CN101802118B - Adhesive composition and bonded body - Google Patents
Adhesive composition and bonded body Download PDFInfo
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- CN101802118B CN101802118B CN200880107505.0A CN200880107505A CN101802118B CN 101802118 B CN101802118 B CN 101802118B CN 200880107505 A CN200880107505 A CN 200880107505A CN 101802118 B CN101802118 B CN 101802118B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
- H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Combinations Of Printed Boards (AREA)
- Wire Bonding (AREA)
Abstract
The invention provides an adhesive composition and a bonded body. The adhesive composition contains a crystalline resin (a) having a melting point of 40-80 DEG C, a radically polymerizable compound (b) and a radical polymerization initiator (c). This adhesive composition is excellent in adhesive strength and handling property, while exhibiting stable performance after a reliability test.
Description
Technical field
The present invention relates to adhesive composite and linker
Background technology
For the object that makes the various parts combinations in element, in semiconductor element and liquid crystal display device, use various adhesive composites always.As the desired characteristic of adhesive composite, be first required to meet cementability, and be required to meet a lot of aspects such as reliability under thermotolerance, humid tropical condition.In addition, as bonding used bonded object, headed by the organic substrate such as printed circuit board (PCB), polyimide, can use by the metal such as copper, aluminium or ITO, SiN, SiO,
2deng the base material with various condition of surface.Therefore, adhesive composite need to carry out molecular designing for each bonded object.
In the past, as semiconductor element or adhesive composite used for liquid crystal display element, use had always shown the thermosetting resins (for example,, with reference to patent documentation 1) such as the epoxy resin of high adhesion and high reliability.As the constituent of this adhesive composite, conventionally use epoxy resin, have with the solidifying agent such as the reactive phenol resins of epoxy resin, promote the hot potentiality catalyzer that epoxy resin reacts with solidifying agent.Hot potentiality catalyzer becomes the important factor that determines solidification value and curing speed, and when the storage stability from room temperature and heating, the angle of curing speed is used various compounds all the time.In actual operation, by solidifying 1～3 hour at the temperature at 170～250 ℃, what obtain wanting is bonding.
But, along with the high-precision refinement of highly integrated, the liquid crystal cell of recent semiconductor element, interelement and narrow and smallization of wiring closet spacing, the heating when solidifying, thereby likely circumferential component is produced to detrimentally affect.
Further, for cost degradation, be necessary to improve turnout, the adhesive composite that requirement is cured under lower temperature and in shorter time, that is to say, requires the adhesive composite of " low temperature fast setting ".In order to reach the low temperature fast setting of adhesive composite, for example, use the low hot potentiality catalyzer of sensitization energy, still, in this case, known having concurrently in the storage stability of near room temperature is very difficult.
In addition, as the adhesive composite that meets the requirement of low temperature fast setting, what gazed at recently is radical-curable caking agent, and this caking agent has also been used the free-radical polymerised compound such as acrylate derivative or methacrylate derivative and the superoxide as radical polymerization initiator.This adhesive composite is because the free radical as reactive behavior source is rich reactive, and therefore, it is possible (for example,, with reference to patent documentation 2) that the short period of time solidifies.And on the other hand, radically curing be caking agent because curing reaction is fast, general bonding strength is poor.Therefore, motion has by add aqueous rubber in caking agent, improves wettability, improves the method (for example, patent documentation 3) of bonding strength.
Patent documentation 1: Japanese kokai publication hei 01-113480 communique
Patent documentation 2: No. 98/44067 brochure of International Publication
Patent documentation 3: No. 04/50779 brochure of International Publication
Summary of the invention
The problem that invention will solve
But, owing in recent years semiconductor element being required to higher performance, therefore the adhesive composite, obtaining by the method for the aqueous rubber of interpolation of record in patent documentation 3 requires further to improve the physical property of the caking agent such as Young's modulus and second-order transition temperature after solidifying., require for example, the characteristic such as bonding force or contact resistance after reliability test (, 85 ℃/85%RH places) to improve.In addition, also has room for improvement at the reduction of the operability causing by using cementability when aqueous rubber to increase, the aspect such as reduction and the generation of obstruction of repairing property.
The object of the present invention is to provide and can obtain excellent bonding strength, even and after reliability test, also can maintain stable performance, meanwhile, the adhesive composite of operability excellence, and use the linker of the circuit block of this adhesive composite.
The means of dealing with problems
Adhesive composite of the present invention is that to contain (a) fusing point be the crystalline resin, (b) free-radical polymerised compound of 40 ℃～80 ℃ and (c) composition of radical polymerization initiator.
Adhesive composite of the present invention is by having above-mentioned formation, can obtain excellent bonding strength, for example, even and if also can maintain stable performance (bonding strength or contact resistance etc.) after reliability test (, high temperature and humidity test).In addition, be 40 ℃～80 ℃ by the fusing point of crystalline resin, the surface glue viscous force step-down of the room temperature range (for example, 25～30 ℃) of adhesive composite, therefore excellent in operability.Further, when generally this resin is heated to fusing point and becomes liquid state above, there is good wettability with respect to connected body.Thus, the adhesive composite that contains this resin is brought into play excellent bonding strength.
In adhesive composite of the present invention, (a) fusing point of crystalline resin is preferably 40 ℃～75 ℃.Be 40 ℃～75 ℃ by the fusing point of (a) crystalline resin, can bring into play more significantly above-mentioned effect.
In adhesive composite of the present invention, (a) crystalline resin preferably contains crystalline polyester resin.Contain vibrin by (a) crystalline resin, can improve cohesive force, obtain excellent bonding strength.
Above-mentioned crystalline polyester resin is preferably the crystalline polyester resin that contains carbonate group or ether.By containing such crystalline polyester resin, can obtain maintaining the crystalline while, there is suitable pliability, there is the adhesive composite of excellent bonding strength.
Adhesive composite of the present invention preferably further contains the vinyl compound at least in (d) molecule with more than one phosphate.By containing such compound, can obtain for substrate, the particularly bonding strength of metal substrate excellence.
At least one the amorphous resin that adhesive composite of the present invention preferably further contains that (e) select from the group of phenoxy resin, urethane resin, urethane modified polyester resin, butyral resin, acrylic resin and polyimide resin composition.By containing such amorphous resin, not only thermotolerance, cementability improve, and can obtain excellent bonding strength, and, by the stable on heating raising of cured article, after reliability test (high temperature and humidity test), also can maintain excellent characteristic.
Adhesive composite of the present invention, preferably further contains (f) electroconductive particle.Thus, can give good electroconductibility or anisotropic conductive to adhesive composite.Therefore, can suitablely especially be used in caking agent purposes of thering is splicing ear between the circuit block of (loop electrode) etc.In addition, can fully reduce the contact resistance between the splicing ear being electrically connected by above-mentioned adhesive composite.
The present invention further provides a kind of linker, it possesses: first circuit block on the interarea of the first circuit substrate with the first splicing ear, on the interarea of second circuit substrate, there are the second splicing ear second circuit parts, and so that the relative state of the first and second splicing ears is arranged between described the first and second circuit blocks, the linker of electric circuit connection member between electrical connection the first and second splicing ears; Wherein, described electric circuit connection member is formed by above-mentioned adhesive composite or its cured article, between the first and second splicing ears, is electrically connected.
The linker of this structure is to connect in the relative mode of splicing ear the linker that two circuit blocks are realized conducting by foregoing circuit interconnecting piece, as electric circuit connection member, can be suitable for adhesive composite or its cured article of the invention described above, therefore can make the bonding strength between circuit block fully high, simultaneously, after reliability test, (for example, 85 ℃/85%RH places) also can maintain stable performance (bonding strength or contact resistance).
The effect of invention
According to the present invention, can provide a kind of and can obtain excellent bonding strength, and after reliability test, also can maintain stable performance, meanwhile, the adhesive composite of operability excellence, and use the linker of the circuit block of this adhesive composite.
Accompanying drawing explanation
Fig. 1 is the figure of the determine with dsc method curve (DSC curve) of demonstration urethane modified polyester resin (UR-1400).
Fig. 2 is the figure that shows the determine with dsc method curve (DSC curve) of poly-(caprolactone) that use in embodiment.
Embodiment
Below, detailed explanation the preferred embodiment of the present invention.In addition, in the present invention, crystalline resin, refers to by determine with dsc method (following, be sometimes referred to as " DSC ") and the determine with dsc method curve obtaining is not stepped caloric receptivity variation, but there is the resin of obvious endotherm(ic)peak.Further, the fusing point of crystalline resin refers to the temperature of the summit of above-mentioned endotherm(ic)peak.
In addition, in the present invention, determine with dsc method is to use differential scanning calorimeter (Perkinelmer Inc.'s system, PerkinElmer, Inc., Pyris DSC7).Condition determination, for flow into air take flow as 10mL/min, remains on 25 ℃, is then warming up to the condition of 120 ℃ with 10 ℃/min.
And on the other hand, amorphous resin refers to that the determine with dsc method curve being obtained by DSC does not show the resin of obvious endotherm(ic)peak.
In the present invention; (methyl) vinylformic acid refers to vinylformic acid or the methacrylic acid corresponding with it; (methyl) acrylate refers to acrylate or the methacrylic ester corresponding with it, and (methyl) acryl refers to acryl or the methacryloyl corresponding with it.
Adhesive composite of the present invention is that to contain (a) fusing point be the crystalline resin, (b) free-radical polymerised compound of 40 ℃～80 ℃ and (c) composition of radical polymerization initiator.Below, detailed explanation is about each composition.
(a) fusing point using in the present invention be the crystalline resin of 40 ℃～80 ℃ be the fusing point measured by above-mentioned DSC be 40 ℃ above and be 80 ℃ following, there is crystalline resin.Together with this crystalline resin and (b) free-radical polymerised compound and (c) radical polymerization initiator, use, become the essential component of the adhesive composite of liquid or solid state, in the time using as film-like adhesive, bring into play film and form ability.(a) fusing point is that the crystalline resin of 40 ℃～80 ℃ is as long as compatible with (b) free-radical polymerised compound (maybe can mix), and then can keep (c) radical polymerization initiator, having in the scope of such character, just can adopt crystalline resin arbitrarily.
The fusing point of above-mentioned crystalline resin is preferably 40 ℃～75 ℃, more preferably 40 ℃～70 ℃, is particularly preferably 40 ℃～65 ℃.The fusing point of crystalline resin during less than 40 ℃, has the surface glue viscous force of the adhesive composite before solidifying to increase, the tendency that operability worsens.If the fusing point of crystalline resin exceedes 80 ℃, the tendency that has the mobility of the adhesive composite before solidifying to reduce.Molecular weight for above-mentioned crystalline resin has no particular limits, and is generally preferably weight-average molecular weight and is 2000～100000 resin, more preferably 5000～80000 resin.This value is less than 2000, and the tendency that has film-forming properties to worsen, if exceed 100000, has the tendency with the consistency variation of other composition.
Here with regard to crystalline resin, there is the region of well-regulated molecular structure at least a portion of molecule; Crystallinity be and near polymer between, the crystallinity of bringing into play by strong performance intermolecular forces and avidity.
As crystalline resin, can enumerate crystalline polyester resin, crystalline polyurethane resin, crystallinity carbamide resin, crystallinity polyamide resin, crystalline polypropylene resin, crystallinity polyacetal resin and crystallinity polyphenol resin etc.These can be independent or mix two or more use, particularly preferably contain crystalline polyester resin.
As crystalline polyester resin, for example, can use and there is crystalline linear polyester resin.
Above-mentioned linear polyester resin for example can have the glycol of hydroxyl and have at two ends of straight chain aliphatics hydrocarbon chain that 2 functional carboxylic acid polycondensations of carboxyl obtain at two ends of straight chain aliphatic chain by making.In addition, 2 functional carboxylic acid can be used the salt of making as 2 functional carboxylic acid chlorine.
Concrete, can pass through ethylene glycol, Diethylene Glycol, triethylene glycol, 1, 2-propylene glycol, 1, ammediol, dipropylene glycol, tripropylene glycol, 1, 4-fourth support glycol, 1, 5-pentanediol, 1, 6-hexylene glycol, 1, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol, neopentyl glycol, 1, two ends of the straight chain aliphatic chains such as 4-butadiene glycol have at least one and oxalic acid of the glycols of hydroxyl, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, propene dicarboxylic acid, nonane diacid, sebacic acid, nonane diacid, decane diacid, undecane diacid, dodecanedioic acid, toxilic acid, anti-divinyl diacid, methylfumaric acid, citraconic acid, methylene-succinic acid, m-phthalic acid, terephthalic acid, positive dodecyl succsinic acid, positive dodecylene succsinic acid, cyclohexane cyclohexanedimethanodibasic, two ends of these the sour straight chain such as acid anhydrides or lower alkyl esters aliphatics hydrocarbon chains have at least a kind of 2 functional carboxylic acid of carboxyl and obtain.
Linear polyester resin is by obtaining the hydroxycarboxylic acids such as 6-caprolactone, oenantholacton (enanthlactone) and caprylolactone or its acid anhydrides or carboxylate polymerization.
In addition, the crystalline polyester resin using in the present invention preferably contains carbonate group or ether.The low molecule that such crystalline polyester resin for example can contain ether or carbonate group by independent use or macromolecule polyol or they are used together with other polyvalent alcohol, be used as forming the diol component of crystalline polyester resin and obtain.
As the polyvalent alcohol that contains ether, for example can enumerate glycol ethers, can enumerate polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-hexylene glycol, poly-heptanediol, poly-decanediol triethylene glycol as glycol ethers.Can enumerate 1,6-hexylene glycol, polycarbonate diol, hexanodioic acid-BDO ester as polycarbonate diol.
In adhesive composite of the present invention, take adhesive composite entirety as benchmark, (a) fusing point is that the content of the crystalline resin of 40 ℃～80 ℃ is preferably 1～60 % by weight, more preferably 3～50 % by weight.If this content less than 1 % by weight, has the tendency that the effect of adhesive composite mobility raising is diminished, if exceed 50 % by weight, have the tendency that crystalline resin self mobility worsens.
(b) free-radical polymerised compound is the compound that forms polymkeric substance by the free radical being produced by (c) radical polymerization initiator.As (b) free-radical polymerised compound, have no particular limits, can use known compound.In addition, (b) free-radical polymerised compound as required can a kind of independent use, or mixes multiple compounds and use.
As (b) free-radical polymerised compound, specifically can enumerate epoxy (methyl) origoester acrylate, ammonia ester (methyl) origoester acrylate, polyethers (methyl) origoester acrylate, the oligopolymer such as polyester (methyl) origoester acrylate, trimethylolpropane tris (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polyalkylene glycol two (methyl) acrylate, dicyclopentenyl (methyl) acrylate, two cyclopentenes oxygen base ethyl (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, tricarbimide modification 2 officials' energy (methyl) acrylate, tricarbimide modification 3 officials' energy (methyl) acrylate, two phenoxyethyl alcohol fluorenes acrylate, make epoxy (methyl) acrylate of the glycidyl addition gained of (methyl) vinylformic acid and bisphenol fluorene diglycidylether, two phenoxyethyl alcohol fluorenes vinylformic acid, make epoxy (methyl) acrylate of the glycidyl addition gained of (methyl) vinylformic acid and bisphenol fluorene diglycidylether, (methyl) acryloxy is directed in the compound of the glycidyl addition gained that makes ethylene glycol or propylene glycol and bisphenol fluorene diglycidylether and the compound obtaining, and following general formula (A) and (B) represented compound.These compounds, except using separately, can also mix as required multiple compounds and use.
[changing 1]
(in formula, R
1and R
2represent independently respectively hydrogen atom or methyl, k and l represent 1～8 integer independently of one another.)
[changing 2]
(in formula, R
3and R
4represent independently respectively hydrogen atom or methyl, m and n represent 0～8 integer independently of one another.)
As (b) free-radical polymerised compound, can also use to be separately wax-like, candle shape, crystalloid, glassy, powdery etc. at 30 ℃ when standing and to there is no the compound of the solid state of mobility.
This compound can be enumerated N, N '-methylene-bisacrylamide, diacetone-acryloamide(DAA), N hydroxymethyl acrylamide, N-phenyl methyl acrylamide, 2-acrylamide-2-methyl propane sulfonic, three (2-acryloxy ethyl) chlorinated isocyanurates, N-phenylmaleimide, N-(o-tolyl) maleimide, N-(tolyl) maleimide, N-(p-methylphenyl) maleimide, N-(o-methoxyphenyl) maleimide, N-(m-methoxyphenyl) maleimide, N-(p-methoxyphenyl) maleimide, N-methyl maleimide, NEM, N-octyl group maleimide, 4,4 '-ditan bismaleimides, meta-phenylene bismaleimide, 3,3 '-dimethyl-5,5 '-diethyl-4,4 '-ditan bismaleimides, 4-methyl isophthalic acid, 3-phenylene bismaleimides, N-methacryloxy maleimide, N-acryloxy maleimide, 1,6-bismaleimides-(2,2,4-trimethylammonium) hexane, N-methacryloxy succinimide, N-acryloxy succinimide, 2-naphthyl methyl acrylate, 2-naphthyl acrylate, tetramethylol methane tetraacrylate, divinyl ethylene urea, divinyl propylene urea, caprolactam, vinylcarbazole, the polystyrene-based ethyl-methyl acrylate of 2-, N-phenyl-N '-(3-methacryloxy-2-hydroxypropyl)-P-pHENYLENE dI AMINE, N-phenyl-N '-(3-acryloxy-2-hydroxypropyl)-P-pHENYLENE dI AMINE, two (4-ethenylphenyl) sulfone, 2-tert.-butoxy-6-vinyl naphthalene, tetramethyl-piperidyl methacrylic ester, tetramethyl-piperidyl acrylate, pentamethyl-piperidino methyl acrylate, pentamethyl-piperidyl acrylate, vinylformic acid stearyl, N tert butyl acrylamide, diacetone acrylamide, N-(hydroxymethyl) acrylamide and with following general formula (C), (D), (E), (F), (G), (H), (I), (J), (K) compound and (L) representing.These compounds can use separately or mix use as required.
[changing 3]
(in formula, P1 represents 1～10 integer.)
[changing 4]
[changing 5]
(in formula, R
5represent hydrogen atom or methyl, R
6represent hydrogen atom or methyl, p represents 15～30 integer.)
[changing 6]
(in formula, R
7represent hydrogen atom or methyl, R
8represent hydrogen atom or methyl, q represents 15～30 integer.)
[changing 7]
(in formula, R
9represent hydrogen atom or methyl.)
[changing 8]
(in formula, R
10represent hydrogen atom or methyl, r represents 1～10 integer.)
[changing 9]
(in formula, R
11represent hydrogen atom or the group with following formula (a) or (b) representing, s represents 1～10 integer.)
[changing 10]
[changing 11]
[changing 12]
(in formula, R
12represent hydrogen atom or the group with following formula (c) or (d) representing, t represents 1～10 integer.)
[changing 13]
[changing 14]
[changing 15]
(in formula, R
13represent hydrogen atom or methyl.)
[changing 16]
(in formula, R
14represent hydrogen atom or methyl.)
In adhesive composite, be the crystalline resin of 40 ℃～80 ℃ with respect to (a) fusing point of 100 weight parts, (b) content of free-radical polymerised compound is preferably 40～2400 weight parts, more preferably 60～1500 weight parts.This content is during less than 40 weight part, have reduce solidify after stable on heating tendency, while exceeding 2400 weight part, while use as film, have the tendency of film-forming properties reduction.
(c) radical polymerization initiator is by producing free radical, the compound that the polyreaction of (b) free-radical polymerised compound is started.(c) radical polymerization initiator, as long as having such character, can use known compound.As (c) radical polymerization initiator, can enumerate superoxide or azo-compound etc., consider from the viewpoint of stability, reactivity, consistency, preferably 1 minute half life temperature is that 90～175 ℃ and molecular weight are 180～1,000 superoxide.Here, " 1 minute half life temperature " refers to that the transformation period is the temperature of 1 minute, and " transformation period " refers to until the concentration of free-radical polymerised compound is reduced to the time of the half of initial value.
As (c) radical polymerization initiator, specifically can enumerate 1,1,3,3-tetramethyl butyl new decanoate ester peroxide, two (4-tert-butylcyclohexyl) peroxy dicarbonate, two (2-ethylhexyl) peroxy dicarbonate, cumyl new decanoate ester peroxide, 1,1,3,3-tetramethyl butyl new decanoate ester peroxide, two bay acyl peroxides, 1-cyclohexyl-1-methylethyl new decanoate ester peroxide, tertiary hexyl new decanoate ester peroxide, tert-butyl hydroperoxide neodecanoic acid ester, tert-butyl hydroperoxide trimethylacetic acid ester, 1，1，3，3-tetra-methylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis-(peroxidation of 2-ethyl hexyl acyl group) hexane, tertiary hexyl peroxidation-2-ethylhexanoate, tert-butyl hydroperoxide-2-ethylhexanoate, the new heptanoate of tert-butyl hydroperoxide, t-amyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide six hydrogen terephthalate, t-amyl peroxy-3,5,5 Trimethylhexanoic acid ester, 3-hydroxyl-1,1-dimethylbutyl new decanoate ester peroxide, 1，1，3，3-tetra-methylbutyl peroxy-2-ethylhexanoate, t-amyl peroxy neodecanoic acid ester, t-amyl peroxy-2-ethylhexanoate, two (3-methyl benzoyl) superoxide, dibenzoyl superoxide, two (4-methyl benzoyl) superoxide, 2,2 '-azo two-2,4-methyl pentane nitrile, 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane), 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), dimethyl-2,2 '-Diisopropyl azodicarboxylate, 4,4 '-azo two (4-cyanopentanoic acid), 1,1 '-azo two (1-cyclohexane nitrile), tertiary hexyl peroxidation sec.-propyl monocarbonate, tert-butyl hydroperoxide toxilic acid, tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester, tert-butyl hydroperoxide laurate, 2,5-dimethyl-2,5-bis-(peroxidation of 3-methyl benzoyl) hexane, tert-butyl hydroperoxide-2-ethylhexyl monocarbonate, tertiary hexyl peroxide benzoate, 2,5-dimethyl-2,5-bis-(benzoyl peroxidation) hexane, tert butyl peroxy benzoate, dibutyl peroxidation trimethyladipic acid ester, t-amyl peroxy n-caprylic acid ester, the different pelargonate of t-amyl peroxy and t-amyl peroxy benzoic ether etc.These compounds can use separately, also can mix compound of more than two kinds and use.
In addition, as (c) radical polymerization initiator, the rayed that can also to use by wavelength be 150～750nm produces the compound of free radical.As such compound, have no particular limits, can use known compound, for example, Photoinitiation, Photopolymerization, and Photocuring, J.-P.Fouassier, Hanser Publishers (nineteen ninety-five), alpha-acetamido-amphyl or the phosphinoxide in 17th～35 pages, recorded, because they are high to light-struck susceptibility, thereby more preferably.These compounds, can use separately a kind, also can mix to use with above-mentioned superoxide or azo-compound.
In adhesive composite, be the crystalline resin of 40 ℃～80 ℃ with respect to (a) fusing point of 100 weight parts, (c) content of radical polymerization initiator is preferably 0.1～500 weight part, more preferably 1～300 weight part.This content during less than 0.1 weight part, may solidify deficiency, while exceeding 500 weight part, has the danger that shelf-stability reduces.
In adhesive composite, can further contain the vinyl compound at least in (d) molecule with 1 above phosphate.By containing such compound, the raisings such as bonding strength.
As the vinyl compound at least in (d) molecule with 1 above phosphate, preferably with following general formula (M), (N) and (O) represented compound.If use such compound, can improve the bonding strength of adhesive composite etc.
[changing 17]
(in formula, R
15represent (methyl) acryl, R
16represent hydrogen atom or methyl, u, v independently represent 1～8 integer separately.In addition, in formula, R
15r each other,
16each other, u each other each other can be identical separately with v, also can be different.)
[changing 18]
(in formula, R
17represent (methyl) acryl, w, x independently represent 1～8 integer separately.In addition, in formula, R
17each other, w each other each other can be identical separately with x, also can be different.)
[changing 19]
(in formula, R
18represent (methyl) acryl, R
19represent hydrogen atom or methyl, y, z independently represent 1～8 integer separately.In addition, in formula, R
18r each other,
19each other, y each other each other can be identical separately with z, also can be different.)
As the vinyl compound at least in (d) molecule with more than one phosphate, specifically can enumerate acid phosphorus oxygen base ethyl-methyl acrylate, acid phosphorus oxygen base ethyl propylene acid esters, acid phosphorus oxygen base propyl methyl acid esters, acid phosphorus oxygen base polyoxyethylene glycol monomethacrylates, acid phosphorus oxygen base polyoxy propylene glycol monomethyl acrylate, 2, 2 '-bis-(methyl) acryloxy diethyl phosphoric acid ester, EO modified phosphate dimethacrylate (oxyethane modified phosphate dimethacrylate), phosphoric acid modification epoxy acrylate, phosphoric acid vinyl acetate etc.
In adhesive composite, it is the crystalline resin of 40 ℃～80 ℃ with respect to (a) fusing point of 50 weight parts, (d) content that at least has the vinyl compound of more than one phosphate in molecule is preferably 0.1～150 weight part, more preferably 0.5～100 weight part.This content during less than 0.1 weight part, has the tendency that is difficult to obtain high-adhesive-strength, while exceeding 150 weight part, easily produces the physical property of adhesive composite after solidifying and declines, the danger that reliability reduces.
Adhesive composite can further contain amorphous resin.By containing amorphous resin, the raising such as thermotolerance, cementability of adhesive composite.
As amorphous resin, have no particular limits, preferably (be preferably polyurethane-modified copolymer polyester resin from (e) phenoxy resin, urethane resin, urethane modified polyester resin.In addition, urethane modified polyester resin is also sometimes referred to as " polyester urethane resin "), at least a kind of amorphous resin selecting in the group of butyral resin, acrylic resin, polyimide resin composition.While using such resin, thermotolerance, cementability further improve.These resins can use separately or be mixed with two or more, but while being mixed with two or more, preferably or completely compatible between the resin mixing, or produce microphase-separated and become gonorrhoea state.In these resins, can further contain siloxane bond or fluoro substituents.
In addition, its molecular weight of above-mentioned amorphous resin is larger, more easily obtains film-forming properties, can in wide scope, set in addition the tendency of melt viscosity, and this melt viscosity impact is as the mobility of caking agent.Above-mentioned molecular weight has no particular limits, and conventionally, is preferably 5,000～150 as weight-average molecular weight, and 000, more preferably 10,000～80,000.This value is less than 5,000, and the tendency that has film-forming properties to decline, if exceed 150,000, has the tendency with the consistency variation of other composition.
In adhesive composite, take adhesive composite total amount as benchmark, the content of amorphous resin is preferably 10～80 % by weight, more preferably 15～70 % by weight.This content during less than 10 % by weight, has the tendency that is difficult to obtain high adhesion, while exceeding 80 % by weight, has the tendency that adhesive composite mobility worsens.
For the object of giving electroconductibility or anisotropic conductive, adhesive composite can further contain (f) electroconductive particle.
As (f) electroconductive particle, can list metallics or the carbon etc. such as Au, Ag, Ni, Cu, scolding tin.In addition, can be also take dielectric glass, pottery, plastics etc. as nucleome, on this nucleome, be coated with the particle of above-mentioned metal, metallics, carbon.When (f) electroconductive particle is take plastics as nucleome, on this nucleome, be coated with the particle of above-mentioned metal, metallics or carbon, or when hot molten metal particle, owing to thering is heating and pressurizing deformability, therefore in the time connecting, increase with the contact area of electrode, reliability improves, thereby preferably.
In addition, further, with the particulate of these electroconductive particle surface gained of the coatings such as macromolecule resin, can suppress to be in contact with one another caused short circuit because the use level of electroconductive particle increases the particle causing, and improve the insulativity between telegraph circuit.Can use separately with the particulate of the coating electroconductive particle such as macromolecule resin surface gained, also can be used in combination with other electroconductive particle.
(f) median size of electroconductive particle is preferably 1～18 μ m.This (f) electroconductive particle is brought into play good dispersiveness and electroconductibility.Therefore, this containing (f) electroconductive particle adhesive composite can be used as well anisotropic conductive adhesive.
The content of (f) electroconductive particle in adhesive composite has no particular limits, and take the cumulative volume of adhesive composite as benchmark, is preferably 0.1～30 volume %, more preferably 0.1～10 volume %.This value is during less than 0.1 volume %, and the tendency that has electroconductibility to worsen, if while exceeding 30 volume %, has the tendency of easy circuit for generating short circuit.In addition, (f) volume of the each composition of the content of electroconductive particle (volume %) based on before 23 ℃ solidify decides.Here, the volume of each composition, can utilize proportion to be scaled to volume by weight.Or, also appropriate solvent (water, alcohol etc.) can be put into graduated cylinder etc., this solvent does not dissolve or the not swelling volumetric composition and can fully soak this composition wanted, and then, to the composition that drops into determination object in graduated cylinder, obtains the volume of increase as the volume of this composition.
To improve crosslinking rate as object, in adhesive composite, except (b) free-radical polymerised compound and (d) at least having the vinyl compound of more than one phosphate in molecule, can also contain as required and there is the compound by the functional group of living radical generation polymerization such as allyl group, dimaleoyl imino, vinyl.As the object lesson of this compound, can enumerate N-vinyl imidazole, N-vinyl pyridine, NVP, N-vinyl formamide, N-caprolactam, 4,4 '-vinylidene, two (N, accelerine), N-vinyl acetamide, N, N-DMAA, NIPA, N, N-diethyl acrylamide, acrylamide etc.
Adhesive composite can also further contain stablizer.By containing stablizer, can control curing speed, pay storage stability, have no particular limits for stablizer, but be preferably the quinone derivative such as benzoquinones and quinhydrones, the amphyls such as 4-methoxyphenol, 4-tert-butyl catechol, 2,2,6,6-tetramethyl piperidine-1-oxygen base and 4-hydroxyl-2, the hindered amine derivatives such as aminooxy (aminoxyl) derivative and tetramethyl-piperidyl methacrylic ester such as 2,6,6-tetramethyl piperidine-1-oxygen base.
The content of stablizer in adhesive composite, with respect to the adhesive composite of 100 weight parts, is preferably 0.01～30 weight part, more preferably 0.05～10 weight part.This content is during less than 0.01 weight part, the danger that has stabilization effect to reduce, if while exceeding 30 weight part, have with adhesive composite in the danger that reduces of the consistency of other composition.
Adhesive composite can also contain the bonding auxiliary agent such as coupling agent and adaptation improving agent, flow agent take alkoxyl silicone alkane derivatives and silazane derivative as representative as required.Concrete is preferably with the represented compound of following general formula (P), can use separately, also can use by two or more compound combination.
[changing 20]
(in formula, R
20, R
21and R
22represent independently of one another the alkyl that hydrogen atom, carbonatoms are 1～5, the alkoxyl group that carbonatoms is 1～5, alkoxy carbonyl, the aryl that carbonatoms is 1～5, R
23represent (methyl) acryl, vinyl, isocyanate group, imidazolyl, sulfydryl, amino, methylamino, dimethylamino, benzylamino, phenyl amino, cyclohexyl amino, morpholinyl, piperazinyl, urea groups or glycidyl, A represents 1～10 integer.)
Adhesive composite can also and be used rubber constituent.By also, by rubber constituent, stress relaxes and cementability raising becomes easy.As the object lesson of this rubber constituent, can list polyisoprene, polyhutadiene, C-terminal polyhutadiene, C-terminal polyhutadiene, 1, 2-polyhutadiene, C-terminal 1, 2-polyhutadiene, C-terminal 1, 2-polyhutadiene, acrylic rubber, styrene butadiene rubbers, C-terminal styrene butadiene rubbers, acrylonitrile-butadiene rubber, contain carboxyl in polymer ends, hydroxyl, the acrylonitrile-butadiene rubber of (methyl) acryl or morpholinyl, carboxylated nitrile rubber, C-terminal gathers (oxypropylene), alkoxysilyl end gathers (oxypropylene), poly-(oxygen tetramethylene) glycol, polyolefin diols etc.
As above-mentioned rubber constituent, preferably contain the rubber constituent as cyano group or the carboxyl of high polar group at side chain or end.By containing such rubber constituent, cementability further improves.As above-mentioned rubber constituent, preferably aqueous rubber.By using aqueous rubber, can further improve the mobility of adhesive composite.As rubber constituent, concrete aqueous acrylonitrile-butadiene rubber and the aqueous carboxylated nitrile rubber that can list aqueous acrylonitrile-butadiene rubber, contain carboxyl, hydroxyl, (methyl) acryl or morpholinyl in polymer ends.In these rubber constituents, be preferably 10～60 % by weight as the content of the vinyl cyanide of polar group.These compounds can use separately a kind, also can two or more be used in combination.
Adhesive composite also can be used together organic fine particles., can seek further to relax stress and improve cementability with organic fine particles by also.As organic fine particles, concrete can list by polyisoprene, polyhutadiene, C-terminal polyhutadiene, C-terminal polyhutadiene, 1, 2-polyhutadiene, C-terminal 1, 2-polyhutadiene, acrylic rubber, styrene butadiene rubbers, acrylonitrile-butadiene rubber, contain carboxyl in polymer ends, hydroxyl, the acrylonitrile-butadiene rubber of (methyl) acryl or morpholinyl, carboxylated nitrile rubber, C-terminal gathers (oxypropylene), alkoxysilyl end gathers (oxypropylene), poly-(oxygen tetramethylene) glycol, polyolefin diols (methyl) alkyl acrylate-butadiene-styrene copolymer, (methyl) alkyl acrylate-Organosiliconcopolymere, the organic fine particles that organosilicon-(methyl) acrylic copolymer or complex body form etc.These organic fine particles may be used alone, two or more kinds can also be used in combination.
Adhesive composite for example, when (25～30 ℃) are aqueous at normal temperatures, can use with pasty state.While being solid under normal temperature, can heat use, also can carry out pasty state and use with solvent.Here, as operable solvent, as long as there is no reactivity with the bonding composition (also comprising additive) that connects, and show that sufficient deliquescent solvent just has no particular limits, preferably the boiling point under normal pressure is the solvent of 50～150 ℃.Boiling point is during less than 50 ℃, and normal temperature may volatilize while placement, and the use in open system can be restricted.In addition, if boiling point exceedes 150 ℃, solvent is difficult to volatilization, has the reliability after bonding is produced to dysgenic danger.
Adhesive composite also can be formed as membranaceous use.Adhesive composite forms when membranaceous, can be formed as membranaceous: in adhesive composite, be added with as required solvent etc. and obtain solution, by this solution coat on the separability base materials such as fluororesin film, polyethylene terephthalate film and release paper, or make the base materials such as above-mentioned solution impregnation non-woven fabrics and be placed on separability base material, remove desolventizing etc., thereby be formed as membranaceous.If adhesive composite of the present invention is formed as membranaceous and uses, become more convenient from operability equal angles.
Adhesive composite conventionally can be used together heating and pressurization and make by convered structure bonding each other.Heating temperature is not particularly limited, and is preferably the temperature of 100～250 ℃.Pressure, as long as can, to produced the scope of damage by convered structure, not just being not particularly limited, is generally preferably 0.1～10MPa.This heating and pressurization are preferably carried out in the scope of 0.5 second～120 seconds.By adhesive composite of the present invention, for example, under 140～200 ℃, the condition of 3MPa, with the heating of 10 seconds and pressurization, just can make by convered structure fully bonding each other.
The caking agent that adhesive composite can be used as the different xenogenesis bonded object of thermal expansivity uses.Specifically, be suitable as take anisotropic conductive adhesive, silver stick with paste and silverskin etc. as the electric circuit connection member (circuit connection material) of representative, take elastomerics CSP for, for CSP, underfill, LOC such as are with at the semiconductor element adhesives as representative.
Below, an example is described, this example is to use adhesive composite and electroconductive particle to make anisotropic conductive film, is connected to the example of the circuit block that is formed with splicing ear on the interarea of circuit substrate each other time with this anisotropic conductive film.That is, anisotropic conductive film is configured between the relative splicing ear on circuit substrate, by heating and pressurizing, carries out bonding between electrical connection between relative splicing ear and circuit substrate, circuit block can be connected to each other.Here as the circuit substrate that forms splicing ear, can use the inorganic materials such as semi-conductor, glass and pottery, the organic materialss such as polyimide, polycarbonate, each combination of the inorganic materials such as glass/epoxy and organic materials.In addition, if connected according to the mode that relative splicing ear is in direct contact with one another, even if do not use above-mentioned electroconductive particle, also can make to be electrically connected between splicing ear.
For example can obtain such linker by above-mentioned method, this linker possesses: first circuit block on the interarea of the first circuit substrate with the first splicing ear, on the interarea of second circuit substrate, there are the second splicing ear second circuit parts, with be arranged between the first and second circuit blocks with the relative state of the first and second splicing ears and be electrically connected the electric circuit connection member between the first and second splicing ears, foregoing circuit interconnecting piece is formed by adhesive composite of the present invention or its cured article, between the first and second splicing ears, be electrically connected by foregoing circuit interconnecting piece.
Such linker, the electric circuit connection member connecting due to a pair of circuit block is to be made up of the cured article of the adhesive composite of the invention described above, therefore can fully improve the bonding strength between circuit block, and, after reliability test, (for example, 85 ℃/85%RH places) also can maintain stable performance.
Embodiment
Below, based on embodiment and comparative example, the present invention is illustrated, but the present invention is not limited to following examples.
[(e) modulation of amorphous resin solution]
Modulation phenoxy resin solution, urethane modified polyester resin solution and polyurethane solution are as amorphous resin solution.Modulator approach is as follows.
[modulation of phenoxy resin solution]
The phenoxy resin of 40g (YP-50, Dongdu change into society's system, trade(brand)name) is dissolved in the methyl ethyl ketone of 60g, and forming solids component is the phenoxy resin solution of 40 % by weight.
[modulation of urethane modified polyester resin solution]
By urethane modified polyester resin (UR-1400, Japan spins society and manufactures, trade(brand)name) be dissolved in the mixed solvent that methyl ethyl ketone and toluene mixes with the ratio of 1: 1 (weight), be modulated into the solution that urethane modified polyester resin composition is 30 % by weight.In addition, Fig. 1 shows the determine with dsc method curve (DSC curve) of urethane modified polyester resin (UR-1400).As shown in Figure 1, the determine with dsc method curve of this resin is the curve without peak value.
[modulation of polyurethane solution]
The urethane resin of 15g (Miractran P22M, softening temperature: 64 ℃, Nippon Polyurethane Industry Co., Ltd.'s system) is dissolved in the methyl ethyl ketone solution of 85g, is modulated into the polyurethane solution that solids component is 15 % by weight.
[preparation of aqueous rubber constituent]
Prepare aqueous nitrile rubber (the Japanese Zeng Rong of Nipol 1312 Co., Ltd.'s system (ZEONCORPORATION), trade(brand)name) as aqueous rubber constituent.
[modulation of crystalline resin (vibrin) solution]
As crystalline resin, prepare poly-(caprolactone) (with Guang Chunyao chemical industry Co., Ltd. system, Mw40000, mp:53 ℃), (society's system is spun to VYLON GA-6400 by Japan for Mw:30000, mp:71 ℃, trade(brand)name) and VYLON GA-6300 (Mw:30000, mp:101 ℃, society's system, trade(brand)name are spun by Japan).Then above-mentioned 3 kinds of each 30g of crystalline resin are dissolved in the toluene of 70g, are modulated into the crystalline resin that solids component is 30 % by weight (vibrin) solution.In addition, Fig. 2 shows the determine with dsc method curve (DSC curve) that has used poly-(caprolactone).As shown in Figure 2, the determine with dsc method curve of this resin is the curve with peak.
[(b) preparation of free-radical polymerised compound]
Prepare tricarbimide EO modification diacrylate (trade(brand)name: M-215, Toagosei Co., Ltd's system, trade(brand)name), as free-radical polymerised compound.In addition, synthetic ammonia ester acrylate (UA), as free-radical polymerised compound.
[synthesizing of ammonia ester acrylate]
Stirrer, thermometer being installed, having in the reflux cooling pipe of calcium chloride tube and the reaction vessel of nitrogen conduit, poly-(pregnancy subunit carbonic ether) glycol (Aldrich society system) that the number-average molecular weight that drops into 860 weight parts (1.00 moles) is 860 and the dibutyl tin laurate (Aldrich society system) of 5.53 weight parts.Then, import after sufficient nitrogen, be heated to 70～75 ℃, with the isophorone diisocyanate that evenly drips 666 weight parts (3.00 moles) for 3 hours, make its reaction.After dropping finishes, continue reaction 10 hours.Drop into therein the vinylformic acid 2-hydroxy methacrylate (Aldrich society system) of 238 weight parts (2.05 moles) and the Hydroquinone monomethylether (Aldrich society system) of 0.53 weight part, further reaction is after 10 hours, measure and confirm after isocyanic ester disappearance by IR, termination reaction, obtains ammonia ester acrylate (UA).The number-average molecular weight of the ammonia ester acrylate UA obtaining is 3,700.
[(d) in molecule, at least thering is the preparation of the vinyl compound (following, according to circumstances also referred to as " compound of phosphoric acid ") of more than one phosphate]
Prepare 2-(methyl) acryloxy ethyl phosphonic acid ester (light ester (ラ イ ト エ ス テ Le) P-2M, Co., Ltd. of common prosperity society system, trade(brand)name), as the vinyl compound at least in (d) molecule with more than one phosphate.
[(c) preparation of radical polymerization initiator]
As radical polymerization initiator, prepare tertiary hexyl peroxidation-2-ethylhexanoate (PERHEXYL O, NOF Corp's system, trade(brand)name).
[(f) making of electroconductive particle]
The nickel dam that thickness is 0.2 μ m is set on the particle surface at polystyrene as core, is the gold layer of 0.02 μ m at the arranged outside thickness of this nickel dam, and making like this median size is 4 μ m, the electroconductive particle that proportion is 2.5.
[embodiment 1～6, comparative example 1～5]
By the material mixing of being prepared by aforesaid method, make with solids component weight ratio, that is, the weight ratio meter during except desolventizing reaches the ratio shown in table 1 and 2, and further the electroconductive particle of blending dispersion 1.5 volume %, makes adhesive composite.Using apparatus for coating is on the fluororesin film of 80 μ m at thickness by the adhesive composite solution coat obtaining, carry out the warm air drying of 10 minutes at 70 ℃, be the membranaceous adhesive composite (following, to be called " film-like adhesive composition ") of 20 μ m thereby obtain thickness.
[table 1]
[table 2]
(evaluation of adhesive composite and linker)
[mensuration of contact resistance and bonding strength]
Use the film-like adhesive composition being obtained by above-mentioned method for making, use thermo-compression bonding device (type of heating: permanent pattern of fever, Dongli Engineering Co., Ltd's system), under the condition of 160 ℃ of temperature, pressure 3MPa, be that 25 μ m, spacing are that 50 μ m, thickness are the flex circuit application (FPC) of 18 μ m copper circuits and are formed with the glass that thickness is 0.2 μ m Indium sesquioxide (ITO) thin layer (thickness is that 1.1mm, surface resistivity are 20 Ω/) heating and pressurizing 10 seconds to thering are 500 live widths, connect, make linker.After bonding with multitester measuring at once and in 85 ℃, the hot and humid groove of 85%RH, keep this linker after 250 hours in abutting connection with the resistance value between circuit.Mean value with 37 of the resistance in abutting connection with between circuit represents contact resistance value.In addition, contact resistance is more low better.
Measure the bonding strength of this linker according to JIS-Z0237 with 90 degree stripping methods, evaluate.Here, that the determinator of bonding strength uses is sky this grand (テ Application シ ロ Application) UTM-4 (peeling rate is 50mm/min, 25 ℃) that Powerleader temperature Co., Ltd. of Japan (East ocean ボ mono-Le ドウイン Co., Ltd.) manufactures.Bonding strength is the bigger the better.
[mensuration of surface glue viscous force]
Use the film-like adhesive composition being obtained by above-mentioned method for making, according to JIS-Z0237-1991, sticking with glue property testing experiment (probe tack) is evaluated the surface glue viscous force of membranaceous adhesive composite.Here, the determinator of surface glue viscous force uses Li Shi section of Co., Ltd. (RHESCA) to manufacture (probe diameter: φ 5.1mm, contact velocity: 2.0mm/s, peels speed: 10mm/s, contact is born a heavy burden: 100gf/cm
2, duration of contact: 1.0s, measures temperature: 30 ℃).Can say that surface glue viscous force is lower, the operability of adhesive composite is more excellent.
Table 3 shows the measurement result of contact resistance, bonding strength and the surface glue viscous force of the linker of being measured by above method.
Table 3
The adhesive composite that known embodiment 1～6 obtains, 160 ℃ of Heating temperatures, after bonding, at once and keep 250 hours in 85 ℃, the hot and humid groove of 85%RH after all show good contact resistance and bonding strength, large-scale Heating temperature is shown to good characteristic.Further known surface glue viscous force is also suitable low, and operability and reparation property are good.In contrast, having used fusing point is the comparative example 1 of the crystalline resin of 101 ℃, is the crystalline resin of 40 ℃～80 ℃ owing to there is no (a) fusing point of use, therefore poor with the consistency of other composition, separates out agglutinator on film surface, and operability worsens.Be, in the comparative example 2,3 of amorphous resin of 64 ℃, to can not get sufficient mobility and used softening temperature, bonding after at once and hot and humid bonding resistance value after treatment high.In addition we know, used in the comparative example 4,5 of aqueous rubber, the contact resistance after hot and humid rise and surface glue viscous force high, operability is treatability deterioration.
Shown in above, a kind of excellent bonding strength that has can be provided according to the present invention, and after reliability test (high temperature and humidity test), also can maintain stable performance (bonding strength, contact resistance), simultaneously, the adhesive composite of operability excellence, and use the linker of the circuit block of this adhesive composite.
Industrial applicability
According to the present invention, can provide a kind of and can obtain excellent bonding strength, even and after reliability test, also can maintain stability, meanwhile, the adhesive composite of operability excellence; The linker of the circuit block that uses this adhesive composite can also be provided.
Claims (6)
1. an adhesive composite is as the application of thermoset circuit connection material, it is characterized in that, it is the crystalline resin, (b) free-radical polymerised compound of 40 ℃～75 ℃ and (c) radical polymerization initiator that described adhesive composite contains (a) fusing point, wherein, (a) crystalline resin contains crystalline polyester resin.
2. application according to claim 1, wherein, described crystalline polyester resin is the crystalline polyester resin with carbonate group or ether.
3. application according to claim 1, wherein, described adhesive composite further contains the vinyl compound at least in (d) molecule with more than one phosphate.
4. application according to claim 1, wherein, at least one the amorphous resin that described adhesive composite further contains that (e) select from the group of phenoxy resin, urethane resin, urethane modified polyester resin, butyral resin, acrylic resin and polyimide resin composition.
5. application according to claim 1, wherein, described adhesive composite further contains (f) electroconductive particle.
6. a linker, is characterized in that, possesses: on the interarea of the first circuit substrate, there is the first circuit block of the first splicing ear,
On the interarea of second circuit substrate, there are the second circuit parts of the second splicing ear, and
So that the relative state of described the first and second splicing ears is arranged between described the first and second circuit blocks, is electrically connected the electric circuit connection member between described the first and second splicing ears;
Wherein, described electric circuit connection member is formed by the described adhesive composite in the application described in any one in claim 1～5 or its cured article, and the first and second splicing ears are electrically connected.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007242217 | 2007-09-19 | ||
| JP2007-242217 | 2007-09-19 | ||
| JP2008-071763 | 2008-03-19 | ||
| JP2008071763 | 2008-03-19 | ||
| PCT/JP2008/067017 WO2009038190A1 (en) | 2007-09-19 | 2008-09-19 | Adhesive composition and bonded body |
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| CN101802118A CN101802118A (en) | 2010-08-11 |
| CN101802118B true CN101802118B (en) | 2014-05-28 |
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| JP (2) | JP5349316B2 (en) |
| KR (1) | KR101240009B1 (en) |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5668636B2 (en) * | 2010-08-24 | 2015-02-12 | 日立化成株式会社 | Method for manufacturing circuit connection structure |
| CN104169389B (en) * | 2012-04-25 | 2018-07-13 | 日立化成株式会社 | Circuit connection material, circuit connection structure, adhesive film and coiling body |
| JP5964187B2 (en) | 2012-09-18 | 2016-08-03 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method, and joined body |
| JP2014102943A (en) * | 2012-11-19 | 2014-06-05 | Dexerials Corp | Anisotropic conductive film, connection method and joined body |
| JP6123547B2 (en) * | 2013-07-26 | 2017-05-10 | 日立化成株式会社 | Circuit connection material, circuit connection structure, method for manufacturing circuit connection structure, adhesive composition, and adhesive sheet |
| CN103774440A (en) * | 2014-01-20 | 2014-05-07 | 南通全技纺织涂层有限公司 | Light elastic wear-resistant nylon fabric |
| JP6285191B2 (en) * | 2014-02-05 | 2018-02-28 | デクセリアルズ株式会社 | Anisotropic conductive film, method for producing the same, connection method and joined body |
| JP6293524B2 (en) * | 2014-03-11 | 2018-03-14 | デクセリアルズ株式会社 | Anisotropic conductive film, method for producing the same, connection method and joined body |
| CN104916346A (en) * | 2015-01-05 | 2015-09-16 | 深圳市思迈科新材料有限公司 | Low-temperature curing photosensitive conductive silver slurry composition |
| JP6352979B2 (en) * | 2016-06-29 | 2018-07-04 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method, joined body, and production method of joined body |
| JP2018044117A (en) * | 2016-09-16 | 2018-03-22 | 日本合成化学工業株式会社 | Thermosetting resin composition, thermosetting adhesive composition, and thermosetting adhesive sheet and diaphragm for thin flat-plate speakers prepared therewith |
| JP6271048B2 (en) * | 2017-01-11 | 2018-01-31 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method, and joined body |
| KR102580259B1 (en) | 2018-01-30 | 2023-09-19 | 타츠타 전선 주식회사 | Conductive adhesive composition |
| JP6542927B2 (en) * | 2018-02-14 | 2019-07-10 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method and joined body |
| TW202043407A (en) | 2019-03-04 | 2020-12-01 | 日商拓自達電線股份有限公司 | Conductive adhesive composition |
| US20230287246A1 (en) * | 2020-06-05 | 2023-09-14 | Dexerials Corporation | Method for manufacturing joined body, joined body, and hot-melt adhesive sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220686A (en) * | 1996-06-03 | 1999-06-23 | 美国3M公司 | Thermomorphic pressure sensitive adhesive |
| CN1786096A (en) * | 2004-12-08 | 2006-06-14 | Lg电线株式会社 | Anisotropic conductive adhesive having PTC characteristics |
| CN1798786A (en) * | 2003-06-04 | 2006-07-05 | 积水化学工业株式会社 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6069180A (en) * | 1983-09-27 | 1985-04-19 | Nitto Electric Ind Co Ltd | Photo-setting adhesive tape or sheet |
| DE4438577A1 (en) * | 1994-10-28 | 1996-05-02 | Basf Ag | Self-supporting dowel compound for chemical fastening technology |
| CA2335567A1 (en) * | 1998-06-19 | 1999-12-29 | Henkel Kommanditgesellschaft Auf Aktien | Adhesive which hardens in several stages |
| JP2004010731A (en) * | 2002-06-05 | 2004-01-15 | Kao Corp | Adhesive for lignocellulose |
| KR20050070028A (en) * | 2002-10-01 | 2005-07-05 | 우베 고산 가부시키가이샤 | Polyol mixture, reactive hot-melt composition obtained from the mixture, and molded article obtained with the composition |
| JP4760070B2 (en) * | 2005-03-16 | 2011-08-31 | 日立化成工業株式会社 | Adhesive, adhesive for circuit connection, connector and semiconductor device |
-
2008
- 2008-09-19 WO PCT/JP2008/067017 patent/WO2009038190A1/en active Application Filing
- 2008-09-19 KR KR1020097017752A patent/KR101240009B1/en active IP Right Grant
- 2008-09-19 JP JP2009533204A patent/JP5349316B2/en active Active
- 2008-09-19 CN CN200880107505.0A patent/CN101802118B/en not_active Expired - Fee Related
-
2012
- 2012-09-04 JP JP2012194008A patent/JP2013007048A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220686A (en) * | 1996-06-03 | 1999-06-23 | 美国3M公司 | Thermomorphic pressure sensitive adhesive |
| CN1798786A (en) * | 2003-06-04 | 2006-07-05 | 积水化学工业株式会社 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| CN1786096A (en) * | 2004-12-08 | 2006-06-14 | Lg电线株式会社 | Anisotropic conductive adhesive having PTC characteristics |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101240009B1 (en) | 2013-03-06 |
| JPWO2009038190A1 (en) | 2011-01-13 |
| JP5349316B2 (en) | 2013-11-20 |
| KR20100009528A (en) | 2010-01-27 |
| WO2009038190A1 (en) | 2009-03-26 |
| CN101802118A (en) | 2010-08-11 |
| JP2013007048A (en) | 2013-01-10 |
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