CN101955735A - Adhesive composite and the syndeton body that uses the circuit block of said composition - Google Patents
Adhesive composite and the syndeton body that uses the circuit block of said composition Download PDFInfo
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- CN101955735A CN101955735A CN2010102269141A CN201010226914A CN101955735A CN 101955735 A CN101955735 A CN 101955735A CN 2010102269141 A CN2010102269141 A CN 2010102269141A CN 201010226914 A CN201010226914 A CN 201010226914A CN 101955735 A CN101955735 A CN 101955735A
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- 0 CC(C)(CCO)Oc1ccc(C2(c3ccccc3-c3ccccc23)c(cc2)cc(I)c2OCC2CC2)cc1* Chemical compound CC(C)(CCO)Oc1ccc(C2(c3ccccc3-c3ccccc23)c(cc2)cc(I)c2OCC2CC2)cc1* 0.000 description 2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
- H01L2224/83101—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus as prepeg comprising a layer connector, e.g. provided in an insulating plate member
Abstract
The invention provides a kind of adhesive composite, even this adhesive composite also can obtain excellent bonding strength under the condition of cure of low temperature and short period of time, and, even after (the long exposure test under the hot and humid condition) after the reliability test, also can fully keep characteristics such as bonding strength, connection resistance.The present invention also provides the syndeton body of the circuit block that uses this adhesive composite.The invention provides a kind of adhesive composite, it contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) branch part and possesses the dendrimer of distal portion and (d) radical polymerization initiator in the core position with the combinations of states of arborizations and at the end of this branch part.
Description
Technical field
The syndeton body that the present invention relates to adhesive composite and use the circuit block of this adhesive composite.
Background technology
For the various parts bonded purposes that make in the element, in semiconductor element and liquid crystal display device, use the caking agent of various kinds always.This caking agent at first requires to satisfy cementability, and requires to satisfy the characteristic of all many-sides such as reliability under thermotolerance, the humid tropical condition.In addition,, can use the organic substrate of printed circuit board (PCB) or polyimide etc., and can use and have by metals such as copper, aluminium or ITO, SiN, SiO as by sticky object
2Etc. the base material of the formed condition of surface of various materials, therefore, need be at adhesive composite being carried out molecular designing by sticky object or desired characteristic.
In the past, as the adhesive composite of semiconductor element, used for liquid crystal display element, what extensively employing demonstrated high adhesion and high reliability was the thermosetting resin (for example, with reference to patent documentation 1) of principal constituent with Resins, epoxy.As the constituent of thermosetting resin, use Resins, epoxy usually, have solidifying agent such as reactive resol, promote the hot potentiality catalyzer of Resins, epoxy and solidifying agent reaction with Resins, epoxy.Hot potentiality catalyzer is the decision solidification value of adhesive composite and the important factor of curing speed, and the viewpoint of the curing speed during from room temperature stability in storage and heating is considered, can use all cpds.
In addition, in the past, in the manufacturing process of the reality of semiconductor element and liquid crystal display device,, obtained desirable bonding by under 170～250 ℃ temperature, above-mentioned adhesive composite being solidified 1～3 hour.But, along with the height highly integrated, liquid crystal cell of semiconductor element in recent years becomes more meticulous, interelement and narrow and smallization of wiring closet pitch, the heating during curing might cause detrimentally affect to circumferential component.In addition, in order to reduce cost, also need to improve turnout, for adhesive composite, people require more low temperature and interior characteristic of solidifying (low temperature rapidly-curable) of short period of time always.In order to realize this low temperature rapidly-curable, need to use the low hot potentiality catalyzer of activation energy, but be difficult to have concurrently near the stability in storage room temperature known this moment.
Be subjected to people's attention recently, and with free-radical polymerised compounds such as acrylate derivative or methacrylate derivative with as the adhesive composite of the radical-curable of the superoxide of radical polymerization initiator.Radically curing is owing to as the rich reactivity of the free radical of reactive behavior kind, therefore can solidify (for example, with reference to patent documentation 2) at short notice.But the curing reaction of the adhesive composite of radical-curable is fast, therefore, exist with insufficient by the wettability of sticky object always, and the problem of bonding strength difference.As the method for improving wettability, the someone proposes annex solution body rubber in adhesive composite, to improve wettability, to improve the method (for example, with reference to patent documentation 3) of bonding strength.
Patent documentation 1: Japanese kokai publication hei 1-113480 communique
Patent documentation 2: the international brochure that discloses No. 98/44067
Patent documentation 3: the international brochure that discloses No. 2004/50779
Summary of the invention
For the cured article of the adhesive composite that is used for semiconductor element or liquid crystal display device, even require it to be exposed to (for example, 85 ℃/85%RH) descend characteristic also stable of hot and humid conditions for a long time.But, in the adhesive composite of patent documentation 3 records, though bonding strength makes moderate progress, but the caking agent rerum naturas such as Young's modulus after solidifying can not be said so fully, after reliability test (in exposure test for a long time under the hot and humid condition), exist the problem that is difficult to fully to keep bonding force, connects characteristics such as resistance.
Therefore, the object of the present invention is to provide a kind of adhesive composite, even it also can obtain excellent bonding strength under the condition of cure of low temperature and short period of time, and, even after reliability test, also can keep characteristics such as bonding strength, connection resistance fully.The present invention also aims to provide a kind of syndeton body that uses the circuit block of this adhesive composite.
The invention provides a kind of adhesive composite, it contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) branch part and possesses the dendrimer of distal portion and (d) radical polymerization initiator in the core position with the combinations of states of arborizations and at the end of this branch part.Said core segment is meant the center of molecule promptly as the part of dividing branch center, and distal portion can be the end of branch part, also can be the functional group that forms on the end of branch part.
Adhesive composite of the present invention can obtain excellent bonding strength by containing above-mentioned each composition (a)～(d) under the condition of cure of low temperature and short period of time, and also can keep characteristic (bonding strength, connection resistance) after reliability test fully.
In addition, the weight-average molecular weight of dendrimer is preferably more than 1000 and less than 10000.By such formation, can improve the thermotolerance of the cured article of adhesive composite, after reliability test, also can keep characteristic (bonding strength, connection resistance) fully.
As dendrimer, at least a portion that can use distal portion is the compound of free-radical polymerised functional group.By using such dendrimer, can satisfy the reaction of dendrimer and other compositions, therefore, can further improve the thermotolerance of the cured article of adhesive composite.In addition, correspondingly be fully to keep characteristic after the reliability test (bonding strength, connect resistance).
Preferably with respect to the dendrimer of average per 1 molecule, the quantity of free-radical polymerised functional group is more than 6.If the number of functional groups with respect to average per 1 molecule is more than 6, then can obtain high cross-linking density, therefore, the thermotolerance of the cured article of adhesive composite significantly improves, and also can keep characteristic (bonding strength, connection resistance) after reliability test fully.
(b) free-radical polymerised compound preferably contains the vinyl compound with phosphate more than a kind and (b) free-radical polymerised compound except the vinyl compound with phosphate more than a kind.By using such free-radical polymerised compound, can improve the especially bonding strength of metal base of adhesive composite and base material.
As (a) thermoplastic resin, can use the resin more than a kind that is selected from the group of forming by phenoxy resin, urethane resin, polyester polyurethane resin, polyvinyl butyral resin, acrylic resin and polyimide resin.If adopt such resin, can improve thermotolerance, cementability, can access excellent bonding strength, and, after reliability test, also can keep characteristic (bonding strength, connection resistance) fully.
Adhesive composite of the present invention can further contain (f) electroconductive particle.By containing electroconductive particle, can give good electrical conductivity or anisotropic conductive, can be particularly suitable for being used to have the circuit block caking agent purposes to each other of circuit electrode.In addition, can reduce more fully by the connection resistance between the circuit of above-mentioned adhesive composite electrical connection.
The present invention also provides a kind of syndeton body of circuit block, and it possesses: first circuit block that has first splicing ear on interarea; The second circuit parts that on interarea, have second splicing ear; Interconnecting piece, wherein, first and second circuit blocks are configured by interconnecting piece with the relative state of first and second splicing ears, and first and second splicing ears are electrically connected, and interconnecting piece is made of the cured article of adhesive composite of the present invention.In the syndeton body of the circuit block of such structure, the interconnecting piece that connects a pair of circuit block is made of the cured article of the adhesive composite of the invention described above, therefore, can obtain the syndeton body of following circuit block: the strength of joint between circuit block can fully be improved, and, also can keep characteristic (bonding strength, connection resistance) after the reliability test (for example, 85 ℃/85%RH environment is placed down) fully.Adhesive composite of the present invention as interconnecting piece does not need completely solidified (curing of the top that can realize) under the regulation condition of cure, as long as can produce above-mentioned characteristic, then partly solidified state also can.
According to the present invention, a kind of adhesive composite can be provided, it also can obtain excellent bonding strength under the condition of cure of low temperature and short period of time, and (for example in reliability test, keeping under the 85 ℃/85%RH 240 hours) after also can keep bonding strength and the characteristic that is connected resistance, also have the processing of excellence.And the present invention can also provide the syndeton body of the circuit block that uses this adhesive composite.
Description of drawings
Fig. 1 is the employing relevant with embodiments of the present invention does not contain the sectional view of syndeton body of circuit block of the adhesive composite of electroconductive particle;
Fig. 2 is the sectional view of first circuit block, second circuit parts and the adhesive composite (do not contain electroconductive particle) relevant with embodiments of the present invention;
Fig. 3 is the employing relevant with embodiments of the present invention contains the sectional view of syndeton body of circuit block of the adhesive composite of electroconductive particle;
Fig. 4 is the sectional view of first circuit block, second circuit parts and the adhesive composite (contain electroconductive particle) relevant with embodiments of the present invention.
Nomenclature
10,20: adhesive composite; 10C, 20C: interconnecting piece; 21: the adhesive composite that does not contain electroconductive particle; 22: electroconductive particle; 21C: the cured article that does not contain the adhesive composite of electroconductive particle; 30: the first circuit blocks; 31: the first circuit substrates; 31a: interarea; 32: the first splicing ears; 40: the second circuit parts; 41: the second circuit substrate; 41a: interarea; 42: the second splicing ears; 100,200: the syndeton body of circuit block
Embodiment
Below, according to circumstances with reference to accompanying drawing, simultaneously suitable embodiment of the present invention is described in detail.In the accompanying drawing, identical or suitable part is marked with identical symbol, and the repetitive description thereof will be omitted.In this manual, said (methyl) vinylformic acid is meant vinylformic acid or corresponding with it methacrylic acid, also does same explanation in having other compounds of identical skeleton.
In this manual, the second-order transition temperature (Tg) of said (a) thermoplastic resin is meant with the undefined main peak temperature that disperses.Promptly, (for example adopt the Measurement of Dynamic Viscoelasticity device, the viscoelastic analyzer " RSA-3 " (trade(brand)name) that TA instrument company makes), to (a) thermoplastic resin film, at 5 ℃/min of heat-up rate, frequency 10Hz, measure under the condition of temperature-150～300 ℃ and measure dynamic viscoelastic, serve as the main peak temperature that disperses with the peak temperature of tan δ.
Weight-average molecular weight of the present invention and number-average molecular weight are according to the condition shown in the table 1, measure resulting polystyrene standard scaled value by gel permeation chromatography (GPC).
Table 1
| Device | The GPC-8020 that east Cao (strain) makes |
| Detector | The RI-8020 that east Cao (strain) makes |
| Chromatographic column | Hitachi changes into industry (strain) and makes Gelpack GL-A-160-S+GL-A150-SG2000Hhr |
| Sample solution concentration | 120mg/3mL |
| Solvent | Tetrahydrofuran (THF) |
| Injection rate | 60μL |
| Pressure | 30kgf/cm 2 |
| Flow | 1.00mL/min |
Adhesive composite of the present invention contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) branch part and possesses the dendrimer of distal portion and (d) radical polymerization initiator with dendroid ramose combinations of states in the core position and at the end of this branch part.
(a) thermoplastic resin (below, sometimes abbreviate (a) composition as) be meant resin (polymer) with following character: become the high liquid state of viscosity by heating, Free Transform under external force, if cooling is also removed external force, then keeping hardening under the state of this shape, this process can repeat.In addition, the resin (polymer) that also comprises band reactive functional groups with above-mentioned character.(a) Tg of thermoplastic resin is preferably 0～190 ℃, more preferably 20～170 ℃.
In addition, even meet the definition of above-mentioned (a) thermoplastic resin, the structure with (c) the described later composition i.e. compound of " branch part possesses distal portion in the core position with the combinations of states of arborizations and at the end of this branch part " structure is also classified in (c) composition.
(a) to be preferably main chain be straight catenate polymer to thermoplastic resin.(a) thermoplastic resin has under the situation of side chain, and preferably this side chain does not form tree-like shaped (being meant the shape that increases more to top branch more).As such thermoplastic resin, can use polyimide resin, polyamide resin, phenoxy resin, (methyl) acrylic resin, urethane resin, polyester urethane resin, polyvinyl butyral resin etc.Further, can contain siloxane bond, fluoro substituents in these polymkeric substance.These resins can be used singly or two or more kinds mixed.As long as these blended resins mix to each other fully, perhaps produce microphase-separated and form the gonorrhoea state, just can suitably use.
Adhesive composite is shaped to when membranaceous, and (a) molecular weight of thermoplastic resin is big more, and the then easy more film that obtains forms property, in addition, the mobile influential melt viscosity when making the film-like adhesive composition can be set at wide range.(a) molecular weight of thermoplastic resin comes in weight-average molecular weight, is preferably 5000～150000, is preferably 10000～80000 especially.Making weight-average molecular weight is more than 5000, then obtains good film formation property easily, on the other hand, is below 150000, obtains the intermiscibility good with other compositions easily.
In adhesive composite, (a) content of thermoplastic resin is benchmark with the adhesive composite total amount, is preferably 5～80 weight %, more preferably 15～70 weight %.If be more than the 5 weight %, then obtain good film formation property easily, in addition, if be below the 80 weight %, then adhesive composite tends to demonstrate good flowability.
(b) free-radical polymerised compound is meant under the effect of radical polymerization initiator the compound that produces radical polymerization, also can be to make and himself produce the compound of free radical by giving activation energy such as light, heat.As free-radical polymerised compound, for example, can suitably use have vinyl, the compound by the functional group of active free radical polymerization such as (methyl) acryl, allyl group, dimaleoyl imino.
Specifically, can enumerate oligopolymer such as epoxy (methyl) origoester acrylate, carbamate (methyl) origoester acrylate, polyethers (methyl) origoester acrylate, polyester (methyl) origoester acrylate; Trimethylolpropane tris (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polyalkylene glycol two (methyl) acrylate, dicyclopentenyl (methyl) acrylate, dicyclopentenyl oxygen base ethyl (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, cyamelide modification 2 officials energy (methyl) acrylate, cyamelide 3 officials energy (methyl) acrylate, two phenoxyethyl alcohol fluorenes acrylate, epoxy (methyl) acrylate that addition on the glycidyl of bisphenol fluorene diglycidylether (methyl) vinylformic acid forms, two phenoxyethyl alcohol fluorenes acrylate, epoxy (methyl) acrylate that addition on the glycidyl of bisphenol fluorene diglycidylether (methyl) vinylformic acid forms, in the compound that forms by addition ethylene glycol or propylene glycol on the glycidyl of bisphenol fluorene diglycidylether, import the compound that (methyl) acryloxy obtains, and by the compound of following general formula (1) and (2) expression.
[Chemical formula 1]
(R here,
1And R
2Represent hydrogen or methyl independently of one another, a and b represent 1～8 integer independently of one another.)
[Chemical formula 2]
(R here,
3And R
4Represent hydrogen or methyl independently of one another, c and d represent 0～8 integer independently of one another.)
In addition, as (b) free-radical polymerised compound,, also can use even be that paraffin shape, wax shape, crystalloid, glassy, powdery etc. do not have flowability to demonstrate the material of solid state when being statically placed in 30 ℃ separately with being not particularly limited.
Specifically, can enumerate N, N '-methylene-bisacrylamide, diacetone acrylamide, N hydroxymethyl acrylamide, N-phenyl methyl acrylamide, 2-acrylamide-2-methyl propane sulfonic acid, three (2-acryloxy ethyl) isocyanuric acid ester, N-phenylmaleimide, N-(o-methyl-phenyl-) maleimide, N-(aminomethyl phenyl) maleimide, N-(p-methylphenyl)-maleimide, N-(o-methoxyphenyl) maleimide, N-(m-methoxyphenyl) maleimide, N-(p-methoxyphenyl)-maleimide, N-methyl maleimide, the N-ethyl maleimide, N-octyl group maleimide, 4,4 '-ditan bismaleimides, meta-phenylene bismaleimide, 3,3 '-dimethyl-5,5 '-diethyl-4,4 '-ditan bismaleimides, the 4-methyl isophthalic acid, 3-phenylene bismaleimides, N-methacryloxy maleimide, N-acryloxy maleimide, 1,6-bismaleimides-(2,2, the 4-trimethylammonium) hexane, N-methacryloxy succinimide, N-acryloxy succinimide, 2-naphthyl methyl acrylate, 2-naphthyl acrylate, tetramethylol methane tetraacrylate, the divinyl ethylidene-urea, divinyl propylidene urea, the polystyrene-based ethyl-methyl acrylate of 2-, N-phenyl-N '-(3-methacryloxy-2-hydroxypropyl)-Ursol D, N-phenyl-N '-(3-acryloxy-2-hydroxypropyl)-Ursol D, the tetramethyl-piperidyl methacrylic ester, the tetramethyl-piperidyl acrylate, pentamethyl-piperidino methyl acrylate, pentamethyl-piperidyl acrylate, the octadecyl acrylate, N tert butyl acrylamide, diacetone acrylamide, N-(hydroxymethyl) acrylamide, compound by following general formula (3)～(12) expression.
[chemical formula 3]
(here, e represents 1～10 integer.)
[chemical formula 4]
[chemical formula 5]
(R here,
5And R
6Represent hydrogen or methyl independently of one another, f represents 15～30 integer.)
[chemical formula 6]
(R here,
7And R
8Represent hydrogen or methyl independently of one another, g represents 15～30 integer.)
[chemical formula 7]
(R here,
9Expression hydroxyl or methyl.)
[chemical formula 8]
(R here,
10Expression hydrogen or methyl, h represents 1～10 integer.)
[chemical formula 9]
(R here,
11Organic group shown in expression hydrogen or following general formula I or the II, i represents 1～10 integer.)
[Chemical formula 1 0]
(in the general formula, * represents to combine with other atoms.)
[Chemical formula 1 1]
(R here,
12The organic group that expression hydrogen or following general formula I II or IV represent, j represents 1～10 integer.)
[Chemical formula 1 2]
(in the general formula, * represents to combine with other atoms.)
[Chemical formula 1 3]
(R here,
13Expression hydrogen or methyl.)
[Chemical formula 1 4]
(R here,
14Expression hydrogen or methyl.)
(b) free-radical polymerised compound can use a kind of compound, also can mix and use multiple compound.
In addition, can be with the compound that belongs to (b) composition promptly from phosphorous acidic group vinyl compound, N-vinyl compound and N, the N-vinyl based compound of selecting in the group that N-dialkyl group vinyl compound is formed is with (b) composition in addition to these and use.With phosphorous acidic group vinyl compound, can improve the cementability of adhesive composite by also to metal base.In addition, with N-vinyl based compound, can improve the crosslinking rate of adhesive composite by also.
As phosphorous acidic group vinyl compound, get final product so long as have the compound of phosphate and vinyl, there is no particular restriction, is preferably the compound with following general formula (35)～(37) expression.
[Chemical formula 1 5]
(R here,
15Expression (methyl) acryl, R
16Expression hydrogen atom or methyl, n, o represent 1～8 integer independently of one another.In the formula, R
15R to each other,
16To each other, n to each other and o identical separately or different to each other.)
[Chemical formula 1 6]
(R here,
17Expression (methyl) acryl, p, q represent 1～8 integer independently of one another.In the formula, R
17To each other, p to each other and q identical separately or different to each other.)
[Chemical formula 1 7]
(R here,
18Expression (methyl) acryl, R
19Expression hydrogen atom or methyl, r and s represent 1～8 integer independently of one another.In the formula, R
18R to each other,
19To each other, r to each other and s identical separately or different to each other.)
Object lesson as phosphorous acidic group vinyl compound, can enumerate acid phosphorus acyloxy ethyl-methyl acrylate, acid phosphorus acyloxy ethyl propylene acid esters, acid phosphorus acyloxy propyl methyl acid esters, acid phosphorus acyloxy polyoxyethylene glycol monomethacrylates, acid phosphorus acyloxy polyoxy propylene glycol monomethyl acrylate, 2,2 '-two (methyl) acryloxy diethyl phosphoric acid ester, EO modified phosphate dimethacrylate, phosphoric acid modification epoxy acrylate, phosphoric acid vinyl acetate etc.
The addition of phosphorous acidic group vinyl compound, be independent of the addition of (b) free-radical polymerised compound except phosphorous acidic group vinyl compound,, be preferably 0.2～300 weight part with respect to (a) thermoplastic resin 100 weight parts, in addition, 1～200 weight part more preferably.By the addition that makes phosphorous acidic group vinyl compound is more than 0.2 weight part, obtains high-adhesive-strength easily, and in addition, by being below 300 weight parts, the rerum natura of the adhesive composite after the curing is difficult for reducing, and guarantees reliability easily, and is therefore preferred.
On the other hand, as N-vinyl based compound, specifically, can enumerate N-vinyl imidazole, N-vinyl pyridine, N-vinyl pyrrolidone, N-vinyl formamide, N-caprolactam, 4, two (the N of 4 '-vinylidene, accelerine), N-vinyl acetamide, N,N-DMAA, N, N-diethyl acrylamide etc.
Addition except (b) free-radical polymerised compound of the included compound of above-mentioned phosphorous acidic group vinyl compound with respect to (a) thermoplastic resin 100 weight parts, is preferably 50～250 weight parts, more preferably 60～150 weight parts.If addition is more than 50 weight parts, obtain enough thermotolerances easily after then solidifying.In addition, if be below 250 weight parts, when then using, obtain good film formation property easily as film.
(c) of the present invention branch part possesses the dendrimer of distal portion with the arborizations combinations of states in the core position and at the end of this branch part, has the tree-like shaped that is made of core position, branch part and distal portion.The core position for example is made of the compound with the reactive functional groups A more than at least 2.Branch part for example is made of the blocking compound, and the reactive functional groups A that described blocking compound has 1 energy and a core position C of functional group of association reaction takes place and the reactive functional groups B (identical or different with the reactive functional groups A of core position) of association reaction can take place with the C of functional group more than 2.Preferred this blocking compound by reactive functional groups A and the C of functional group combination, and combines with the core position, by combination between the blocking compound that carries out reactive functional groups B and the C of functional group repeatedly, forms branch part, and the result produces arborizations.Distal portion for example is equivalent to the reaction end of branch part.Distal portion can be exactly the form of unreacted reactive functional groups B, also can its all or part of can carry out modification with the compound that the D of functional group of association reaction takes place reactive functional groups B by having.The blocking compound of branch part can be made of the compound more than 2 kinds, and reactive functional groups B and/or the C of functional group can be more than 2 kinds.The compound of distal portion and the D of functional group are too.
As the example of reactive functional groups A and/or B, can enumerate carboxyl, hydroxyl, amino, epoxy group(ing) etc.In addition, as having the compound that the D of functional group of association reaction can take place with the reactive functional groups B of distal portion, for example, can enumerate monohydroxy-alcohol, monocarboxylic acid, lipid acid etc.
In addition, the key that the reaction by reactive functional groups A and/or B and the C of functional group generates is preferably ester bond, amido linkage.In addition, the key that reaction generated by reactive functional groups B and the D of functional group is preferably ester bond, amido linkage.The key that key that reaction by reactive functional groups A and/or B and the C of functional group generates and the reaction by reactive functional groups B and the D of functional group generate, be respectively ester bond or amido linkage, thus, interaction, the wettability of organic substrates such as printed circuit board (PCB), polyimide are tended to improve, obtain high bonding strength easily, connection reliability tends to improve.
Dendrimer is preferably the compound with said structure, and dendrimer can be that polymer also can be an oligopolymer.In addition, also comprise the high dendrimer of ramose systematicness, the hyperbranched polymer that systematicness is low in the aforementioned dendrimer.
Object lesson as dendrimer, for example, can enumerate polyester dendrimer, poly-(amide amine) dendrimer, poly-imines dendrimer, polyamine dendrimer, the tree-shaped macromole of polymeric amide, polyetheramides dendrimer, polyethers dendrimer, polyether ester dendrimer, polyetherketone dendrimer, the tree-shaped macromole of polycarbonate etc.
In addition, the core position is by a kind of compound formation of selecting from the compound group of following general formula (13)～(20) expression, branch part is formed by the structure that constitutes more than a kind or 2 kinds of the repeating structure of representing from following general formula (21)～(33), all or part of bonded compound of position and reactive functional groups B comprises the compound of following general formula (34) expression endways, and these compounds that constitute are as mentioned above also enumerated as the object lesson of dendrimer.In addition, the combination of the core position of this dendrimer and the combination of branch part, the combination between branch part and branch part and distal portion is preferably ester bond or amido linkage respectively.These keys are ester bond or amido linkage, make interaction, the wettability of organic substrates such as printed circuit board (PCB), polyimide are tended to improve, and obtain high bonding strength easily, and connection reliability tends to improve.
[Chemical formula 1 8]
[Chemical formula 1 9]
[Chemical formula 2 0]
[Chemical formula 2 1]
[Chemical formula 2 2]
[Chemical formula 2 3]
[Chemical formula 2 4]
[Chemical formula 2 5]
(in the general formula, k, l represent 1～5 integer.In addition, * represents to combine with other atom.)
[Chemical formula 2 6]
(m represents 2～26 integer.In addition, * represents to combine with other atoms.)
(c) composition can contain multiple dendrimer.In addition; consider from stable on heating angle, (c) composition contain preferably that compound that usefulness more than a kind has free-radical polymerised functional group such as (methyl) acryl, vinyl, styryl and a D of functional group carries out modification to all or part of of the reactive functional groups B of distal portion and aforementioned dendrimer.As this dendrimer, consider and (b) reactivity of free-radical polymerised compound, more preferably the material that carries out modification with compound with (methyl) acryl and the D of functional group.In addition, with regard to this dendrimer, the quantity of free-radical polymerised functional group is more than 6 in preferred average per 1 molecule, and the quantity of free-radical polymerised functional group is 6～15 in more preferably average per 1 molecule.Number of functional groups by making free-radical polymerised functional group in average per 1 molecule is more than 6, tends to make that thermotolerance improves fully.
(c) addition of composition with respect to (a) thermoplastic resin 100 weight parts, is 0.2～100 weight part, is preferably 0.5～70 weight part.If addition is more than 0.2 weight part, then the thermotolerance of the cured article of adhesive composite is tended to improve, and in addition, if be below 100 weight parts, obtains good film formation property when then using as film easily.
As (d) radical polymerization initiator, can use superoxide or azo-compound etc. by giving the compound that activation energy produces free radical, consider from stability, viewpoint reactive, intermiscibility, half life temperature was 90～175 ℃ in preferred 1 minute, and molecular weight is 180～1000 superoxide.By 1 minute half life temperature is in this scope, not only stability in storage excellence, and free radical reaction also fully uprises, and can solidify at short notice.In addition, be in this scope, make the intermiscibility excellence of adhesive composite and other compositions by making molecular weight.
Object lesson as such (d) composition; can enumerate 1; 1; 3; 3-tetramethyl butyl new decanoate ester peroxide; two (4-tert-butylcyclohexyl) peroxy dicarbonate; two (2-ethylhexyl) peroxy dicarbonate; the cumyl new decanoate ester peroxide; two bay acyl peroxides; 1-cyclohexyl-1-methylethyl new decanoate ester peroxide; uncle's hexyl new decanoate ester peroxide; tert-butyl hydroperoxide neodecanoic acid ester; the tert-butyl hydroperoxide pivalate; 1; 1; 3; 3-tetramethyl butyl peroxidation-2-ethylhexanoate; 2; 5-dimethyl-2; 5-two (peroxidation of 2-ethyl hexanoyl base) hexane; uncle's 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-tri-methyl hexanoic acid ester; 3-hydroxyl-1; 1-dimethylbutyl new decanoate ester peroxide; 1; 1; 3; 3-tetramethyl butyl peroxidation 2-ethylhexanoate; t-amyl peroxy neodecanoic acid ester; two (3-methyl benzoyl) superoxide; the dibenzoyl superoxide; two (4-methyl benzoyl) superoxide; 2; 2 '-azo two-2; the 4-methyl pentane nitrile; 1; 1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane); 2; 2 '-azobis isobutyronitrile; 2; 2 '-azo two (2-methylbutyronitrile); dimethyl-2; 2 '-azobis isobutyronitrile; 4; 4 '-azo two (4-cyanovaleric acid); 1; 1 '-azo two (1-cyclohexane nitrile); uncle's hexyl peroxidation sec.-propyl monocarbonate; the tert-butyl hydroperoxide toxilic acid; tert-butyl hydroperoxide-3; 5; 5-tri-methyl hexanoic acid ester; the tert-butyl hydroperoxide laurate; 2; 5-dimethyl-2; 5-two (peroxidation of 3-methyl benzoyl) hexane; tert-butyl hydroperoxide-2-ethylhexyl monocarbonate; uncle's hexyl peroxide benzoate; 2; 5-dimethyl-2,5-two (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; t-amyl peroxy benzoic ether etc.These compounds are except can using separately, and the compound that can also mix more than 2 kinds uses.
In addition, as (d) composition, also can suitably use the compound that generates free radical by the light that shines 150～750nm.As such compound, for example, more preferably use at Photoinitiation, Photopolymerization, and Photocuring, J.-P.Fouassier, Hanser Publishers (nineteen ninety-five), the alpha-acetamido-amphyl of the 17th～35 page of record or phosphine oxide derivative are because they are to light-struck susceptibility height.
These compounds except independent use, can also mix use with aforementioned superoxide, azo-compound.
(d) addition of composition with respect to (a) thermoplastic resin 100 weight parts, is preferably 0.1～500 weight part, more preferably 1～300 weight part.If (d) addition of composition is more than 0.1 weight part, then adhesive composite solidifies easily fully, in addition, if be that then shelf-stability tends to well below 500 weight parts.
(f) electroconductive particle when being used to connect the circuit block with splicing ear, uses the median size material littler than distance between splicing ear so long as particle integral body has the material of electroconductibility gets final product.As the object lesson of (f) electroconductive particle, can enumerate metallicss such as Au, Ag, Ni, Cu, soldering or carbon etc.In addition, can also be to be nuclear, to the material of this nuclear lining aforementioned metal, metallics or carbon with dielectric glass, pottery, plastics etc.(f) electroconductive particle is for plastics being nuclear and when this nuclear is covered the material of above-mentioned metal, metallics or carbon or hot molten metal particle, because because of heating and pressurizing has deformability, therefore, during connection with the increase of the contact area of electrode, reliability increases, and is therefore preferred.
In addition, further with the particulate on the surface of these (f) electroconductive particles of lining such as macromolecule resin, can suppress when increasing the electroconductive particle use level because of the caused short circuit of particle contact to each other, can improve the insulativity between telegraph circuit, therefore, can suitably use this particle separately or mix use with electroconductive particle.
Consider that from viewpoint dispersed, electroconductibility the median size of being somebody's turn to do (f) electroconductive particle is preferably 1～18 μ m.When containing such (f) electroconductive particle, adhesive composite can suitably use as the anisotropic conductive adhesive composite.
(f) addition of electroconductive particle, the whole volumes with respect to the composition beyond (f) electroconductive particle of adhesive composite are preferably 0.1～30 volume %, more preferably 0.1～10 volume %.By containing more than the 0.1 volume %, the electroconductibility of the adhesive composite after the curing becomes well, and is therefore preferred.In addition,, be difficult to produce short circuit by being below the 30 volume %, therefore preferred.The volume of each composition of volume % before according to 23 ℃ curing decides, and the volume of each composition can be obtained by utilizing proportion to be converted into volume from weight.In addition, also can try to achieve by the following method: in graduated cylinder etc., add and be unlikely to make this composition dissolving or swelling and the abundant appropriate solvent of wetting this composition (water, alcohol etc.), add this composition then, with the volume of increase as this volume.
In order to control curing speed or to give stability in storage, can add stablizer in the adhesive composite.As such stablizer, can there is no particular restriction ground use known compound as stablizer, be preferably quinone derivatives such as benzoquinones, quinhydrones; Amphyls such as 4-methoxyphenol, 4-tert-butyl catechol; 2,2,6,6-tetramethyl piperidine-1-oxygen base, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-aminooxy derivatives such as 1-oxygen base; Hindered amine derivatives such as tetramethyl piperidine methacrylic ester.
The addition of aforementioned stable agent with respect to adhesive composite 100 weight parts, is 0.01～30 weight part, is preferably 0.05～10 weight part.By making addition is more than 0.01 weight part, embodies the additive effect of stablizer easily, in addition, by being below 30 weight parts, is difficult to the intermiscibility with other compositions is produced detrimentally affect.
In adhesive composite, can suitably add alkoxyl silicone alkane derivatives, silazane derivative and be bonding auxiliary agents such as the coupling agent of representative and adaptation rising agent, flow agent.Specifically, be preferably compound with following general formula (38) expression, except independent use, the compound that can be mixed with two or more.
[Chemical formula 2 7]
(R here,
20, R
21, R
22Alkyl, the alkoxyl group of carbonatoms 1～5, the alkoxy carbonyl of carbonatoms 1～5, the aryl of representing hydrogen, carbonatoms 1～5 independently, R
23Expression (methyl) acryl, vinyl, isocyanate group, imidazolyl, sulfydryl, amino, methylamino, dimethylamino, benzylamino, phenyl amino, cyclohexyl amino, morpholino base, piperazinyl, uride base, glycidyl, t represents 1～10 integer.)
For the purpose that relaxes stress and raising cementability, adhesive composite can contain rubber constituent.Said rubber constituent is meant the composition that directly shows the composition of caoutchouc elasticity (for example, JIS K6200) with this state or go out caoutchouc elasticity by reaction and display.Rubber constituent can be that solid also can be a liquid down in room temperature (25 ℃), considers from improving mobile viewpoint, is preferably liquid.As rubber constituent, be preferably compound with polyhutadiene skeleton.Rubber constituent can have cyano group, carboxyl, hydroxyl, (methyl) acryl or morpholinyl.In addition, consider, be preferably in side chain or the terminal rubber constituent that contains high polar group cyano group, carboxyl from the viewpoint that improves cementability.Even have the polyhutadiene skeleton, demonstrate and classify under the thermoplastic situation in (a) composition, demonstrate that free-radical polymerised situation is next classifies in (b) composition.
As the object lesson of above-mentioned rubber constituent, can enumerate liquid propene nitrile-divinyl rubber; Liquid propene nitrile-the divinyl rubber that contains carboxyl, hydroxyl, (methyl) acryl or morpholinyl in polymer ends; The liquid carboxylated nitrile rubber is preferably 10～60 quality % as the acrylonitrile content of polar group.
For the purpose that relaxes stress and raising cementability, adhesive composite of the present invention can further contain organic fine particles.Said organic fine particles is meant the particulate (for example, median size is 0.05～1.0 μ m) that is formed by organic compound.When organic fine particles was formed by above-mentioned rubber constituent, not as organic fine particles but classify in rubber constituent, organic fine particles was by above-mentioned (a) when thermoplastic resin forms, not as organic fine particles but classify in thermoplastic resin.
As organic fine particles; for example; can enumerate by polyisoprene; polyhutadiene; the C-terminal polyhutadiene; the C-terminal polyhutadiene; 1; the 2-polyhutadiene; C-terminal 1, the 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 terminal poly-(oxypropylene); poly-(oxygen tetramethylene) glycol; polyolefin diols; polyolefin diols (methyl) alkyl acrylate-butadiene-styrene polymkeric substance; (methyl) alkyl acrylate-silicone copolymer; the organic fine particles that silicone (methyl) acrylic copolymer or mixture form.These compounds except can using separately, the also compound that can be mixed with two or more.
When adhesive composite is liquid at normal temperatures, can use with pasty state.When at room temperature being solid, except heating the back use, also can use solvent carry out pasteization.As the solvent that can use, so long as do not have reactivity, and demonstrate enough deliquescent materials and get final product with adhesive composite and additive, there is no particular restriction, and preferably the boiling point under normal pressure is 50～150 ℃ a material.Boiling point is under the situation more than 50 ℃, even at room temperature place, also is difficult to volatilization, and the use in open system is unrestricted, and is therefore preferred.In addition,, then make solvent evaporates easily, obtain the reliability after bonding easily if boiling point is below 150 ℃.
Adhesive composite also can be made membranaceous use.As required adhesive composite is added solvent etc., with the solution coat so made on separability base materials such as fluororesin film, polyethylene terephthalate film, release paper, perhaps, make aforementioned solution soak into base material such as non-woven fabrics and be placed on the separability base material, removing desolvates waits and then uses as film.Consider from aspects such as the property handled, use more convenient with the film shape.
Adhesive composite also can and with heating with pressurize and make it bonding.There is no particular restriction for Heating temperature, is preferably 100～250 ℃ temperature.Pressure so long as do not damage by the scope of sticky object gets final product, and there is no particular restriction, and the preferred usually pressure that uses i.e. 0.1～10MPa.These heating and pressurization are preferably carried out in the scope in 0.5 second～120 second.In addition, adhesive composite of the present invention can be realized bonding under 140～200 ℃, 3MPa, the heating in 10 seconds and such condition of pressurizeing.
Adhesive composite can be used as different different types of of thermal expansivity and is used by the caking agent of sticky object.Specifically, can be used as anisotropically conducting adhesive, silver-colored paste, silverskin etc. and be the circuit connection material of representative; CSP uses with the semiconductor element adhesives for representative such as underfill, LOC adhesive tape with elastomerics, CSP.
In order to obtain the connected to each other syndeton body of circuit block and circuit terminal, semiconductor device, can use adhesive composite.
Fig. 1 is the sectional view that the syndeton body of the circuit terminal that the embodiment of the adhesive composite of the present invention do not contain (f) electroconductive particle relates to is used in expression.
The syndeton body 100 of circuit terminal shown in Figure 1 possesses: first circuit block 30 that has first splicing ear 32 on the interarea 31a of first circuit substrate 31; The second circuit parts 40 that on the interarea 41a of second circuit substrate 41, have second splicing ear 42; And, connect the interconnecting piece 10C of the interarea 41a of the interarea 31a of first circuit substrate 31 and second circuit substrate 41 in first splicing ear 32 mode relative with second splicing ear 42.First splicing ear 32 and second splicing ear 42 are electrically connected by being in contact with one another.In addition, interconnecting piece 10C is formed by adhesive composite 10 of the present invention.
The syndeton body 100 of circuit terminal shown in Figure 1 can be made as followsly.
At first, as shown in Figure 2, prepare first circuit block 30, second circuit parts 40 and be shaped to membranaceous adhesive composite 10.Then, bonding composition 10 is placed on the interarea 42a that is formed with second splicing ear 40 of second circuit parts 40, further, on adhesive composite 10, in first splicing ear 32 mode relative, place first circuit block 30 with second splicing ear 42.Then, make its curing across first circuit block 30 and 40 pairs of adhesive composites of second circuit parts, 10 limit heating edge, simultaneously, on direction, pressurize perpendicular to interarea 31a, 41a, between first and second circuit blocks 30,40, form interconnecting piece 10C, obtain the syndeton body 100 of the circuit terminal of Fig. 1.
Fig. 3 is the sectional view that the syndeton body of the circuit terminal that the embodiment of the adhesive composite of the present invention that contains (f) electroconductive particle relates to has been used in expression.
The syndeton body 200 of circuit terminal shown in Figure 3 possesses: first circuit block 30 that has first splicing ear 32 on the interarea 31a of first circuit substrate 31; The second circuit parts 40 that on the interarea 41a of second circuit substrate 41, have second splicing ear 42; And, connect the interconnecting piece 20C of the interarea 41a of the interarea 31a of first circuit substrate 31 and second circuit substrate 41 in first splicing ear 32 mode relative with second splicing ear 42.Interconnecting piece 20C be in the composition except the electroconductive particle of adhesive composite 21, be dispersed with electroconductive particle 22 adhesive composite 20 cured article (promptly, in the cured article 21C of the composition except the electroconductive particle of adhesive composite, be dispersed with the material of electroconductive particle 22), between relative first splicing ear 32 and second splicing ear 42, electroconductive particle 22 contacts with two splicing ears, thus, by electroconductive particle 22, two splicing ears are electrically connected.
The syndeton body 200 of circuit terminal shown in Figure 3, for example, as shown in Figure 4, prepare first circuit block 30, second circuit parts 40 and be shaped to membranaceous adhesive composite 20, by the method same, make with the syndeton body 100 that obtains the foregoing circuit terminal.
Here, as the circuit substrate that possesses splicing ear, can use inanimate matters such as semi-conductor, glass, pottery; Organism such as polyimide, polycarbonate; The various combinations of their compound such as glass/epoxy.
Embodiment
Below, based on embodiment the present invention is specifically described, but the present invention is not limited to these embodiment.
[preparation of thermoplastic resin (phenoxy resin (YP-50))]
Phenoxy resin (goods name: YP-50, Dongdu changes into society and makes) is dissolved in resin 40g among the methyl ethyl ketone 60g, makes the solution of solids component 40 weight %.
[preparation of thermoplastic resin (polyester urethane resin (UR-1400))]
Polyester urethane resin (goods name: UR-1400, Japan spin society and make) adopts the methyl ethyl ketone of resinous principle 30% and 1: 1 mixed solvent solute of toluene.
[synthesizing of thermoplastic resin (urethane resin)]
Poly adipate succinic acid ester glycol (goods name: poly adipate succinic acid ester glycol with weight-average molecular weight 2000, Aldrich company makes) 450 weight parts, the polyoxy tetramethylene glycol of molecular-weight average 2000 (goods name: polyoxy tetramethylene glycol, Aldrich company makes) 450 weight parts, 1,4-butyleneglycol (goods name: 1, the 4-butyleneglycol, Aldrich company makes) 100 weight parts, be dissolved in methyl ethyl ketone (goods name: 2-butanone, make with the pure pharmaceutical worker's industry of light (strain)) 4000 weight parts, add diphenylmethanediisocyanate (goods name: diphenylmethanediisocyanate, Aldrich company makes) 390 weight parts, it was reacted 60 minutes down at 70 ℃, obtain urethane resin.Measure the weight-average molecular weight of resulting urethane resin by the GPC method, the result is 100000.
[synthesizing of dendrimer (DA-1)]
In the reactor that possesses reflux exchanger, stirrer, thermometer, temperature control equipment and water separator, add the BOLTORN H20 that Perstorp company makes (OH value: 504mgKOH/g) 55.7g, as the toluene 150mL of reaction solvent, as the quinhydrones 0.143g of stopper, as the pyridine 39.6g of basic catalyst, drip acrylate chloride (Tokyo changes into industry (strain) manufacturing) 49.8g (0.55 mole) while stirring.Drip the back and refluxed 2 hours, behind the naturally cooling, in reaction mixture, add water, extract with toluene.With 10% sodium sulfate the toluene extraction liquid that obtains is washed 3 times.The decompression gold-plating removes toluene, obtains the dendrimer (DA-1) of 80.5g.Functional group's number of the dendrimer that obtains is 16 officials energy (acryl), and weight-average molecular weight (Mw) is 1580.Functional group's number (acryl) of dendrimer is that the combined amount (equivalence ratio) according to reaction raw materials is calculated resulting theoretical value.
[preparation of dendrimer (H2004 and #1000)]
Prepare polyester polyol terminal acrylate #1000 (Mw:1850; functional group's number: 12 officials energy (acryl); Osaka Organic Chemical Industry Co., Ltd. makes) and BOLTORN H2004 (Mw:3200 does not have free-radical polymerised functional group, and Perstorp company makes).
[preparation of free-radical polymerised compound (M-215)]
Prepare cyamelide EO modification diacrylate (goods name: M-215, Toagosei Co., Ltd makes).
[synthesizing of free-radical polymerised compound (urethane acrylate (UA))]
In the reaction vessel of the reflux condensing tube that possesses stirrer, thermometer, band calcium chloride tube, nitrogen ingress pipe, drop into poly-(hexa-methylene carbonic ether) glycol (manufacturing of Aldrich company) 860 weight parts (1.00 moles), dibutyl tin laurate (manufacturing of Aldrich company) 5.53 weight parts of number-average molecular weight 860.After fully importing nitrogen, be heated to 70～75 ℃, spend 3 hours with certain speed and drip isophorone diisocyanate (manufacturing of Aldrich company) 666 weight parts (3.00 moles), make its reaction.Drip and finish about 10 hours of back continuation reaction.Drop into 2-hydroxyethylmethacry,ate (manufacturing of Aldrich company) 238 weight parts (2.05 moles), hydroquinone monomethyl ether (manufacturing of Aldrich company) 0.53 weight part therein, further make its reaction 10 hours, measure affirmation isocyanic ester disappearance end reaction by IR, obtain urethane acrylate (UA).The number-average molecular weight of the UA that obtains is 3700.
[preparation of phosphorous acidic group vinyl compound (P-2M)]
Prepare 2-(methyl) acryloxy ethyl phosphonic acid ester (goods name: light ester P-2M, Kyoeisha Chemical Co., Ltd.'s manufacturing).
[preparation of radical polymerization initiator (PERHEXYL zero)]
Preparation is as uncle's hexyl peroxidation-2-ethylhexanoate (goods name: PERHEXYL zero, NOF Corp makes) of radical polymerization initiator.
[making of electroconductive particle]
On the surface that with the polystyrene is the particle of nuclear, the nickel dam of thickness 0.2 μ m is set, in the outside of this nickel dam, the gold layer of thickness 0.02 μ m is set, make the electroconductive particle of median size 4 μ m, proportion 2.5.
(embodiment 1～6, comparative example 1～3)
Compare to cooperate shown in the table 2 according to solid weight, further cooperate the electroconductive particle that disperses 1.5 volume %, adopt apparatus for coating to be coated on the fluororesin film of thickness 80 μ m, by 70 ℃, 10 minutes warm air drying, the thickness that obtains bond layer was the film-like adhesive composition of 20 μ m.
Table 2
[mensuration that connects resistance, bonding strength]
The film-like adhesive composition that makes embodiment 1～6, comparative example 1～3 is between the flexible PCB (FPC) of the copper circuit with 500 live widths, 25 μ m, pitch 50 μ m, thickness 18 μ m and be formed with between the glass (thickness 1.1mm, surface resistivity 20 Ω/℃) of thin layer of Indium sesquioxide (ITO) of 0.2 μ m.Adopt thermo-compression bonding device (type of heating: permanent pattern of fever, Dongli Engineering Co., Ltd makes),, in the scope of wide 2mm, connect, make linker its 10 seconds of heating and pressurizing under 170 ℃, 3MPa.After keeping 240 hours in firm bonding back with in 85 ℃, the hot and humid groove of 85%RH (test back), with this linker of multitester measuring in abutting connection with the resistance value between circuit.Resistance value is used on average representing in abutting connection with 37 of the resistance between circuit.
In addition, adopt 90 degree to peel off the bonding strength that method is measured this linker, estimate according to JIS-Z0237.Here, the determinator of bonding strength adopts the TensilonUTM-4 (peeling rate 50mm/min, 25 ℃) that Japan Baldwin Co., Ltd. makes.The connection resistance of the above film-like adhesive composition that carries out and the measurement result of bonding strength are shown in following table 3.
Table 3
The adhesive composite that obtains among the embodiment 1～6, after keeping 240 hours in the bonding down back of 170 ℃ of Heating temperatures and in 85 ℃, the hot and humid groove of 85%RH (after the reliability test), all show following good connection resistance of about 3 Ω and the above good bonding strength of 600N/m.
Relative therewith, do not use the adhesive composite of the comparative example 1,2 of (c) of the present invention dendrimer, though demonstrate good connection resistance, but, keep 240 hours in firm bonding back and in 85 ℃, the hot and humid groove of 85%RH after the connection resistance height of (after the reliability test).In addition, in comparative example 3,4, keep 240 hours in bonding back and in 85 ℃, the hot and humid groove of 85%RH after the connection resistance height of (after the reliability test).
Claims (8)
1. adhesive composite, it contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) branch part and possesses the dendrimer of distal portion and (d) radical polymerization initiator in the core position with the combinations of states of arborizations and at the end of this branch part.
2. adhesive composite according to claim 1, wherein, the weight-average molecular weight of described dendrimer is more than 1000 and less than 10000.
3. adhesive composite according to claim 1, wherein, at least a portion of described distal portion is free-radical polymerised functional group.
4. adhesive composite according to claim 3, wherein, the quantity of described free-radical polymerised functional group is more than 6 with respect to the described dendrimer of average per 1 molecule.
5. adhesive composite according to claim 1, wherein, (b) free-radical polymerised compound contains vinyl compound with phosphate and the free-radical polymerised compound in addition of this compound more than a kind more than a kind.
6. adhesive composite according to claim 1, wherein, (a) thermoplastic resin is the resin more than a kind that is selected from the group of being made up of phenoxy resin, urethane resin, polyester polyurethane resin, polyvinyl butyral resin, acrylic resin and polyimide resin.
7. adhesive composite according to claim 1 wherein, further contains (f) electroconductive particle.
8. the syndeton body of a circuit block, it possesses: first circuit block that has first splicing ear on interarea; The second circuit parts that on interarea, have second splicing ear; Interconnecting piece, wherein, described first and second circuit blocks are configured with the relative state of described first and second splicing ears by described interconnecting piece, and, described first and second splicing ears are electrically connected, and described interconnecting piece is made of the cured article of each described adhesive composite in the claim 1～7.
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| CN111433303A (en) * | 2017-12-18 | 2020-07-17 | 三键有限公司 | Radical polymerizable adhesive composition for bonding laminated steel sheets, bonded laminate, motor, and method for producing bonded laminate |
| CN114051647A (en) * | 2020-01-29 | 2022-02-15 | 株式会社村田制作所 | Passive component with electrode and assembly of passive components with electrode |
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| JP5338753B2 (en) * | 2009-07-17 | 2013-11-13 | 日立化成株式会社 | Adhesive composition and connection structure |
| CN115449326B (en) * | 2022-10-11 | 2023-05-19 | 东莞市德聚胶接技术有限公司 | Impact-resistant UV (ultraviolet) curing cofferdam adhesive and preparation method thereof |
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| JP2009001765A (en) * | 2007-05-23 | 2009-01-08 | Hitachi Chem Co Ltd | Adhesive composition, circuit connecting structure, and semiconductor device |
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| JPH11193318A (en) * | 1997-11-04 | 1999-07-21 | Toyo Ink Mfg Co Ltd | Curable composition |
| US6448337B1 (en) | 1999-10-07 | 2002-09-10 | 3M Innovative Properties Company | Pressure sensitive adhesives possessing high load bearing capability |
| JP2002184487A (en) | 2000-12-15 | 2002-06-28 | Sony Chem Corp | Anisotropic conductive adhesive |
| JP4590732B2 (en) | 2000-12-28 | 2010-12-01 | 日立化成工業株式会社 | Circuit connection material, circuit board manufacturing method using the same, and circuit board |
| JP2003277489A (en) * | 2002-03-27 | 2003-10-02 | Dainippon Ink & Chem Inc | Multi-branched polymer and method for producing the same |
| JP4231748B2 (en) * | 2003-07-10 | 2009-03-04 | 太陽インキ製造株式会社 | Prepreg for printed wiring board and multilayer printed wiring board produced using the same |
| JP4872125B2 (en) * | 2006-06-28 | 2012-02-08 | Ｄｉｃ株式会社 | Curable resin composition for multilayer printed wiring board, thermosetting adhesive film, and multilayer printed circuit board |
| JP5292838B2 (en) * | 2007-08-30 | 2013-09-18 | 日立化成株式会社 | Adhesive and circuit member connection structure |
| JP5338753B2 (en) * | 2009-07-17 | 2013-11-13 | 日立化成株式会社 | Adhesive composition and connection structure |
-
2010
- 2010-05-14 JP JP2010112509A patent/JP5418399B2/en not_active Expired - Fee Related
- 2010-05-27 TW TW099117032A patent/TWI419950B/en not_active IP Right Cessation
- 2010-07-09 CN CN201010226914.1A patent/CN101955735B/en not_active Expired - Fee Related
- 2010-07-16 KR KR1020100068807A patent/KR101194523B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6187897B1 (en) * | 1997-09-01 | 2001-02-13 | Toyo Ink Manufacturing Co., Ltd. | Vinyl-group-containing dendrimer and curable composition |
| CN101547989A (en) * | 2006-12-07 | 2009-09-30 | 3M创新有限公司 | Blends of block copolymer and acrylic adhesives |
| JP2009001765A (en) * | 2007-05-23 | 2009-01-08 | Hitachi Chem Co Ltd | Adhesive composition, circuit connecting structure, and semiconductor device |
| WO2009031472A1 (en) * | 2007-09-05 | 2009-03-12 | Hitachi Chemical Company, Ltd. | Adhesive and connecting structure using the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111433303A (en) * | 2017-12-18 | 2020-07-17 | 三键有限公司 | Radical polymerizable adhesive composition for bonding laminated steel sheets, bonded laminate, motor, and method for producing bonded laminate |
| CN114051647A (en) * | 2020-01-29 | 2022-02-15 | 株式会社村田制作所 | Passive component with electrode and assembly of passive components with electrode |
| CN114051647B (en) * | 2020-01-29 | 2023-02-03 | 株式会社村田制作所 | Passive component with electrode and assembly of passive components with electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011038075A (en) | 2011-02-24 |
| TW201113346A (en) | 2011-04-16 |
| KR20110007968A (en) | 2011-01-25 |
| KR101194523B1 (en) | 2012-10-25 |
| JP5418399B2 (en) | 2014-02-19 |
| TWI419950B (en) | 2013-12-21 |
| CN101955735B (en) | 2016-09-14 |
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