CN1737078A - Wiring-connecting material and process for producing circuit board with the same - Google Patents
Wiring-connecting material and process for producing circuit board with the same Download PDFInfo
- Publication number
- CN1737078A CN1737078A CN 200510099951 CN200510099951A CN1737078A CN 1737078 A CN1737078 A CN 1737078A CN 200510099951 CN200510099951 CN 200510099951 CN 200510099951 A CN200510099951 A CN 200510099951A CN 1737078 A CN1737078 A CN 1737078A
- Authority
- CN
- China
- Prior art keywords
- wiring
- resin
- connecting material
- connection terminal
- mentioned
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- DCVWZWOEQMSMLR-UHFFFAOYSA-N silylperoxysilane Chemical compound [SiH3]OO[SiH3] DCVWZWOEQMSMLR-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- KVWOTUDBCFBGFJ-UHFFFAOYSA-N tert-butyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(C)(C)C KVWOTUDBCFBGFJ-UHFFFAOYSA-N 0.000 description 1
- WJXKWIFHRZWPET-UHFFFAOYSA-N tert-butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC(C)(C)C WJXKWIFHRZWPET-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a wiring-connecting material comprising from 2 to 75 parts by weight of a polyurethane resin, from 30 to 60 parts by weight of a radical-polymerizable substance and from 0.1 to 30 parts by weight of a curing agent capable of generating a free radical upon heating, and a process for producing a wiring-connected board by using the wiring-connecting material. The wiring-connecting material of the present invention may preferably further contain a film-forming material and/or conductive particles.
Description
Technical field
The present invention relates to use the wiring-connecting material of binder composition and electroconductive particle and the manufacture method of wiring board.
Background technology
Metabond be owing to can obtain reasons such as high bond strength, water tolerance and excellent heat resistance, is widely used in the various uses such as electric, electronics, building, automobile, aircraft.Wherein, one-component epoxy resin class tackiness agent does not need host is mixed with solidifying agent, and is therefore easy to use, is widely used with film like, paste body shape, pulverous form.In the one-component epoxy resin class tackiness agent, owing to can make Resins, epoxy and solidifying agent and properties-correcting agent carry out multiple combination, therefore, open put down in writing in the clear 62-141083 communique such, can obtain desirable performance by selecting this to make up aptly just as for example spy.
But, this spy opens the film like tackiness agent shown in the clear 62-141083 communique, because in order to obtain more satisfactory stability aspect short period of time solidified nature (rapidly-curable) and the storage stability (keeping quality) two, use and be inert catalyst type solidifying agent under the normal temperature, can not get sufficient reaction when therefore solidifying, so, though operation is good, but must be heated to about 140～180 ℃ in the tie-time about 20 seconds, and in 10 seconds, must be heated to about 180～210 ℃.
But in recent years, developed into the circuit densification in the precision electronic device field, the width of connection terminal, the interval of connection terminal become very narrow.Therefore, if connect according to the condition of contact of in the past epoxy resin wiring-connecting material, take place sometimes distribution come off or peel off, phenomenon such as displacement.In addition, in order to enhance productivity, also requirement can 10 seconds with interior connection, thereby will shorten the tie-time.In order to satisfy these requirements, just require to have at low temperatures and the wiring-connecting material of solidified low temperature rapidly-curable at short notice.
Disclosure of an invention
The purpose of this invention is to provide epoxy resin a kind of and in the past is connected material and compares better and electric, the electronics with work-ing life of low temperature rapidly-curable with wiring-connecting material and the manufacture method of using the wiring board of this material.
Among the present invention, provide a kind of like this wiring-connecting material, wherein contain urethane resin 2～75 weight parts, free-radical polymerised material 30～60 weight parts and be subjected to solidifying agent 0.1～30 weight part of the free free radical of thermogenesis.Wiring-connecting material of the present invention is particularly suitable for making it between the connection terminal of relative configuration as a kind of like this connection material, to the connection terminal pressurization of relative configuration, thereby reaches circuit between connection terminal and connects making on the compression aspect.
Wish further to contain film forming material and/or electroconductive particle in the wiring-connecting material of the present invention.The use level of film forming material wishes to be 0～40 weight part, is preferably polyimide resin.
In addition, as urethane resin, a kind of yield point that adopts the flow test method to measure of preferred use is 40 ℃～140 ℃ a resin, as solidifying agent, wish that a kind of 25 ℃, 24 hours weight conservation rate of use (i.e. the ratio of the quality before the of poor quality and placement of 24 hours front and back of unlimited placement under room temperature (25 ℃), normal pressure) is the solidifying agent more than the 20 weight %.As free-radical polymerised material, urethane acrylate is suitable.
In addition, provide a kind of manufacturing method of wiring board that comprises with the operation that couples together between the terminal of wiring-connecting material of the present invention among the present invention with distribution.Promptly, the invention provides a kind of like this manufacturing method of wiring board, but this method is to comprise coupling together between the distribution component of connection terminal having respectively so that the manufacturing method of wiring board of the connection operation of conducting between this connection terminal, wherein, connect operation and comprise wiring-connecting material of the present invention is clamped between the plural distribution component of the mutual subtend configuration of the face with connection terminal, and by the operation of distribution component to its limit pressurization, limit heating.Manufacture method of the present invention is specially adapted at least one surface of connection terminal by being selected from least a kind of occasion that constitutes in gold and silver and the platinum metals.
The simple declaration of accompanying drawing
Fig. 1 is the explanatory view that the manufacturing method of wiring board of embodiment 1 is shown.
Fig. 2 is the sectional view that the connection portion of the flexible wiring that uses among the embodiment 3 is shown.
Fig. 3 is the sectional view that the wiring substrate of the liquid crystal panel connection portion of using among the embodiment 4 is shown.
The preferred plan that is used to carry out an invention
A. solidifying agent
The solidifying agent that uses among the present invention is the compound that decomposes such as superoxide, azo compound produce free free radical.Solidifying agent can be selected aptly according to wiring temperature, setting up time, the storage period of target waiting, in order to realize hyperergy and long storage life, the temperature of preferred 10 hours transformation period is more than 40 ℃ and the temperature of 1 minute transformation period is a organo-peroxide below 180 ℃, and more preferably the temperature of 10 hours transformation period is more than 60 ℃ and the temperature of 1 minute transformation period is a organo-peroxide below 170 ℃.
Making setting up time is occasion below 10 seconds, and in order to obtain enough reactivities, the use level of solidifying agent is preferably 0.1～30 weight part, more preferably 1～20 weight part.During use level less than 0.1 weight part of solidifying agent, can not get enough reactivities, thereby be difficult to obtain good bonding strength or less connection resistance.If use level surpasses 30 weight parts, then there is the flowability of wiring-connecting material to reduce or connection resistance rising or the tendency that shortens the storage period of wiring-connecting material.
As the preferred organo-peroxide of solidifying agent of the present invention, can enumerate peroxidation two acyls, peroxy dicarbonate, peroxyester, ketone peroxide acetal, dialkyl peroxide, hydroperoxide, silyl superoxide etc.
As peroxidation two acyl classes, can enumerate isobutyl peroxide, peroxidation 2,4-dichloro-benzoyl, peroxidation 3,5,5-trimethyl acetyl, peroxidation decoyl, lauroyl peroxide, stearoyl, succinyl peroxide, benzoyl peroxide toluene, benzoyl peroxide etc.
As peroxy dicarbonates, can enumerate peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, two (4-tert-butylcyclohexyl) peroxy dicarbonate, two-2-ethoxyethyl group peroxy dicarbonate, two (peroxidation of 2-ethylhexyl), two carbonic ethers, dimethoxy butyl peroxyization two carbonic ethers, two (3-methyl-3-methoxyl group butyl peroxyization) two carbonic ethers etc.
As peroxyesters; can enumerate peroxidation neodecanoic acid isopropyl benzene ester; 1; 1; 3; 3-tetramethyl butyl new decanoate ester peroxide; 1-cyclohexyl-1-methylethyl new decanoate ester peroxide; the own ester of peroxidation neodecanoic acid uncle; the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester; 1; 1; 3; 3-tetramethyl butyl peroxidation-2-ethylhexanoate; 2; 5-dimethyl-2; 5-two (peroxidation of 2-ethyl hexanoyl base) hexane; 1-cyclohexyl-1-methylethyl peroxidation-2-ethylhexanoate; peroxidation-own the ester of 2 ethyl hexanoic acid uncle; peroxide-2-ethyl hexanoic acid tert-butyl; the peroxidation tert-butyl isobutyrate; 1; 1-two (tert-butyl hydroperoxide) hexanaphthene; uncle's hexyl peroxidation sec.-propyl monocarbonate; peroxidation-3; 5; the 5-tri-methyl hexanoic acid tert-butyl ester; the peroxidation lauric acid tert-butyl ester; 2; 5-dimethyl-2,5-two (peroxidation of toluoyl base) hexane; tert-butyl hydroperoxide sec.-propyl monocarbonate; tert-butyl hydroperoxide-2-ethylhexyl monocarbonate; the own ester of peroxidation phenylformic acid uncle; peroxide acetic acid butyl ester etc.
In the ketone peroxide acetal, can enumerate 1,1-two (peroxidation of uncle's hexyl)-3,3,5-trimethyl-cyclohexane, 1,1-two (peroxidation of uncle's hexyl) hexanaphthene, 1,1-two (tert-butyl hydroperoxide)-3,3,5-trimethyl-cyclohexane, 1,1-(tert-butyl hydroperoxide) cyclododecane, 2,2-two (tert-butyl hydroperoxide) decane etc.
In the dialkyl peroxide class, can enumerate α, α '-two (tert-butyl hydroperoxide) diisopropylbenzene(DIPB), dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, tertiary butyl cumyl peroxide etc.
In the hydroperoxide type, can enumerate diisopropylbenzenehydroperoxide, isopropyl benzene hydroperoxide etc.
As the silyl peroxide, can enumerate tertiary butyl trimethyl silyl superoxide, two (tertiary butyl) dimetylsilyl superoxide, tertiary butyl trivinyl silyl superoxide, two (tertiary butyl) divinyl silyl superoxide, three (tertiary butyl) vinyl silyl superoxide, tertiary butyl triallyl silyl superoxide, two (tertiary butyl) diallyl silyl superoxide, three (tertiary butyl) allyl group silyl superoxide etc.
Among the present invention, can use, also the compound more than 2 kinds can be merged and use as a kind in these compounds of solidifying agent.In addition, also these solidifying agent (free free radical generating agent) can be merged use with decomposition accelerating agent, inhibitor etc.
Should illustrate that for the corrosion of the connection terminal that suppresses distribution component, preferably make the chlorion that contains in the solidifying agent and organic acid content below 5000ppm, the organic acid that produces after the further preferred thermal degradation is few.In addition, consider, preferably opening wide the weight conservation rate of placement after 24 hours room temperature (25 ℃), normal pressure under more than 20 weight % from the stability of the wiring-connecting material that improves made.
In addition, these solidifying agent being coated and the micro encapsulation solidifying agent that forms with the polymer substance of polyurethanes, polyester etc., owing to prolong work-ing life, is preferred.
B. urethane resin
As urethane resin, stress relaxation when solidifying is good, owing to have polarity aspect such as binding property raising is considered, is preferably among the present invention that the vulcabond that is had the glycol of 2 hydroxyls and had 2 isocyanate group by intramolecularly reacts and the resin that obtains.
As glycol; just can use so long as the line style compound also has the dibasic alcohol of hydroxyl endways, can enumerate polyethylene glycol adipate, polydiethylene glycol adipate, polypropylene adipate (PPA), poly adipate succinic acid ester, poly-hexanodioic acid hexylene glycol ester, polyneopentyl glycol adipate, polycaprolactone polyol, poly-carbonic acid hexylene glycol ester, siloxane polyol, acryl polyvalent alcohol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. particularly.Any compound can be used separately in them, also use can be merged more than 2 kinds.
As vulcabond, can enumerate isophorone diisocyanate, tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, naphthalene-1,5-vulcabond, two isocyanic acids are to phenylene ester, 4,4 '-methylene-bis-cyclohexyl diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate etc.They can use any compound separately, also can merge use more than 2 kinds.
The weight-average molecular weight of the urethane resin that uses among the present invention is preferably 10000～1000000.During weight-average molecular weight less than 10000, the cohesive force of wiring-connecting material reduces, and is difficult to obtain enough bonding strengths, and surpasses 1000000, and then Combination, flowability have the tendency of variation.
In addition, when the synthesis of polyurethane resin, except these two pure and mild vulcabond, can also cooperate polyvalent alcohol, amine, acid anhydrides etc. to react aptly, the urethane that contains imino-that itself and anhydride reaction are obtained because binding property and thermotolerance improve, is preferred.
The urethane resin that uses among the present invention also can be the urethane resin through modification.Particularly using the urethane resin of free-radical polymerised functional group modification, because thermotolerance improves, is preferred.
The urethane resin that uses among the present invention, its yield point that adopts flow test method mensuration is preferably in 40 ℃～140 ℃ scopes, more preferably in 50 ℃～100 ℃ scopes.Should illustrate that the yield point that adopts the flow test method to measure is meant when the mouth mould that uses diameter 1mm, applies the pressure of 3MPa and barrel comes into play when heating up with 2 ℃/minute heat-up rate temperature, use flow test machine is measured.When adopting 40 ℃ of yield point less thaies that the flow test method measures, film-forming properties, binding property be variation sometimes, and when surpassing 140 ℃, the mobile deterioration is taken place sometimes, to being electrically connected with detrimentally affect.
C. film forming material
As the film forming material that uses among the present invention, can enumerate polyimide resin, vinyl-formal resin, polystyrene resin, polyvinyl butyral resin, vibrin, acrylic resin, polyamide resin, xylene resin, phenoxy resin etc.They can use any separately, also can merge use more than 2 kinds.
Should illustrate, film forming material is meant in that solid shapeization and making constitutes under the occasion that composition formation has self supportive film shape with liquid object, give the film mechanical characteristics, thereby make the processing ease of this film, and the sort of material that under the common state that is difficult for tearing, breaking or be clamminess, can operate as film.
As film forming material, consider that from the thermotolerance aspect polyimide resin is specially adapted to the present invention.Polyimide resin can use the polyimide resin that for example makes tetracarboxylic dianhydride and diamines addition reaction synthetic polyamic acid add thermal condensation and imidization takes place.The weight-average molecular weight of polyimide resin is considered from the viewpoint of film-forming properties, is preferably about 10000～150000.
Acid dianhydride that uses during the synthesis of polyimides resin and diamines can be according to selecting aptly to the solvability of solvent or with the intermiscibility of free-radical polymerised material etc.In addition, can use independent compound respectively, also the compound more than 2 kinds can be merged and use.Should illustrate, consider that from improving binding property and flexibility at least a kind of compound has siloxane backbone in preferred acid dianhydride and the diamines.
Should illustrate that the film forming material that uses among the present invention also can carry out modification with free-radical polymerised functional group.
D. free-radical polymerised material
The free-radical polymerised material that uses among the present invention is to have to utilize free radical to carry out the material of polymeric functional group, can enumerate acrylate, methacrylic ester, maleimide compound etc.These can use any separately, also can merge use more than 2 kinds.
Should illustrate that free-radical polymerised material can use with monomer and any state of oligopolymer, also monomer and oligopolymer can be merged use.
Concrete example as preferred acrylate among the present invention, can enumerate methyl acrylate, ethyl propenoate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, the diacrylate binaryglycol ester, trimethyol propane triacrylate, tetrapropylene acid tetramethylol methane ester, 2-hydroxyl-1,3-two propylene acyloxy propane, 2,2-two [4-(acryloyl-oxy ylmethoxy) phenyl] propane, 2,2-two [4-(acryloyl-oxy Quito oxyethyl group) phenyl] propane, the dicyclopentenyl acrylate, three ring decyl acrylate, three (acryloxy ethyl) chlorinated isocyanurates, tricarbimide oxyethane modification diacrylate and urethane acrylate.In addition, also be applicable to the present invention with the corresponding methacrylic ester of these acrylate.
Should illustrate to have in dicyclopentenyl, three ring decyls and the triamine rings thermotolerance that at least a kind free-radical polymerised material can improve the wiring-connecting material of acquisition, be preferred therefore.
As the free-radical polymerised material that uses among the present invention, good in order to make binding property, preferred especially urethane acrylate.The intramolecularly of urethane acrylate has at least 1 above carbamate groups, can enumerate for example resultant of reaction of the acrylic compound of polyvalent alcohol such as polytetramethylene glycol and polyisocyanates and hydroxyl.
In addition, consider that except these free-radical polymerised materials, preferred further merging use has the free-radical polymerised material of phosphate ester structure from the bonding strength on inorganics surfaces such as raising and metal.
As the free-radical polymerised material that preferably has phosphate ester structure among the present invention, can enumerate the reactant of the 2-hydroxyethyl methacrylate of phosphoric anhydride and vinylformic acid 2-hydroxy methacrylate or methacrylic ester corresponding with it.Can use list (2-methacryloxyethyl) phosphate ester acid, two (2-methacryloxyethyl) phosphate ester acid etc. particularly.They can use a kind of compound, also can merge use more than 2 kinds.
As maleimide compound, the maleimide that contains 2 above maleimide base groups in the molecule at least is applicable to the present invention.As this maleimide compound, can enumerate for example 1-methyl-2,4-dimaleoyl imino benzene, N, N '-meta-phenylene bismaleimide, N, N '-TOPOT 2,2 maleimide, N, a N '-tolylene bismaleimides, N, N '-4,4-diphenylene bismaleimides, N, N '-4,4-(3,3 '-dimethyl diphenylene) bismaleimides, N, N '-4,4-(3,3 '-dimethyl diphenylmethane) bismaleimides, N, N '-4,4-(3,3 '-diethyl ditan) bismaleimides, N, N '-4,4-ditan bismaleimides, N, N '-4,4-diphenyl propane bismaleimides, N, N '-4,4-diphenyl ether bismaleimides, N, N '-3,3 '-sulfobenzide bismaleimides, 2,2-two (4-(4-maleimide phenoxyl) phenyl) propane, 2,2-two (3-sec-butyl-3,4-(4-maleimide phenoxyl) phenyl) propane, 1,1-two (4-(4-maleimide phenoxyl) phenyl) decane, 4,4 '-cyclohexylene-two (1-(4-maleimide phenoxyl)-2-cyclohexyl) benzene, 2,2-two (4-(4-maleimide phenoxyl) phenyl) HFC-236fa etc.
Should illustrate, among the present invention, except these free-radical polymerised materials, also can use stoppers such as hydroquinone type, methyl ether hydroquinone type as required aptly.
E. proportioning
More than the use level of each composition in wiring-connecting material of the present invention, urethane resin is that 2～75 weight parts, free-radical polymerised material are 30～60 weight parts, to be subjected to the solidifying agent of the free free radical of thermogenesis be 0.1～30 weight part, containing the occasion of film forming material, its content is 0～40 weight part.The use level of these compositions can be determined in above-mentioned scope aptly.
During use level less than 2 weight parts of urethane resin, wiring-connecting material lacks the effect of stress relaxation when solidifying, during thermal load etc., and bonding strength reduces.And if above 75 weight parts, then connection reliability might reduce.
During use level less than 30 weight parts of free-radical polymerised material, the physical strength of the wiring-connecting material after the curing has the tendency of reduction, and surpasses 60 weight parts, and the viscosity of the wiring-connecting material before then solidifying increases, and operability worsens.
In addition, during use level less than 0.1 weight part of the solidifying agent that can produce free free radical of being heated, can not obtain sufficient reactivity as described above, thereby be difficult to obtain good bonding strength and less connection resistance.Further, if the use level of this solidifying agent surpasses 30 weight parts, then there is the flowability of wiring-connecting material to reduce or connection resistance rising or the tendency that shortens the storage period of wiring-connecting material.
If the use level of film forming material surpasses 40 weight parts, then the flowability of wiring-connecting material reduces, or connecting resistance rises.Should illustrate, if, then also can mismatch film forming material with so-called urethane resin, free-radical polymerised material, other compositions such as solidifying agent film forming fully of being subjected to the free free radical of thermogenesis.
F. electroconductive particle
Even wiring-connecting material of the present invention does not contain electroconductive particle, also can reach purpose of connecting by the direct contact between connection terminal, therefore also can not contain electroconductive particle.But, consider from obtaining more stable connection, wish to contain electroconductive particle.
As electroconductive particle, can use metallicss such as Au, Ag, Ni, Cu, scolding tin and carbon particles etc.In order to obtain sufficiently long storage period, the top layer of particle preferably is not transition metal-type such as Ni, Cu but the precious metal of Au, Ag, platinum family, preferred especially Au.
Should illustrate, particle surfaces such as composite particles that forms as the surface of transition metal-types such as Ni is coated with precious metal such as Au and dielectric glass, pottery, plastics are further used with conductting layer coating, its surface of formation such as above-mentioned metal the composite particles of the outermost layer coating that is formed by precious metal, and those particles that the part in the particle has electroconductibility also can be used as electroconductive particle and are used for the present invention.
The thickness of precious metal coating layer has no particular limits in this composite particles, and in order to obtain good resistance, its thickness is preferably more than 100 .But, on the surface of transition metal such as Ni, lay when layer of precious metal, because redoxomorphism takes place the precious metal break damage that produces etc., produce the free radical that dissociates sometimes when the conducting particles blending dispersion, thereby cause shortening storage period.Therefore, the thickness of precious metal layer is preferably more than 300 .In addition, if the thickness of precious metal layer is thicker than 1 μ m, then effect can reach capacity, and therefore, considers that from viewpoints such as costs thickness is effective below 1 μ m.
Should illustrate, with composite particles and the hot molten metal particle of plastics, owing to heated and the deformability height when pressurizeing as the nuclear core, heating when being subjected to connecting and pressurization deform easily, thereby increasing with the connection terminal contact area, reliability is improved, is preferred therefore.
Cooperate under the occasion of electroconductive particle in the wiring-connecting material of the present invention, its use level is wished 0.1～30 volume % for binder constituents, can determine aptly according to purposes.In order to prevent that superfluous electroconductive particle from causing adjacent circuit short circuit etc., is preferably 0.1～10 volume %.
G. additive
Wiring-connecting material of the present invention except each composition of above-mentioned A～F, can also further contain filler, tenderizer, promotor, protective agent, tinting material, fire retardant, thixotropic agent, coupler etc.
If the cooperation filler then can make the raisings such as connection reliability of the wiring-connecting material of acquisition, is preferred.Preferably less than the particle diameter of electroconductive particle, its use level is preferably 5～60 volume % to the maximum diameter of filler.If surpass 60 volume %, the effect that then improves reliability is saturated.
As coupler, consider from improving fusible viewpoint, preferably contain the compound of vinyl, acryl, amino, epoxy group(ing) and isocyanate group.
H. membrane structure
Needn't there be all compositions in the wiring-connecting material of this formation in simple layer, can make the laminate film more than 2 layers.For example, if the layer that forms the layer contain the solidifying agent that produces free free radical and contain electroconductive particle totally 2 layers of structure are opened these component separating, except can reaching the effect that height becomes more meticulous, can also obtain the effect that prolongs storage period so.
I. the characteristic of wiring-connecting material
Wiring-connecting material of the present invention is a tackiness agent generation melt-flow when connection, makes relative connection terminal contact and after reaching connection, the material of connection takes place to solidify and keep, and the flowability of tackiness agent is an important factor.Wiring-connecting material of the present invention is used the glass of thick 0.7mm, 15mm * 15mm, the wiring-connecting material of thick 35 μ m, 5mm * 5mm is clipped between this glass, under 160 ℃, 2MPa, 10 seconds condition, heat and when pressurizeing, value with the flowability (B)/(A) of area (B) expression after the area (A) at initial stage and the heating and pressurizing is preferably 1.3～3.0, and more preferably 1.5～2.5.If more than 1.3, then have enough flowabilities, can obtain good connection effect.And if, then be difficult to produce bubble, thereby make reliability good below 3.0.
Further, wiring-connecting material of the present invention is used the occasion of differential scanning calorimetry (DSC) with 10 ℃/minute determination of heating rate, the acceleration temperature (Ta) of preferred thermopositive reaction is in 70～110 ℃ scope, top temperature (Tp) is Ta+5～30 ℃, and final temperature (Te) is below 160 ℃.By having this specific character, can have the storage stability under low temperature connectivity and the room temperature simultaneously.
In addition, from the internal stress that reduce to connect the back resin, favourable and obtain good on state characteristic and consider to improving bonding force, the storage modulus that wiring-connecting material of the present invention is solidified under back 25 ℃ is preferably 100～2000MPa, more preferably 300～1500MPa.
J. the manufacture method of wiring board
Wiring-connecting material of the present invention also can be assembled the film like tackiness agent that being connected of substrate or circuit interconnect usefulness as IC chip and chip.
That is to say, use wiring-connecting material of the present invention, make relative first distribution component and second distribution component that has first connection terminal to the ground configuration of first connection terminal with second connection terminal with second connection terminal, between first distribution component and second distribution component, sandwich wiring-connecting material of the present invention (film like tackiness agent), through heating and pressurization, the circuit of first connection terminal and second connection terminal is coupled together, can make wiring board thus.
Should illustrate,, can enumerate as distribution component:
Unicircuit parts such as semiconductor integrated circuit piece, resistance integrated circuit block, electrical condenser integrated circuit block,
Be equipped with tellite integrated circuit block and/or that carried out processing against corrosion,
TAB (tape automated bonding) be with the assembling integrated circuit block, carry out processing against corrosion TCP (tape carrier package),
Liquid crystal panel etc.,
On the insulated substrate that constitutes by plastics (plastics film, plastics sheet etc.) such as the matrix material (glass epoxy resin complex body etc.) of silicon, potassium arsenic, glass, pottery, glass heat thermosetting resin, polyimide etc., by tackiness agent form the conductive metal paper tinsel and form the distribution that comprises connection terminal parts,
On insulated substrate with electrochemical plating or vapour deposition method form conductive wires parts,
The material of coating plating catalyst etc. forms the parts of conductive wires etc.As the preferred distribution component that uses manufacture method of the present invention to connect, its typical example can be enumerated TAB band, FPC (flexible printed wiring board), PWB (tellite), ITO (indium tin oxide), have the semiconductor integrated circuit piece that connects pad.
There is no particular limitation for the material of distribution component, can be the silicon of chip type semiconductor and potassium arsenic etc., glass, pottery, polyimide, glass heat thermosetting resin matrix material (glass epoxy resin complex body etc.), plastics etc. any.
The occasion that the surface of the electroconductibility connection terminal that is connected with wiring-connecting material is made of transition metal such as copper or nickel is owing to its redoxomorphism produces free free radical.Therefore, if be connected to wiring-connecting material on first connection terminal and place certain hour temporarily, then radical polymerization can take place, make to connect material and become and be difficult to flow, when unsurpassed formal connection of second connection terminal that overlaps with the position, just might be able to not carry out sufficient circuit connection.Therefore, the surface of preferred at least one side's connection terminal constitutes by a kind in metal that is selected from gold and silver, platinum family or the tin at least.Also can be to resemble several metallic combinations to be got up to form multilayered structure copper/nickel/gold.
Further, in the manufacturing method of wiring board of the present invention, preferably the connection terminal with at least one side directly disposes on the surface of plastic basis material.,, can enumerate the film or the sheet material of pet resin, PEN resin, polyethersulfone resin, polycarbonate resin, polyimide resin herein, preferably constitute by polyimide resin as plastic basis material.
By using this plastic basis material, can make the thickness of wiring board thinner, and can lightweight.In the manufacture method of the present invention, the wiring-connecting material of the application of the invention can connect at low temperatures, therefore, can use the lower plastics of second-order transition temperature or fusing point, thereby can obtain the wiring board of economical.
Should illustrate,, will constitute the plastics of interconnecting piece with it with tackiness agent and the connection terminal of electro-conductive material couples together, more preferably the distribution component that constitutes without adhesive floor directly is present on the plastics connection terminal in order to reach slim, light-weighted purpose.Do not use tackiness agent and adopt direct coating method on tinsels such as Copper Foil, directly to form certain thickness resin solution, the polyimide resin of the metal-foil-clad of Huo Deing existing sale on market like this makes this metal-foil circuit figure and the distribution component that constitutes is applicable to the present invention.In addition, will directly be extruded into membranaceous film and tinsel hot pressing with forcing machine etc. after, the distribution component of this metal-foil circuit figure also be can be used among the present invention.
Embodiment
Below specifically describe the present invention based on embodiment.
Embodiment 1
(1) urethane resin is synthetic
With poly adipate succinic acid ester glycol 450 weight parts of molecular-weight average 2000, polytetramethylene glycol 450 weight parts, 1 of molecular-weight average 2000,4-butyleneglycol 100 weight parts mix, add butanone 4000 weight parts, behind the uniform mixing, add diphenylmethanediisocyanate 390 weight parts, 70 ℃ of reactions down, obtaining solid substance is the urethane resin A solution of 20 weight %, 15Pas (25 ℃).The weight-average molecular weight of this urethane resin is 350,000, and the yield point that the flow test method is measured is 80 ℃.
(2) modulation of wiring-connecting material
By the solid substance weight ratio, cooperate above-mentioned synthetic urethane resin A (by solid substance) 40g, dihydroxymethyl tristane diacrylate 39g, phosphate type acrylate (Kyoeisha Chemical Co., Ltd.'s system, trade(brand)name: P2M) 1g, phenoxy resin 20g, lauroyl peroxide 5g (by butanone solution 25g), further cooperate the electroconductive particle of 3 volume % and make its dispersion, on the thick surface treated PET of one side (polyethylene terephthalate) film of 80 μ m, be coated with apparatus for coating, with 70 ℃ warm air dryings 10 minutes, the thickness that obtains binder layer was the wiring-connecting material of 35 μ m.
Should illustrate,, use dihydroxymethyl tristane diacrylate as free-radical polymerised material.As film forming material, use phenoxy resin (union carbide corporation system, trade(brand)name " PKHC ", weight-average molecular weight 45000).In addition, as the solidifying agent that is subjected to the free free radical of thermogenesis, use 20 weight % butanone solutions of lauroyl peroxide (the weight conservation rate that room temperature (25 ℃), normal pressure open wide when placing 24 hours down is 97%).As electroconductive particle, make and use a kind of like this electroconductive particle, on the particle surface that with the polystyrene is the nuclear core, to lay the thick nickel dam of 0.2 μ m, and lay the thick gold layer of 0.04 μ m in the outside of this nickel dam, its median size is 10 μ m.
(3) connection of distribution
Shown in Fig. 1 (c), use and a kind ofly the thick Copper Foil of 18 μ m is adhered to the Kapton that posts Copper Foil that forms 3-tier architecture on the Kapton 18 by tackiness agent 17, make this Copper Foil form the circuitous pattern of live width 100 μ m, spacing 200 μ m, after carrying out processing against corrosion, on the surface of distribution that forms by Copper Foil and connection terminal 16, plate Sn, assembling integrated circuit block (not shown), seal with the resin (not shown) down at 200 ℃, make TCP (tapecarrier package) 19.
In addition, shown in Fig. 1 (a), use a kind of laminated substrate 11 that lays the thick Copper Foil of 35 μ m, make Copper Foil form the circuitous pattern of live width 100 μ m, spacing 200 μ m, form circuit 12, carry out processing against corrosion, gold-plated on copper foil surface, make printed circuit substrate (PWB) 10.
Then, the adhesive face that will contain the wiring-connecting material 15 of resin combination 13 and electroconductive particle 14 in advance pastes on the surface as the PWB 10 of the 1st distribution component, 5 seconds of heating and pressurizing under 70 ℃, 0.5MPa then, after interim the connection, peel off PET film (Fig. 1 (b)), make thereon to overlap the luggage of going forward side by side as TCP 19 positions of the 2nd distribution component and join (Fig. 1 (c)), exert pressure 20 while heat, its circuit is coupled together, obtain wiring board 21 (Fig. 1 (d)).
Embodiment 2
(1) urethane acrylate is synthetic
With polycaprolactone glycol 400 weight parts of molecular-weight average 800 and vinylformic acid 2-hydroxy propyl ester 131 weight parts, as dibutyltin dilaurate 0.5 weight part of catalyzer, be heated to 50 ℃ while stirring, mix as hydroquinone monomethyl ether 1.0 weight parts of stopper.Then, splash into isophorone diisocyanate 222 weight parts, be warming up to 80 ℃, carry out the urethane reaction while further stir.After the reactivity of affirmation NCO reaches more than 99%, reduce temperature of reaction, obtain amino methyl ester acrylate B.
(2) polyimide resin is synthetic
Will be as 2 of acid dianhydride, 2-two (4-(3, the 4-di carboxyl phenyloxy) phenyl) propane dianhydride (26.1g) is dissolved among the pimelinketone 120g, obtains the solution of acid dianhydride.
In addition, will be as 2 of diamines, 2-two (4-(4-amino-benzene oxygen) phenyl) propane (14.4g), 1,3-two (3-aminopropyl)-1,1,3,3-tetramethyl disiloxane (3.8g) is dissolved among the pimelinketone 120g, obtains two amine aqueous solutions.
On one side with the temperature regulation of reaction system to being no more than 50 ℃, on one side this diamines solution is splashed in the flask that acid dianhydride solution is housed, drip and finish back restir 10 hours.Then, moisture is installed is distillated pipe, add toluene 50g and be warming up to 120 ℃, kept 8 hours, carry out imidization.
The solution that obtains is cooled to after the room temperature in methyl alcohol precipitation once more,, obtains the polyimide resin of weight-average molecular weight 32000 drying precipitate that obtains.It is dissolved in the tetrahydrofuran (THF), makes the polyimide solution C of 20 weight %.
(3) manufacturing of the modulation of wiring-connecting material and wiring board
Use synthetic urethane resin (by solid substance) 40g among the embodiment 1 as urethane resin, use synthetic urethane acrylate B 39g and phosphate type acrylate 1g in (1) as free-radical polymerised material, use synthetic polyimide resin C (by solid substance) 20g in (2) as film forming material, in addition, modulate wiring-connecting material similarly to Example 1, make wiring board.
Embodiment 3
As shown in Figure 2, the Kapton that posts Copper Foil of 2 layers of structure that use is made of the thick Copper Foil of Kapton 22 and 18 μ m, make this Copper Foil form the circuitous pattern of live width 100 μ m, spacing 200 μ m, form circuit and connection terminal 23, after carrying out processing against corrosion, on the surface of connection terminal 23, plate Au, make flexible wiring (FPC) 24.Replace TCP 19 with this FPC 24, in addition, obtain wiring board similarly to Example 2.
Embodiment 4
Replace tellite (PWB) 10, use and adopt ITO to lay the liquid crystal panel 27 of connection terminal and distribution 26 on the surface of glass substrate 25, in addition, carry out similarly to Example 3, the wiring-connecting material of used thickness 15 μ m obtains wiring board.
Comparative example 1
Use phenoxy resin (PKHC union carbide corporation system, trade(brand)name " PKHC ": weight-average molecular weight 45000), bisphenol A type epoxy resin (oiling Shell epoxy Co., Ltd. system, trade(brand)name " YL980 ") and imidazoles microcapsule-type curing agent (Asahi Chemical Industry Co., Ltd's system, trade(brand)name " 3941HP "), the solid substance weight ratio that makes phenoxy resin/bisphenol A type epoxy resin/imidazoles microcapsule-type curing agent is 40/20/40, similarly to Example 1 to wherein fitting into electroconductive particle, use synthetic like this wiring-connecting material, in addition, make wiring board similarly to Example 1.
Comparative example 2
Use phenoxy resin (PKHC) to replace urethane resin A, in addition, obtain wiring-connecting material similarly to Example 1, make wiring board.
Use in above embodiment 1～4 and the comparative example 1,2 wiring-connecting material and the wiring board that obtain, measure and estimate bonding force, connection resistance, keeping quality, insulativity, urethane resin flowability, wiring-connecting material flow its, modulus, DSC after solidifying.The results are shown in the table 1.Should illustrate that mensuration and evaluation method are as follows.
(1) mensuration of bonding force
The linker (wiring board) of the distribution component that obtains is peeled off with the peeling rate that 50mm/ divides on 90 degree directions, measured bonding force.Bonding force is to measure after wiring board is made the initial stage and keep 500 hours in 85 ℃, the hot and humid groove of 85%RH.
(2) mensuration of connection resistance
Use the wiring-connecting material that obtains, with dispose 100 live widths, 100 μ m, spacing 200 μ m, thick 18 μ m plating Sn copper circuit flexible electric circuit board (FPC) and on whole, form the sheet glass of ITO film, in 10 seconds of heating and pressurizing under 160 ℃, 3MPa, in the wide scope of 2mm, connect.
In the early stage and after in 85 ℃, the hot and humid groove of 85%RH, keeping 500 hours, with the resistance value between the adjacent circuit of this linker of multitester measuring.Resistance value is represented with the mean value of the resistance of 50 points between adjacent circuit.
(3) conservatory evaluation
The wiring-connecting material that obtains was kept 30 days in 30 ℃ thermostatic bath, similarly carry out circuit with above-mentioned (2) and be connected, estimate keeping quality.
(4) evaluation of insulativity
Use the wiring-connecting material that obtains, with the flexible electric circuit board (FPC) of the printed circuit board (PCB) with comb type circuit and the copper circuit that 500 live widths, 100 μ m, spacing 200 μ m, thick 18 μ m are arranged of copper circuit that disposes 250 live widths, 100 μ m, spacing 200 μ m, thick 35 μ m alternately 10 seconds of heating and pressurizing under 160 ℃, 3MPa, in wide 2mm scope, connect.Comb type circuit to this linker applies 100V voltage, measures 85 ℃, the insulating resistance value of high temperature and humidity test after 500 hours of 85%RH.
(5) yield point of urethane resin is measured
With flow test machine (Shimadzu Scisakusho Ltd's system, trade(brand)name " CFT-100 type "), use the mouth mould of diameter 1mm, under the pressure of 3MPa,, measure barrel and the active temperature occurs with 2 ℃/minute heat-up rate, with it as yield point.
(6) fluidity evaluating of wiring-connecting material
Use the wiring-connecting material of thick 35 μ m, 5mm * 5mm, it is clipped in the glass of thick 0.7mm, 15mm * 15mm, under 160 ℃, 2MPa, 10 seconds condition, carry out heating and pressurizing.The value of obtaining flowability (B)/(A) with the area (A) and the area (B) after the heating and pressurizing at initial stage, with it as flowability.
(7) modulus after the curing
Wiring-connecting material was flooded 1 minute in 160 ℃ oil, make its curing.(5 ℃/minute of heat-up rates 10Hz), are measured 25 ℃ modulus to the storage modulus of the film that has used the Measurement of Dynamic Viscoelasticity device to measure to solidify.
(8) mensuration of DSC
Use the wiring-connecting material that obtains, use differential scanning calorimetry (DSC, TAInstrument corporate system, trade(brand)name " 910 type "), obtain acceleration temperature (Ta), top temperature (Tp) and the final temperature (Te) of thermopositive reaction in 10 ℃/minute mensuration.
Table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| Bonding force (gf/cm) | Initial stage | 1000 | 1000 | 800 | 1000 | 100 | 200 |
| 85℃， 85％RH， 500h | 800 | 900 | 600 | 900 | Peel off | Peel off | |
| Connection resistance (Ω) | Initial stage | 2.2 | 2.3 | 2.1 | 2.1 | 90.6 | 2.1 |
| 85℃， 85％RH， 500h | 2.6 | 2.6 | 2.5 | 2.5 | ＞500 | 2.6 | |
| Keeping quality [connection resistance (Ω)] | 2.2 | 2.4 | 2.3 | 2.2 | 120 | 2.3 | |
| Insulation resistance (Ω) | Initial stage | 1×10 9＜ | 1×10 9＜ | 1×10 9＜ | 1×10 9＜ | 1×10 9＜ | 1×10 9＜ |
| 85℃， 85％RH， 500h | 1×10 9＜ | 1×10 9＜ | 1×10 9＜ | 1×10 9＜ | 1×10 9＜ | 1×10 9＜ | |
| Mobile | 1.9 | 1.9 | 1.9 | 1.9 | 2.4 | 1.8 | |
| Modulus (25 ℃) (MPa) | 800 | 600 | 600 | 600 | 1800 | 1400 | |
| Thermopositive reaction (DSC) (℃) | Quicken temperature (Ta) | 89 | 92 | 92 | 92 | 98 | 86 |
| Top temperature (Tp) | 107 | 106 | 106 | 106 | 125 | 101 | |
| Final temperature (Te) | 148 | 150 | 150 | 150 | 160 | 142 | |
Among any embodiment, the initial value of bonding force is all at 7.85～9.81N/cm (about 800～1000gf/cm), even after humidity test, also at 5.88～8.83N/cm (about 600～900gf/cm), bonding strength does not significantly reduce, and demonstrates good binding property.Curing reaction is insufficient in the comparative example 1, in the comparative example 2 because not use urethane resin, bonding strength be that bonding force is low about 1.96N/cm (200gf/cm).
The connection resistance at the initial stage of the wiring-connecting material that obtains among the embodiment 1 is lower, and resistance also only rises a little behind the high temperature and humidity test, demonstrates good connection reliability.In addition, the wiring-connecting material of embodiment 2,3,4, comparative example 2 obtains good connection reliability too.In contrast, comparative example 1 is because curing reaction is insufficient, and adhering state is poor, and the connection resistance at initial stage uprises.
Among the embodiment 1～4, obtain with not in 30 ℃ of thermostatic baths 30 days state (initial stage) of processing equal be connected effect.In addition, among the embodiment 1～4, obtain 1.0 * 10
9The good insulation performance that Ω is above is not observed insulativity and is reduced.
For flowability, embodiment 1 and embodiment 2 are all 1.9.In addition, learn when the wiring-connecting material of measuring embodiment 1 is solidified modulus under back 25 ℃, be 800MPa.
Further, in the curing reaction of the wiring-connecting material of embodiment 1, quickening temperature is 89 ℃, and top temperature is 107 ℃, and final temperature is 148 ℃.The acceleration temperature of embodiment 2 is 92 ℃, and top temperature is 106 ℃, and final temperature is 150 ℃.Demonstrate thus under lower temperature and solidify, in addition, find out that keeping quality is also good by conservatory evaluation result.
In addition, in the mensuration of connection resistance, prepare plating Sn's and do not plate the copper circuit of Sn, use the wiring-connecting material of making among the embodiment 1, under condition similarly to Example 1, be connected on the FPC temporarily, place after 1 day, formally connecting, learn when measuring connection resistance, is 2.3 Ω under the occasion of plating Sn, and expose on the copper surface of not plating Sn, reaches 5 Ω.
Utilize possibility on the industry
As described in detail above, according to the present invention, can provide a kind of low temperature rapidly-curable of comparing with epoxy resin in the past good and have service life the electric and electronic wiring-connecting material that circuit corrosivity is few.
Claims (12)
1, a kind of wiring-connecting material comprises urethane resin, free-radical polymerised material and is subjected to the solidifying agent of thermogenesis radical, and the energy storage Young's modulus under 25 ℃ after described wiring-connecting material is solidified is 100～2000MPa.
2, the described wiring-connecting material of claim 1 wherein contains film forming material.
3, the described wiring-connecting material of claim 2, wherein, above-mentioned film forming material is selected from polyimide resin, vinyl-formal resin, polystyrene resin, polyvinyl butyral resin, vibrin, acrylic resin, polyamide resin, xylene resin, phenoxy resin.
4, the wiring-connecting material described in each of claim 1～3, wherein, the weight-average molecular weight of above-mentioned urethane resin is 10000～1000000.
5, the wiring-connecting material described in each of claim 1～3, wherein, the yield point that above-mentioned urethane resin adopts the flow test method to measure is 40 ℃～140 ℃.
6, the wiring-connecting material described in each of claim 1～3 wherein also contains electroconductive particle.
7, a kind of wiring board, it obtains by following method: make relative first distribution component and second distribution component with second connection terminal that has first connection terminal to the ground configuration with second connection terminal of first connection terminal, between first distribution component of ground configuration and second distribution component, sandwich wiring-connecting material relatively at these, through heating and pressurization, the circuit of above-mentioned first connection terminal and second connection terminal is coupled together, above-mentioned wiring-connecting material is to comprise urethane resin, free-radical polymerised material, be subjected to the wiring-connecting material of the solidifying agent of thermogenesis radical, the energy storage Young's modulus under 25 ℃ after the curing is 100～2000MPa.
8, the described wiring board of claim 7 wherein contains film forming material.
9, the described wiring board of claim 8, wherein, above-mentioned film forming material is selected from polyimide resin, vinyl-formal resin, polystyrene resin, polyvinyl butyral resin, vibrin, acrylic resin, polyamide resin, xylene resin, phenoxy resin.
10, the wiring board described in each of claim 7～9, wherein, the weight-average molecular weight of above-mentioned urethane resin is 10000～1000000.
11, the wiring board described in each of claim 7～9, wherein, the yield point that above-mentioned urethane resin adopts the flow test method to measure is 40 ℃～140 ℃.
12, the wiring board described in each of claim 7～9, wherein, above-mentioned wiring-connecting material also contains electroconductive particle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP238409/1999 | 1999-08-25 | ||
| JP23840999 | 1999-08-25 | ||
| JP92978/2000 | 2000-03-28 |
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| CNB2004100955023A Division CN100335582C (en) | 1999-08-25 | 2000-08-25 | Wiring-connecting material and wiring-connected board production process using the same |
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| CN1737078A true CN1737078A (en) | 2006-02-22 |
| CN100335586C CN100335586C (en) | 2007-09-05 |
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| CNB200510099951XA Expired - Fee Related CN100335586C (en) | 1999-08-25 | 2000-08-25 | Wiring-connecting material and process for producing circuit board with the same |
| CNB2005100999505A Expired - Fee Related CN100335585C (en) | 1999-08-25 | 2000-08-25 | Wiring-connecting material and process for producing circuit board with the same |
| CNB2005100999492A Expired - Fee Related CN100335584C (en) | 1999-08-25 | 2000-08-25 | Wiring-connecting material and process for producing circuit board with the same |
| CNB2005100999488A Expired - Fee Related CN100335583C (en) | 1999-08-25 | 2000-08-25 | Wiring-connecting material and process for producing circuit board with the same |
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| CNB2005100999492A Expired - Fee Related CN100335584C (en) | 1999-08-25 | 2000-08-25 | Wiring-connecting material and process for producing circuit board with the same |
| CNB2005100999488A Expired - Fee Related CN100335583C (en) | 1999-08-25 | 2000-08-25 | Wiring-connecting material and process for producing circuit board with the same |
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| CN101787245B (en) * | 2006-07-21 | 2012-05-23 | 日立化成工业株式会社 | Circuit connection material and connection structure and connection method of circuit component |
| CN102167964B (en) * | 2006-07-21 | 2013-10-16 | 日立化成株式会社 | Circuit connecting material, connecting structure for circuit parts and connecting method for circuit parts |
| ATE540426T1 (en) | 2006-07-21 | 2012-01-15 | Hitachi Chemical Co Ltd | MATERIAL FOR CONNECTING CIRCUIT BOARDS, CIRCUIT CONNECTION STRUCTURE AND METHOD FOR CONNECTING THE CIRCUIT BOARD ELEMENT |
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| US3994764A (en) * | 1975-06-13 | 1976-11-30 | Pratt & Lambert, Inc. | Adhesive compositions |
| TW301843B (en) * | 1994-11-15 | 1997-04-01 | Ibm | Electrically conductive paste and composite and their use as an electrically conductive connector |
| JPH10130600A (en) * | 1996-11-01 | 1998-05-19 | Sumitomo Metal Mining Co Ltd | Electrically conductive adhesive |
| JP4402750B2 (en) * | 1997-09-18 | 2010-01-20 | 日立化成工業株式会社 | How to connect circuit electrodes |
| JPH11185526A (en) * | 1997-12-17 | 1999-07-09 | Murata Mfg Co Ltd | Anisotropic conductive adhesive, electronic circuit parts, and piezoelectric parts, and bonding method for electric parts |
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| CN1737075A (en) | 2006-02-22 |
| CN100335583C (en) | 2007-09-05 |
| CN100335586C (en) | 2007-09-05 |
| CN100335584C (en) | 2007-09-05 |
| CN100335585C (en) | 2007-09-05 |
| CN1737077A (en) | 2006-02-22 |
| CN1737076A (en) | 2006-02-22 |
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