first bond layer and second bond layer contains free-radical polymerised material.
The present invention's 10 is 69 any described adhesive for circuit connection to the present invention according to the present invention, the thickness ratio that it is characterized by first bond layer and second bond layer is that thickness=0.3 of the thickness of first bond layer/second bond layer is to 3.0.
The present invention's 11 is 6 10 any described adhesive for circuit connection to the present invention according to the present invention, and the one deck at least that it is characterized by first bond layer and second bond layer contains acid equivalent counts 5 to 500 compound by KOH milligram/gram.
The present invention's 12 is, with the present invention 6 to 11 any described adhesive for circuit connection of the present invention between between substrate with circuit electrode in opposite directions, to having the substrate pressurization of circuit electrode in opposite directions, the method that between the electrode of compression aspect, is electrically connected, it is characterized by the foregoing circuit connecting adhesive and have first bond layer and second bond layer, Tg after the pressurization that Tg after the pressurization of first bond layer connects is higher than second bond layer connects, and the first higher bond layer of Tg is to be arranged in to have the higher substrate-side of substrate spring rate of circuit electrode in opposite directions.
The present invention's 13 is, with the present invention 6 to 11 any described adhesive for circuit connection of the present invention between between substrate with circuit electrode in opposite directions, to having the substrate pressurization of circuit electrode in opposite directions, the syndeton body that between the electrode of compression aspect, is electrically connected, it is characterized by above-mentioned bonding agent and have first bond layer and second bond layer, Tg after the pressurization that Tg after the pressurization of first bond layer connects is higher than second bond layer connects, and the first higher bond layer of Tg is to be arranged in to have the higher substrate side surfaces of substrate spring rate of circuit electrode in opposite directions.
Embodiment
Adhesive for circuit connection of the present invention and using in the circuit connecting method and circuit connection structure of this bonding agent, after carrying out various reliability tests such as humidity test, thermal cycling test, do not take place to come off, peel off phenomenon from the substrate yet, do not rise so bonding force is descended or connect resistance, present excellent connection reliability.
The present invention 1 in, can use with the acid equivalent of potassium hydroxide titration measuring compound in 5 to 500 (KOH milligram/gram) scope, it is desirable to use the compound that contains carboxyl.If acid equivalent is less than 5 then do not see the rising of bonding force, and if big to surpassing 500, then the water absorption rate because of bonding agent becomes big, so the reduction of moisture-proof reliability.The compound that contains carboxyl is just passable as long as contain the compound of carboxyl at molecule, has no particular limits.And weight average molecular weight also had no particular limits, but the weight average molecular weight that it is desirable to compound is less than 1,000, and 000.If molecular weight is greater than 1,000, and the flowability of 000 bonding agent descends.Specifically being exemplified as of compound of containing carboxyl, carboxylic acid such as oxalic acid, malonic acid and the compound that in polymer such as polybutadiene, polyvinyl butyral resin, (methyl) acrylic resin, polyimides, polyamide, polystyrene, vinyl-formal resin, mylar, xylene resin, phenoxy resin, polyurethane resin, urea resin, imports carboxyl.When in macromolecule, importing carboxyl, the compound that contains carboxyl can be used as copolymer composition, also can after polymer is synthetic, import carboxyl again.Proportional quantity employed among the present invention, the compound in macromolecule behind the importing carboxyl better is 1 to 80 weight %, is more preferably 5 to 70 weight %.Cementability is poor during less than 1 weight %, surpasses the then mobile decline of 80 weight %.
Except using the above-mentioned compound that contains carboxyl, also use styrene-butadiene-styrol copolymer among the present invention, thermoplastic resins such as styrene-isoprene-styrene copolymer-, or epoxy resin, (methyl) acrylic resin, maleimide resin, the citraconimide resin, the norbornene imide resin, heat-curing resins such as phenolic resin, it is desirable to use thermosetting resin from the viewpoint of thermal endurance or reliability, be that using (methyl) acrylic acid is resin from the viewpoint of curability at low temperatures, maleimide resin, the citraconimide resin, the radical polymerization syzygy of norbornene imide resin is especially desirable.
The present invention's 2 adhesive for circuit connection is made of first bond layer and second bond layer, and wherein the Tg after the connection of first bond layer must be higher than the Tg after the connection of second bond layer.The Tg of first bond layer it is desirable to 50 to 200 ℃, and better is 60 to 150 ℃.And the Tg of second bond layer is at 40 to 100 ℃, and it is desirable that the Tg of the Tg of first bond layer after than the connection of second bond layer exceeds more than 5 ℃, is optimal and exceed more than 10 ℃.
And, the thickness of first bond layer and second bond layer than be thickness=0.3 of thickness/second bond layer of first bond layer to 3.0, and it is desirable to 0.8 to 3.0.Thickness beyond this scope has generation to come off, peel off and can't obtain the tendency of good connection reliability from substrate after various reliability tests such as humidity test, thermal cycling test.
In addition, in the present invention, when using the bond layer of above-mentioned two layers of structure to be electrically connected the circuit electrode of substrate in opposite directions, it is desirable to first bond layer that Tg is higher and be arranged at the higher substrate-side of spring rate in opposite directions the substrate.
Above-mentioned thermoplastic resin or heat-curing resin all can be used as first bond layer used in the present invention or second bond layer, and from the viewpoint of thermal endurance and reliability, it is desirable to use heat-curing resin, especially from the viewpoint of hardening at subcritical temerature, it is desirable using the radical polymerization syzygy of (methyl) acrylic resin, maleimide resin, citraconimide resin, norbornene imide resin.
(methyl) acrylic resin can be got by the radical polymerization of (methyl) esters of acrylic acid, can exemplify and be (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylene glycol four (methyl) acrylate, 2-hydroxyl-1,3-two propylene acyloxy propane, 2, two [4-(acryloyl-oxy ylmethoxy) phenyl] propane of 2-, 2, two [4-(acryloyl-oxy base oxethyl) phenyl] propane of 2-, dicyclopentenyl (methyl) acrylate, tristane base (methyl) acrylate, three (acryloxy ethyl) isocyanates, ammonia ester (methyl) acrylate etc. can use more than two kinds alone or in combination.And in not damaging indurative scope, as required, used radical polymerization inhibitors 1 such as quinhydrones, methyl ether quinhydrones.
In addition, when use has the free-radical polymerised material of phosphate structure, can improve bonding force to inorganic matters such as metals.Use amount with free-radical polymerised material of phosphate structure is, 0.1 to 10 weight portion of adhesive composite total amount, and desirable use amount is 0.5 to 5 weight portion.Free-radical polymerised material with phosphate structure can derive from the product of phosphoric anhydride and 2-carboxy ethyl (methyl) acrylate.Particularly, list (2-methacryloxyethyl) acid phosphate, two (2-methacryloxyethyl) acid phosphate etc. is arranged, can be used alone or as a mixture.
Maleimide resin is the resin that has at least one dimaleoyl imino in the molecule, phenyl maleimide for example, 1-methyl-2,4-bismaleimides benzene, N, N '-adjacent phenylene bismaleimides, N, N '-to the di-2-ethylhexylphosphine oxide maleimide, N, N '-4,4-biphenylene bismaleimides, N, N '-4,4-(3,3-dimethyl biphenylene) bismaleimides, N, N '-4,4-(3, the 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 '-4,4-diphenyl ether bismaleimides, N, N '-4,4-diphenyl sulfone bismaleimides, 2, two (4-(4-maleimide) phenyl) propane of 2-, 2, two (the 3-secondary butyl-3 of 2-, 4-(4-maleimide phenoxy group) phenyl) propane, 1, two (4-(the 4-maleimide phenoxy group) phenyl) decane of 1-, 4, the two (1-(4-maleimide phenoxy group)-2-cyclohexyl benzene of 4 '-cyclohexylidene, 2, two (4-(4-maleimide phenoxy group) phenyl) HFC-236fa of 2-etc. can separately or be mixed more than two kinds and use.
The citraconimide resin is the polymer that has the citraconimide compound of at least one citraconimide base in molecule, the citraconimide compound is that for example phenyl citraconimide is arranged, 1-methyl-2,4-dual-citraconic imide benzene, N, N '-adjacent phenylene dual-citraconic imide, N, N '-TOPOT 2,2 citraconimide, N, N '-4,4-biphenylene dual-citraconic imide, N, N '-4,4-(3,3-dimethyl biphenylene) dual-citraconic imide, N, N '-4,4-(3, 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 sulfone dual-citraconic imide, 2, two (4-(the 4-citraconimide phenoxy group) phenyl) propane of 2-, 2, two (3-secondary butyl-3,4-(the 4-citraconimide phenoxy group) phenyl) propane of 2-, 1,1-two (4,4 (citraconimide phenoxy group) phenyl) decane, 4,4 '-cyclohexylidene-two (1-(4-citraconimide phenoxy group) phenoxy group)-2-cyclohexyl benzene, 2, two (4-(4-citraconimide phenoxy group) phenyl) HFC-236fa of 2-etc. can separately or be mixed more than two kinds and use.
The norbornene imide resin is the polymer that has the norbornene imide compound of at least one norbornene imide base in the molecule, the norbornene imide compound is that for example phenyl norbornene imide is arranged, 1-methyl-2, the two norbornene imide benzene of 4-, N, the two norbornene imide of N '-adjacent phenylene, N, N '-TOPOT 2,2 norbornene imide, N, N '-4, the two norbornene imide of 4-biphenylene, N, N '-4,4-(3,3-dimethyl biphenylene) two norbornene imide, N, N '-4,4-(3, the 3-dimethyl diphenylmethane) two norbornene imide, N, N '-4,4-(3,3-diethyl diphenyl methane) two norbornene imide, N, N '-4, the two norbornene imide of 4-diphenyl methane, N, N '-4, the two norbornene imide of 4-diphenyl propane, N, N '-4, the two norbornene imide of 4-diphenyl ether, N, N '-4, the two norbornene imide of 4-diphenyl sulfone, 2, two (4-(the 4-norbornene imide phenoxy group) phenyl) propane of 2-, 2, two (the 3-secondary butyl-3 of 2-, 4-(4-norbornene imide phenoxy group) phenyl) propane, 1, two (4-(the 4-norbornene imide phenoxy group) phenyl) decane of 1-, 4,4 '-cyclohexylidene-two (1-(4-norbornene imide phenoxy group) phenoxy group)-2-cyclohexyl benzene, 2, two (4-(4-norbornene imide phenoxy group) phenyl) HFC-236fa of 2-etc. can separately or be mixed more than two kinds and use.
When using above-mentioned free-radical polymerised compound, can use polymerization initiator.As polymerization initiator, so long as the compound that produces free radical by heat or light just has no particular limits, peroxide, azo-compound etc. are for example arranged, can consider the connection temperature, connect hours, storage stability etc. of target and suitably select.Viewpoint from high response and storage stability, with the temperature of 10 hours half-life more than 40 ℃, and the temperature of 1 minute half-life is desirable at the organic peroxide below 180 ℃, and with the temperature of 10 hours half-life more than 50 ℃, and the temperature of 1 minute half-life is optimal at the organic peroxide below 170 ℃.The desirable curing agent proportional quantity that can access abundant reactivity when the connect hours is 10 seconds is, 1 to 20 weight % of adhesive composite total amount, and it is desirable to 2 to 15 weight % especially.The particular compound of the organic peroxide that the present invention uses can be selected from diacyl peroxide, peroxide two carbonic esters, peroxy esters class, peroxy ketal, dialkyl peroxide, hydroperoxides, silylation peroxide etc.; wherein it is desirable to peroxy esters class, dialkyl peroxide, hydroperoxides, silylation peroxide especially; be because initator in chloride ion or organic acid 5; below the 000ppm, the organic acid that is produced after the heating and decomposition is few and can suppress corrosion to the connecting terminal of circuit member.
The diacyl peroxide class can be enumerated isobutyl group and cross vapour, 2; 4-dichloro-benzoyl base peroxide, 3; 5,5-trimethyl acetyl base peroxide, sim peroxides, lauroyl peroxide, stearyl peroxide, succinyl group peroxide, benzene methyl base peroxidating toluene, benzoyl peroxide etc.
Peroxide two carbonates can be enumerated di n propyl peroxy dicarbonate, diisopropyl peroxydicarbonate, two (three grades of butyl cyclohexyl of 4-) peroxide two carbonic esters, two-2-ethyoxyl methoxy base peroxide, two carbonic esters, two-(2-ethylhexyl peroxy) two carbonic esters, dimethoxy butyl peroxy two carbonic esters, two (3-methyl-3-methoxyl group butyl peroxy) two carbonic esters etc.
The peroxy esters class can be enumerated the cumenyl new decanoate ester peroxide; 1; 1; 3; the 3-tetramethyl butyl is crossed gasification neodecanoic acid ester; 1-cyclohexyl-1-Methylethyl new decanoate ester peroxide; three grades of hexyl new decanoate ester peroxides; three grades of butyl peroxy pivalic esters; 1; 1; 3; 3-tetramethyl butyl peroxidating-2 ethyl hexanoic acid ester; 2; 5-dimethyl 1; 5-two (2 ethyl hexanoic acid base peroxy) hexane; 1-cyclohexyl-1-Methylethyl peroxidating-2 ethyl hexanoic acid ester; three grades of hexyl peroxidating-2 ethyl hexanoic acid esters; three grades of butyl peroxyization-2 ethyl hexanoic acid esters; three grades of butyl peroxy isobutyrates; 1; two (the three grades of butyl peroxies) cyclohexanes of 1-; three grades of hexyl peroxidating isopropyl monocarbonates; three grades of butyl peroxyization-3; 5; 5-tri-methyl hexanoic acid ester; three grades of butyl peroxy moons are hung acid esters; 2; 5-dimethyl-2,5-two (a methyl benzoyl peroxy) hexane; three grades of butyl peroxy isopropyl monocarbonates; three grades of butyl peroxyization-2-ethylhexyl monocarbonates; three grades of hexyl peroxide benzoates; three grades of butyl peroxy acetates etc.
The peroxy ketal class can enumerate 1, two (the three grades of hexyl peroxies)-3 of 1-, 3,5-trimethyl-cyclohexane, 1, two (the three grades of hexyl peroxies) cyclohexanes, 1 of 1-, two (the three grades of butyl peroxies)-3 of 1-, 3,5-trimethyl-cyclohexane, 1,1-(three grades of butyl peroxies) cyclododecane, 2, two (three grades of butyl peroxies) decane of 2-etc.
Dialkyl peroxide gas can be enumerated α, α '-two (three grades of butyl peroxies) diisopropyl benzene, diisopropylbenzyl peroxide, 2, and 5-first 1,5-two (three grades of butyl peroxies) hexane, three grades of butyl different third be basic peroxide etc. not.
Hydroperoxide type can be enumerated diisopropyl benzene hydroperoxides, cumene hydroperoxide etc.
The silylation peroxide can be enumerated three grades of butyl TMS peroxide, two (three grades of butyl) dimethylsilyl peroxide, three grades of butyl trivinyl silylation peroxide, two (three grades of butyl) divinyl silylation peroxide, three (three grades of butyl) divinyl peroxide, three grades of butyl triallyl silylation and cross vapour, two (three grades of butyl) diallylsilane base peroxide, three (three grades of butyl) allyl silicane base peroxide etc.
For the corrosion of the connecting terminal that suppresses circuit member or the corrosion of circuit electrode, it is desirable in curing agent or the chloride ion that is contained in the above-mentioned organic peroxide or organic acid amount less than 5,000ppm, and the less organic peroxide of the organic acid that is produced after the heating and decomposition is better.And, for the stability of the circuit connection material that improves made, it is desirable to open under room temperature (25 ℃), the normal pressure place 24 hours after the weight conservation rate greater than 20 weight %.Can suitably mix above-mentioned organic peroxide during use.
Above-mentioned free free-radical generating agent can be used alone or as a mixture, and also can mix use with decomposition accelerating agent, inhibitor etc.
And, coated by the polymer substance of polyurethane series, polyester system etc. and by the curing agent of microencapsulation, so be desirable because of prolonging service time.
Heat-curing resin is except the radical polymerization syzygy, also has epoxy resin, it is varnish type epoxy resin, cresols varnish type epoxy resin, bisphenol-A varnish type epoxy resin, Bisphenol F varnish type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanuric acid ester type epoxy resin, aliphat chain epoxy resin etc. that epoxy resin has bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol, above-mentioned epoxy resin also can be by halogenation, also can be by hydrogenation.Also can make up the above-mentioned epoxy resin more than two kinds and use.
In addition, above-mentioned curing agent for epoxy resin has common epoxy curing agents such as amine, phenols, anhydrides, imidazoles, dicyandiamide class.In addition, also can suitably use used tertiary amine class, organophosphor based compound usually as curing accelerator.
And, can use the cationic polymerization method of utilizing above-mentioned curing agent and sulfonium salt, salt compounded of iodine etc. to carry out as the method that makes the epoxy resin reaction.
Stress relaxation when giving adhesive for circuit connection of the present invention with film forming, cementability, curing is used high molecular components such as polyvinyl butyral resin, vinyl-formal resin, mylar, polyamide, polyimide resin, xylene resin, phenoxy resin, polyurethane resin, urea resin.The weight average molecular weight of above-mentioned high molecular component is 10,000 to 10,000,000th, and is desirable.And above-mentioned resin also can be modified as free-radical polymerised functional group, and this moment, thermal endurance was improved.In addition, when in above-mentioned resin, containing carboxyl, it can be used as the carboxylic compound among the present invention.The proportional quantity of high molecular component is 2 to 80 weight % of adhesive composite total amount, it is desirable to 5 to 70 weight %, and 10 to 60 weight % is optimal.If less than 2 weight %, then lax the or bonding force of stress is insufficient, if surpass 80 weight %, then mobile variation.
Also can suitably add filler, softening agent, promoter, aging chemical defence agent, colouring agent, fire retardant, couplant in the adhesive for circuit connection of the present invention.
The used adhesive for circuit connection of the present invention is, even do not contain conducting particles, also connected by the direct contact of electrode in opposite directions during connection, but can obtain more stable connection when containing conducting particles.Can use metallic or the particles after coating precious metal such as Au, Ag, platinum on the non-conductive particle surface such as carbon, glass, pottery, plastic cement such as Au, Ag, Ni, Cu, scolding tin as conducting particles.In order to suppress the oxidation on metal ion surface, it is desirable using by the metallic after the precious metal coating.In the above-mentioned conducting particles, the heating and pressurizing distortion when connecting of particle that coats as core, by Au, Ag etc. with plastic cement or hot molten metal particle increases contact area and improves reliability.The thickness of precious metal coating layer is more than 100 dusts, it is desirable at this moment can obtain good connection more than 300 dusts.And, also can use with the conducting particles after the insulative resin coating as above-mentioned conductive ion.With respect to bonding agent composition 100 volume %, conducting particles accounts for 0.1 to 30 volume %, it is desirable to suitably cooperate according to purposes in 0.1 to 10 volume % scope.
And, the present invention 1 in, the Tg when adhesive for circuit connection of the present invention also can be solidfied material (glass transition temperature) differs the multi-ply construction that layer constituted more than two kinds more than 5 ℃.
In addition, the present invention 2 in, containing acid equivalent in one deck at least of first bond layer and second bond layer is desirable at the compound of 5 to 500 (KOH milligrams/gram).
Use adhesive for circuit connection of the present invention to carry out bonding substrate to be, be electrically connected the just passable of required electrode as long as form, not special restriction, employed glass or the plastic substrate that is formed with transparent electrode thin film electrodes such as (ITO) of LCD arranged, printed circuit board (PCB), ceramic circuit board, flexible circuit board, semiconductor silicon chips etc., use capable of being combined in case of necessity.
Use aforesaid substrate to do when connecting, it is desirable that the first higher bond layer of Tg in the present invention's 2 the adhesive for circuit connection is arranged at the higher substrate side surfaces of spring rate.Can further reduce the generation that comes off thus.
Condition during connection there is no particular restriction, and connecting temperature is 90 to 250 ℃, and the connect hours is 1 second to 10 minutes, can do suitably to select according to the purposes of using, bonding agent, substrate etc., also can carry out the back cured in case of necessity.And, though connect by heating and pressurizing, and as required, use heat other energy in addition, for example light, ultrasonic wave, electromagnetic wave etc. also are fine.
Embodiment
More specifically describe the present invention by the following examples, but scope of the present invention is not limited only to this embodiment.
Mix respectively according to following prescription, using simple and easy coating machine (tester industry corporate system) to be coated in thickness is on 50 microns the surface treated PET of single face (PETG) film, utilize 70 ℃, 5 minutes heated-air drying is made film.
(synthesizing of ammonia ester acrylate)
Polycaprolactone glycol 400 weight portions with weight average molecular weight 800,2-hydroxypropyl acrylate 131 weight portions, as dibutyl tin two lauryls 0.5 weight portion of catalyst, reach Hydroquinone monomethylether 1.0 weight portions as polymerization inhibitor, mix while stir 50 ℃ of heating.Then splash into IPDI 222 weight portions, then, be warming up to 80 ℃ and carry out the ammonia esterification while stir.After confirming reactivity oneself reaching 99% or more, reduce reaction temperature and must ammonia ester acrylate.
Use above-mentioned ammonia ester acrylate as free-radical polymerised material.And, the butyral resin (6000EP of use carboxylic acid upgrading; Electrochemical Industries, Inc system trade name, acid equivalent 250 (KOH milligram/gram)) and phenoxy resin (PKHC; The system merchant of Union Carbide Corp name name, weight average molecular weight 45,000) form material as film.
50 weight %DOP (dioctyl phthalate) solution that use three grades of hexyl peroxidating-2 ethyl hexanoic acid esters are as the curing agent that can produce free free radical by heating.
Use with polystyrene to be core, be provided with the nickel dam of 0.2 micron of thickness at its particle surface, be provided with the gold layer of 0.04 micron of thickness in the outside of this nickel dam and the conducting particles of 4 microns of the average grain diameters of making as conducting particles.
Embodiment 1
In the solid constituent weight ratio, to restrain through the butyral resin (with solid component meter) 20 that carboxylic acid transforms, phenoxy resin (with solid component meter) 30 grams, ammonia ester acrylate 49 grams, phosphate type acrylate (grease limited company of common prosperity society system, trade name P2M) 1 gram, three grades of hexyl peroxidating-2 ethyl hexanoic acid ester 5 grams (counting 10 grams with DOP solution) mix, the conducting particles that disperses 3 volume % again, the thickness that be coated with, drying obtains bond layer are 8 microns circuit connection material.
(making of circuit connection structure)
80 ℃, 5 seconds, under the 1MPa condition, the interim connection made the rectangular foregoing circuit connection material of 1.5 mm wides on the glass substrate that is formed with the ITO electrode.The PET base material is peeled off, aimed at the electrode that it installs TCP,, 20 seconds, do formal connection under the 4MPa condition at 150 ℃.
Embodiment 2
In the solid constituent weight ratio, the butyral resin (with solid component meter) 30 that carboxylic acid is transformed restrains, phenoxy resin (with solid component meter) 30 grams, ammonia ester acrylate 39 grams, phosphate type acrylate (grease limited company of common prosperity society system, trade name P2M) 1 gram, three grades of hexyl peroxidating-2 ethyl hexanoic acid ester 5 grams (counting 10 grams with DOP solution) mix, the thickness that the conducting particles of dispersing and mixing 3 volume % again, coating, drying obtain bond layer is 8 microns circuit connection material.
(making of circuit connection structure)
80 ℃, under 5 seconds, 1MPa condition, the interim connection makes the rectangular foregoing circuit of 1.5 mm wides and connects material on the glass substrate that forms the ITO electrode.The PET base material is peeled off, aimed at the electrode that it installs TCP,, 20 seconds, do formal connection under the 4Mpa at 150 ℃.
Embodiment 3
In the solid constituent weight ratio, the butyral resin (with solid component meter) 10 that carboxylic acid is transformed restrains, phenoxy resin (with solid component meter) 35 grams, ammonia ester acrylate 54 grams, phosphate type acrylate (grease limited company of common prosperity society system, trade name P2M) 1 gram, three grades of hexyl peroxidating-2 ethyl hexanoic acid ester 5 grams (counting 10 grams with DOP solution) mix, dispersing and mixing conducting particles 3 volume % again, the thickness that coating, drying obtain bond layer are 8 microns circuit connection material.
(making of circuit connection structure)
Foregoing circuit is connected material make the rectangular of 1.5 mm wides, on the glass substrate that forms the ITO electrode, 80 ℃, do interim connection under 5 seconds, 1MPa condition.The PET base material is peeled off, aimed at the electrode that it installs TCP,, 20 seconds, do formal connection under the 4Mpa at 150 ℃.
Comparative example 1
In the solid constituent weight ratio, with phenoxy resin (with solid component meter) 45 grams, ammonia ester acrylate 54 grams, phosphate type acrylate (grease limited company of common prosperity society system, trade name P2M) 1 gram, three grades of hexyl peroxidating-2 ethyl hexanoic acid esters 5 grams (then is 10 grams in DOP solution) mix, dispersing and mixing conducting particles 3 volume % again, and the thickness that obtains bond layer is 8 microns circuit connection material.
(making of circuit connection structure)
Foregoing circuit is connected material make the rectangular of 1.5 mm wides, on the glass substrate that forms the ITO electrode, 80 ℃, do interim connection under 5 seconds, 1MPa condition.The PET base material is peeled off, aimed at the electrode that it installs TCP,, 20 seconds, do formal connection under the 4Mpa at 150 ℃.
(method of evaluating characteristic)
(1) connects resistance: use the universal instrument TR6848 of atobandeisto (strain) system, measure in abutting connection with the resistance between circuit with the fixed current of 1 milliampere.
(2) adhesive strength: carry out according to J1S Z-0237, use the smart mechanism of Japan to make the STOROGRAPH E-S type of institute's (strain) system, peel off with 90 degree and do mensuration.
(3) observation of coupling part: have or not with metal microstructure sem observation coupling part peel off, bubble.
(4) reliability assessment: about above-mentioned connection resistance, bonding force carries out high temperature and humidity test at 80 ℃, the condition of 95%RH, takes out after 240 hours, does the test of project (1) to (3).
Its measurement result is shown in table 1.
(table 1)
Embodiments of the invention 1 to 3 all demonstrate good connection resistance, bonding force and coupling part appearance characteristics, also show good reliability after the humidity test.With respect to this, use in the comparative example of acid equivalent less than the compound of 5 (KOH milligrams/gram), the initial value of bonding force is low, and connection resistance uprises after humidity test, the bonding force step-down peels off and connection reliability is poor.
Embodiment 4
(first bond layer)
Use dihydroxymethyl tristane diacrylate and above-mentioned ammonia ester acrylate as free-radical polymerised material.
Use phenoxy resin (PKHC; Union Carbide Corp's system trade name, weight average molecular weight 45,000) form material as film.
Use three grades of hexyls to cross 50 weight %DOP (dioctyl phthalate) solution of gasification-2 ethyl hexanoic acid ester as the curing agent that produces free free radical by heating.
Polystyrene be the particle surface of core thickness is set is 0.2 micron nickel dam, at the gold layer of 0.04 micron of the arranged outside thickness of this nickel dam, make the conducting particles of 4 microns of average grain diameters.
In the weight ratio of solid composition, mix phenoxy resin (with solid component meter) 50 grams, dihydroxymethyl tristane acrylate 30 grams, ammonia ester acrylate 19 grams, phosphate type acrylate (grease limited company of common prosperity society system trade name; P2M) 1 gram, three grades of hexyl peroxidating-2 ethyl hexanoic acid esters 5 grams (then is 10 grams in DOP solution), the conducting particles of dispersing and mixing 3 volume % again, it is 8 microns circuit connection material (Tg of solidfied material is 110 ℃) that coating, drying obtain bond layer thickness.
(second bond layer)
Use ammonia ester acrylate as free-radical polymerised material.
Use phenoxy resin (PKHC; Union Carbide Corp's system trade name, weight average molecular weight 45,000) form material as film.
50 weight %DOP (dioctyl phthalate) solution that use three grades of hexyl peroxidating-2 ethyl hexanoic acid esters are as the curing agent that produces free free radical by heating.
At polystyrene is the nickel dam that the particle surface of core is provided with 0.2 micron of thickness, at the gold layer of 0.04 micron of the arranged outside thickness of this nickel dam, makes the conducting particles of 4 microns of average grain diameters.
Weight ratio in the solid composition, mix phenoxy resin (with solid component meter) 50 grams, 10 g of dihydroxymethyl tristane acrylate, the above-mentioned ammonia ester acrylate that synthesizes 39 grams, phosphate type acrylate (grease limited company of common prosperity society system trade name; P2M) 1 gram, three grades of hexyl peroxidating-2 ethyl hexanoic acid esters 5 grams (then is 10 grams in DOP solution), the conducting particles of dispersing and mixing 3 volume % again, coating, dry bond layer thickness are 18 microns circuit connection material (Tg of solidfied material is 60 ℃).
First bond layer and second bond layer are fitted into the adhesive for circuit connection of two layers of structure with the roller stacking-up machine.
Embodiment 5
(first bond layer)
Except that the thickness of bond layer is 12 microns, obtain circuit connection material (Tg of solidfied material is 110 ℃) with quadrat method with first bond layer of embodiment 4.
(second bond layer)
Except that the thickness of bond layer is 15 microns, obtain circuit connection material (Tg of solidfied material is 60 ℃) with quadrat method with second bond layer of embodiment 4.
First bond layer and second bond layer are fitted into the adhesive for circuit connection of two layers of structure with the roller stacking-up machine.
Embodiment 6
(first bond layer)
Except that the thickness of bond layer is 18 microns, be connected with material (Tg of solidfied material is 110 ℃) to obtain circuit with quadrat method with first bond layer of embodiment 4.
(second bond layer)
Except that the thickness of bond layer is 14 microns, be connected with material (Tg of solidfied material is 60 ℃) to obtain circuit with quadrat method with second bond layer of embodiment 4.
First bond layer and second bond layer are fitted into the adhesive for circuit connection of two layers of structure with the roller stacking-up machine.
Embodiment 7
(first bond layer)
Use phenoxy resin (PKHC; Union Carbide Corp's system trade name, weight average molecular weight 45,000) form material as film.
50 weight %DOP (dioctyl phthalate) solution that use three grades of hexyl peroxy-2 ethyl hexanoic acid esters are as the curing agent that can produce free free radical by heating.
At the particle surface that with the polystyrene is core the nickel dam of 0.2 micron of thickness is set,, makes the conducting particles of 4 microns of average grain diameters at the gold layer of 0.04 micron of the arranged outside thickness of this nickel dam.
Weight ratio in solid constituent: mix phenoxy resin (with solid component meter) 40 grams, dihydroxymethyl tristane diacrylate 20 grams, 39 g of ammonia ester acrylate, phosphate type acrylate (grease limited company of common prosperity society system trade name; P2M) 1 g, three grades of hexyl peroxidating-5 g of 2 ethyl hexanoic acid esters (then being 10 g) in DOP solution, the conducting particles of dispersing and mixing 3 volume % again, obtaining bond layer thickness through coating, drying is that 8 microns circuit connects with material (Tg of solidfied material is 68 ℃).
(second bond layer)
Utilize phenoxy resin (PKHC; Union Carbide Corp system trade name, weight average molecular weight 45,000) and the butyral resin (6000EP that transforms through carboxylic acid; Electrochemical Industries, Inc system trade name, acid equivalent 250 (KOH milligram/gram)) form material as film.
50 weight %DOP (dioctyl phthalate) solution that utilize three grades of hexyl peroxidating-2 ethyl hexanoic acid esters are as the curing agent that can produce free free radical by heating.
At the particle surface that with the polystyrene is core thickness being set is 0.2 micron nickel dam, is that 0.04 micron gold layer is made the conducting particles of 4 microns of average grain diameters at the arranged outside thickness of this nickel dam then.
Weight ratio in solid constituent, mix phenoxy resin (with solid component meter) 30 grams, the butyral resin (with solid component meter) 20 that transforms through carboxylic acid restrains, dihydroxymethyl tristane diacrylate 10 grams, the above-mentioned ammonia ester acrylate that synthesizes 39 grams, phosphate type acrylate (grease limited company of common prosperity society system, trade name P2M) 1 gram, three grades of hexyl peroxidating-2 ethyl hexanoic acid ester 5 grams (counting 10 grams) with DOP solution, the conducting particles of dispersing and mixing 3 volume % again is through coating, it is 18 microns circuit connection material (Tg of solidfied material is 52 ℃) that drying obtains bond layer thickness.
First bond layer and second bond layer are fitted into the adhesive for circuit connection of two layers of structure with the roller stacking-up machine.
Comparative example 2
Only use first bond layer of embodiment 4, acquisition bond layer thickness is 25 microns circuit connection material (Tg of solidfied material is 110 ℃).
Comparative example 3
Only use second bond layer of embodiment 4, acquisition bond layer thickness is 25 microns circuit connection material (Tg of solidfied material is 60 ℃).
(making of syndeton)
The adhesive for circuit connection of above-mentioned two layers of structure is made the rectangular of 1.5 mm wides, on the glass substrate that forms the ITO electrode (substrate-side that spring rate is higher), first bond layer that Tg is higher is arranged at glass side, at 80 ℃, 5 seconds, do interim connection under the condition of 1MPa.Then, the PET base material is peeled off, formal connection at 140 ℃, 20 seconds, is done in the position of the electrode of aligning ITO and the electrode of TCP under the condition of 4MPa.
In addition, the second lower bond layer of Tg in two layers of structure bonding agent of embodiment 4 is arranged at glass side, connects under the same conditions, as reference example of the present invention.And, the adhesive for circuit connection of comparative example 2 and 3 is also carried out above-mentioned operation.
(method of evaluating characteristic)
Similarly carry out with embodiment 1 to 3 and comparative example 1.
Characteristic evaluation the results are shown in table 2.
(table 2)
Arbitrary example of embodiment 4 to 7 all has the resistance of connection, adhesive force, and the good result of outward appearance, shows good connection reliability.
With respect to this, in the comparative example 2 and 3 of monolayer constructions will, Tg is 110 ℃ a comparative example 2, though connection resistance does not change and keeps good after humidity test, bonding force descends to some extent and comes off.And Tg is low to be 60 ℃ comparative example 3, finds to have the rising of connection resistance after 240 hours in humidity test, and bonding force also reduces.And the coupling part also comes off.
On the other hand,, the situation that comes off is arranged then, be arranged at the glass substrate side so it is desirable to first bond layer that Tg is higher in the present invention if second bond layer that Tg is lower is arranged at the glass substrate side.
1 bonding force that can improve after initial stage and the humidity test according to the present invention, and the adhesive for circuit connection of having realized connecting the low temperatureization of temperature and having shortened the connect hours can be provided, and the circuit connection structure that uses this bonding agent.
And, the present invention's 2 adhesive for circuit connection and use circuit connecting method, the circuit connection structure of this bonding agent, providing can be according to the low temperatureization that connects temperature and the requirement of the shorteningization of connect hours, can connect with 20 seconds at 140 ℃, and not peel off in the humidity test after connection to come off yet, demonstrate the circuit connection structure of excellent connection reliability.
Claims (2)
1. circuit connection structure, it is characterized in that, make adhesive for circuit connection between between substrate with circuit electrode in opposite directions, to having the substrate pressurization of circuit electrode in opposite directions, thereby be electrically connected the electrode of compression aspect, described adhesive for circuit connection contains the butyral resin of carboxylic acid upgrading, and also contains phenoxy resin and have the free-radical polymerised material that phosphate is constructed.
2. circuit connection structure according to claim 1 is characterized in that, in the described adhesive for circuit connection, the content of electroconductive particle is 0.1～30 volume % with respect to bonding agent composition 100 volume %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000128937 | 2000-04-25 | ||
| JP2000128936 | 2000-04-25 | ||
| JP2000128936 | 2000-04-25 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018082556A Division CN1214455C (en) | 2000-04-25 | 2001-04-25 | Adhesive for circuit connection, circuit connection method using the same, and circuit connection structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1722395A CN1722395A (en) | 2006-01-18 |
| CN100524674C true CN100524674C (en) | 2009-08-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100764482A Expired - Fee Related CN100524674C (en) | 2000-04-25 | 2001-04-25 | Circuit connection method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100524674C (en) |
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2001
- 2001-04-25 CN CNB2005100764482A patent/CN100524674C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1722395A (en) | 2006-01-18 |
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