CN101016402A - Curing resin composition, adhesive epoxy resin paste, adhesive epoxy resin sheet, conductive connection paste, conductive connection sheet, and electronic component joined body - Google Patents

Abstract

A curing resin composition which is excellent in mechanical strength, heat resistance, moisture resistance, flexibility, temperature cycle resistance, solder reflow resistance and dimensional stability after curing and exhibits high adhesion reliability and high conduction reliability is disclosed. An adhesive epoxy resin paste, adhesive epoxy resin sheet, conductive connection paste, conductive connection sheet, and electronic component joined body respectively using such a curing resin composition are also disclosed. The curing resin composition contains an epoxy resin, a solid polymer having a functional group reactive with an epoxy group, and an epoxy resin curing agent. When a cured product of this curing resin composition is dyed with a heavy metal and observed with a transmission electron microscope, no phase separation structure is observed in the matrix resin.

Description

Curable resin composition, adhesive epoxy resin cream, adhesive epoxy resin thin slice, conduction connect cream, conductive connection sheet and electronic component joined body

The application is that application number is 200380108393.8, the applying date is that December 6, denomination of invention in 2003 are that curable resin composition, adhesive epoxy resin cream, adhesive epoxy resin thin slice, conduction connect dividing an application of cream, conductive connection sheet and electronic component joined body

Technical field

The curable resin composition, adhesive epoxy resin cream, adhesive epoxy resin thin slice, the conduction that the present invention relates to have high reliability connect cream, conductive connection sheet and electronic component joined body.In addition, said thin slice also comprises film among the present invention.

Background technology

At for the miniaturization of semiconductor device and the requirement of high performance, various electronic material caking agents have been developed in recent years.These electronic materials need possess the reliability of height with caking agent, and in order to ensure this reliability, the most frequent use be cure shrinkage few, have high bonding force and kind is abundant, matching design is easy to Resins, epoxy.As this Resins, epoxy,, use for example general liquid epoxy resin such as bisphenol A-type liquid epoxy resin or Bisphenol F type liquid epoxy resin usually because of its operability is good.But, use the electronic material of these general liquid epoxy resins can not adapt to present extreme high reliability requirement with caking agent, therefore need develop a kind of new high performance Resins, epoxy.In addition, said caking agent also comprises pressure sensitive adhesive among the present invention.

At present, as the performance of electronic material being used the relevant reliability of caking agent institute specific requirement, can enumerate for example thermotolerance, wet fastness, cold-resistant thermal cycling, anti-scolding tin backflow etc., wherein, about wet fastness and anti-scolding tin backflow, the general requirement indispensability is the feature that water-intake rate is low, water regain is little of curing adhesive.This is that then the water capacity easily immerses bonding interface because if the water-intake rate of curing adhesive is higher, might reduce the bonding force at interface.In addition,, then reach sharply gasification of moisture behind 200-260 ℃ the scolding tin reflux temperature if the water regain of curing adhesive is bigger, might destroy electronic devices.

On the other hand, if will improve cold-resistant thermal cycling, need a large amount of mineral fillers that are used to dwindle linear expansivity (linear expansivity) of filling usually.This is much smaller because compare the linear expansivity of mineral filler with organic filler.But, if fill mineral filler in a large number, though then linear expansivity can diminish, because of the spring rate of caking agent increases the problem that can cause curing adhesive stress to be difficult to relax.That is, improve on the method for cold-resistant thermal cycling and have certain limit by filling mineral filler.In addition, when caking agent being processed into laminar adhesive sheet and using, the mineral filler meeting of being filled reduces the intensity of solidifying the front attachment sheet, perhaps has the problem that is difficult to laser processing or is difficult to form the high through hole of precision when need to be used to the substrate of through hole.

In addition, aspect the cold-resistant thermal cycling of improvement,, also adopt the method (for example, with reference to speciallyying permit No. 3342703 communique) of adding rubber polymers such as acrylic rubber usually in order to reduce the stress of generation.

Yet, if add rubber polymer, though can improve cold-resistant thermal cycling, owing to being that cost realizes stress relaxation, so be difficult to obtain simultaneously high heat resistance or wet fastness and high cold-resistant thermal cycling to reduce thermotolerance.That is, if will realize cold-resistant thermal cycling with high level, the stress that produces when just needing to relax cold cycling.

In order to reach the effect of lax above-mentioned stress, also adopt usually to make carboxylic acid or glycidyl modified polyolefin for example diene series rubber polymkeric substance, paracril, end reaction base silicone, acrylic rubber, styrene series elastomer etc. with functional group such as CTBN and ATBN are given flexible composition and Resins, epoxy mixes or mode and Resins, epoxy blended method to be separated.But, when these are given flexible composition and mix with the Resins, epoxy that becomes matrix resin, can cause stable on heatingly descending significantly, also can't embody high heat-resisting bonding force under the high temperature.In addition, take phase separation structure,, also have the thermotolerance downward trend because this interface portion of giving flexible composition and Resins, epoxy mixes even these give flexible composition.In addition, because above-mentioned phase separation structure is not necessarily stable with respect to temperature variation, so also can become the state of mixing sometimes according to temperature variation.

In addition, the solidification compound of epoxy resin was a solidifying agent with acid anhydrides etc. mostly in the past, but sometimes can remaining unreacted reactant in the cured article after curing.Can be acid or alkaline after this unreacted reactant reacts by moisture absorption etc., thereby cause cured article surface and the acidic substance on every side and the outflow of alkaline matter, cause the corrosion of electrode metals such as aluminium and copper.In addition, also can be because of dechlorination reaction flow out chlorion, thus cause the infringement reliability problems, be that acid with the generations such as hydrolysis in cured article is catalyzer at above-mentioned dechlorination reaction.

On the other hand, at liquid-crystal display, Personal Computer, carry in the manufacturing processed of electronic products such as communicating machine, when minicomponents such as semiconductor element are electrically connected with substrate, need under the state that fine electrode is opposite each other, connect.In addition, in the manufacturing processed of glass circuit substrate, when on the glass surface that the Lighting Division at automobile grades turning circuit being set, need under the opposed state of electrode surface, be connected glass surface and turning circuit.

As the method that connects these electrodes, the common method that connects protuberance or the direct opposed protuberance of crimping with scolding tin or conduction connection cream etc. that adopts.In addition, in order to protect the electrode after the connection, use the electrode after the resin-sealed connection usually.

Yet, since fine electrode its to connect distance shorter, evenly inject resin within the short period of time and seal so be difficult in.In addition, when connecting the electrode surface of glass surface and turning circuit, with regard to the method that connects with scolding tin, there is the too high problem of connection portion temperature.

Therefore, in order to solve such problem, someone has studied the anisotropic conductive caking agent (for example, with reference to No. 3114162 communique of special permission and special fair 7-73066 communique) that forms laminar or paste behind the caking agent of mixed conductivity particulate and insulativity.

But, with regard to laminar anisotropic conductive caking agent in the past, press electrically conductive microparticle and during enclosed electrode when being crimped on by heating to press on electrode or the protuberance, can residual insulativity caking agent between electrode and electrically conductive microparticle, thus the problem that causes connection reliability to descend.

In addition, anisotropic conductive caking agent with regard to paste, when coating cream, need possess good coatings such as good coating precision and coating efficiency, but filling in the past the flowability of paste-like anisotropic conductive caking agent of a large amount of mineral fillers not too abundant sometimes, so there is the problem that can't fully satisfy coating.In addition, even when making the anisotropic conductive adhesive sheet, also require to possess good coating with casting.In addition, also exist because of electrically conductive microparticle can not be dispersed in the insulativity caking agent to cause electrically conductive microparticle to be assembled each other, and make the adjacent electrode problem of short-circuit thus.

Therefore, the inventor waits and has at first developed the conductive connection sheet that electrically conductive microparticle also is maintained on the adhesive resin thin slice and the part of electrically conductive microparticle is exposed from the adhesive resin thin slice when handling.When using this conductive connection sheet, because not residual insulativity caking agent and particulate are not assembled between electrode and electrically conductive microparticle, so can obtain high connection reliability (for example, opening 2002-313143 number) with reference to the spy.

But, discoveries such as the inventor, when the Lighting Division of connection portion that this conductive connection sheet is used for electronic product for example and automobile grades, if being exposed to pressure kettle test (PCT) is under the hot and humid environment of representative, then be difficult to keep simultaneously the shape of electrically conductive microparticle and thin slice in its use.

Specifically, in this conductive connection sheet, if improve thin slice before solidifying under the normal temperature for the confining force that improves electrically conductive microparticle with respect to the cementability of electrically conductive microparticle, even then after curing, if be in hot and humid following, thin slice also can soften, and shape-retentivity descends, and produces the problem that connection reliability descends.In addition, make it hot and humid also softening down if improve the shape-retentivity of the thin slice under hot and humid, then since normal temperature thin slice down descend with respect to the cementability of electrically conductive microparticle, so also can produce the problem of the confining force decline of electrically conductive microparticle.

In addition, the epoxy resin solidification compound also can be used as the insulated substrate material, and for the insulated substrate that is used for multilayer printed board etc., require it to possess and be difficult for influencing characteristics such as electrical characteristic, water absorbability are low, and in order to reach the effect that is easy to the laser aligned position, also need to possess the transparency etc., the dimensional change when high temperature is handled when an urgent demand scolding tin refluxes in addition etc. is little.

Also have, the epoxy resin solidification compound also can be used as the insulated substrate material, and for the insulated substrate that is used for multilayer printed board etc., require it to possess and be difficult for influencing electrical characteristic, characteristic that water absorbability is low, and be easy to the align effect of position of each thin slice of optical system lens in order to reach, also need to possess the transparency etc., the dimensional change when high temperature is handled when an urgent demand scolding tin refluxes in addition etc. is little.

For the die attachment thin film dielectric material that engages organic substrate, ceramic substrates etc. such as silicon chip and metal frame, multi-ply wood, assembled substrate, also require to possess performance same as described above.In addition, as the silicon chip of subsidiary die attachment film, also have in the wafer scale of the direct sticking film of wafer stage and the mode of pasting on every silicon chip respectively, still desired performance does not have difference.

Summary of the invention

In view of the foregoing and problem, the object of the present invention is to provide the electronic component joined body that has good physical strength, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc. after the curing and can show high bonding reliability and when forming conductive material, can show the curable resin composition of high conducting reliability and use adhesive epoxy resin cream, adhesive epoxy resin thin slice, the conduction of this curable resin composition to connect cream, conductive connection sheet and use these.

The curable resin composition of the invention of being put down in writing in the technical scheme 1 (below be recited as " the 1st the present invention "), it is characterized in that, be contain Resins, epoxy, have can with the solid polymer of the functional group of epoxy reaction and the curable resin composition of hardener for epoxy resin, when after utilizing heavy metal dyeing cured article, observing, in the matrix of forming by resin, do not observe phase separation structure with transmission electron microscope.

The curable resin composition of the invention of being put down in writing in the technical scheme 2 is characterised in that, in the curable resin composition of in technique scheme 1, being put down in writing, the crest of tan δ is single in the visco-elasticity spectral measurement of cured article, and the temperature of above-mentioned crest is more than 120 ℃.

The curable resin composition of the invention of being put down in writing in the technical scheme 3 is characterised in that, in the curable resin composition of being put down in writing in technique scheme 1 or 2, the swelling capacity of the cured article of measuring in being heated to 120 ℃ dimethyl sulphoxide solution is in 50%.

The curable resin composition of the invention of being put down in writing in the technical scheme 4 is characterised in that, in the curable resin composition of being put down in writing in technique scheme 1,2 or 3, the pH that goes out the extraction water that is stripped to timesharing of cured article with 110 ℃ water hot extractions (does not contain 8.5) more than 5.0, below 8.5.

The curable resin composition of the invention of being put down in writing in the technical scheme 5 is characterised in that, in the curable resin composition of being put down in writing in technique scheme 1,2,3 or 4, the extraction electrical conductivity of water that is stripped to timesharing that goes out cured article with 110 ℃ water hot extractions is below the 100 μ S/cm.

The curable resin composition of the invention of being put down in writing in the technical scheme 6 is characterised in that in the curable resin composition of being put down in writing, the specific inductivity of cured article is below 3.5 in technique scheme 1,2,3,4 or 5, dielectric dissipation factor is below 0.02.

The curable resin composition of the invention of being put down in writing in the technical scheme 7 is characterised in that, in the curable resin composition of in technique scheme 1,2,3,4,5 or 6, being put down in writing, Resins, epoxy is the Resins, epoxy that has the polynuclear hydrocarbon skeleton on the main chain, and have to be the high molecular polymer with epoxy group(ing) with the solid polymer of the functional group of epoxy reaction, and, do not contain mineral filler.

The curable resin composition of the invention of being put down in writing in the technical scheme 8 is characterised in that, in the curable resin composition of being put down in writing in technique scheme 7, the Resins, epoxy that has the polynuclear hydrocarbon skeleton on the main chain is the Resins, epoxy that has the Resins, epoxy of Dicyclopentadiene (DCPD) skeleton or have the naphthalene skeleton.

The curable resin composition of the invention of being put down in writing in the technical scheme 9 is characterised in that in the curable resin composition of being put down in writing, the weight-average molecular weight with high molecular polymer of epoxy group(ing) is more than 10,000 in technique scheme 7 or 8.

The curable resin composition of the invention of being put down in writing in the technical scheme 10 is characterised in that in the curable resin composition of being put down in writing, the epoxy equivalent (weight) with high molecular polymer of epoxy group(ing) is 200-1000 in technique scheme 7,8 or 9.

The curable resin composition of the invention of being put down in writing in the technical scheme 11 is characterised in that in the curable resin composition of being put down in writing, to have the high molecular polymer suspension polymerization manufactured of epoxy group(ing) in technique scheme 7,8,9 or 10.

The curable resin composition of the invention of being put down in writing in the technical scheme 12 is characterised in that, in the curable resin composition of being put down in writing in technique scheme 1,2,3,4,5,6,7,8,9,10 or 11, also containing spring rate under 20 ℃ (G ') is 1 * 10 ⁵～1 * 10 ⁸The low elasticity rate material of Pa, and this material is with respect to Resins, epoxy with have can be with the solid polymer of the functional group of epoxy reaction immiscible and be separated into island.

The curable resin composition of the invention of being put down in writing in the technical scheme 13 (below be recited as " the 2nd the present invention ") is characterised in that, contain: mixing the second-order transition temperature with composition epoxy resin that the Resins, epoxy of Dicyclopentadiene (DCPD) skeleton, the Resins, epoxy with naphthalene skeleton and hardener for epoxy resin form and core is below 20 ℃ and the second-order transition temperature of shell portion is the rubber particles of core shell (core shell) structure more than 40 ℃.

The adhesive epoxy resin cream of the invention of being put down in writing in the technical scheme 14 (below be recited as " the 3rd the present invention ") is characterised in that, is made up of the curable resin composition of being put down in writing in technique scheme 1,2,3,4,5,6,7,8,9,10,11,12 or 13.

The interlayer caking agent of the invention of being put down in writing in the technical scheme 15 (below be recited as " the 4th the present invention ") is characterised in that, is made up of the adhesive epoxy resin cream of being put down in writing in the technique scheme 14.

The nonconductive paste of the invention of being put down in writing in the technical scheme 16 (below be recited as " the 5th the present invention ") is characterised in that, is made up of the adhesive epoxy resin cream of being put down in writing in the technique scheme 14.

The invention of being put down in writing in the technical scheme 17 (below be recited as " the 6th the present invention ") fill out thanks to that filler (underfill) is characterised in that, form by the adhesive epoxy resin cream of being put down in writing in the technique scheme 14.

The adhesive epoxy resin thin slice of the invention of being put down in writing in the technical scheme 18 (below be recited as " the 7th the present invention ") is characterised in that, is configured as laminar forming by the curable resin composition that will be put down in writing in technique scheme 1,2,3,4,5,6,7,8,9,10,11,12 or 13.

The adhesive epoxy resin thin slice of the invention of being put down in writing in the technical scheme 19 is characterised in that, in the adhesive epoxy resin thin slice that aforesaid right requires in the 18th to be put down in writing, and the storage spring rate of the thing that is heating and curing that is heating and curing by heating up with 45 ℃/minute heat-up rate (G ') surpass 1 * 10 ³Pa.

The adhesive epoxy resin thin slice of the invention of being put down in writing in the technical scheme 20 is characterised in that, in the adhesive epoxy resin thin slice of in technique scheme the 18th or 19, being put down in writing, crest temperature based on the tan δ of dynamic viscoelastic is-20 ℃～40 ℃ before curing, is more than 120 ℃ after the curing.

The non-conductive film of the invention of being put down in writing in the technical scheme 21 (below be recited as " the 8th the present invention ") is characterised in that, is made of the adhesive epoxy resin thin slice of being put down in writing in technique scheme 18,19 or 20.

The die attachment film of the invention of being put down in writing in the technical scheme 22 (below be recited as " the 9th the present invention ") is characterised in that, is made of the adhesive epoxy resin thin slice of being put down in writing in technique scheme 18,19 or 20.

The conduction of the invention of being put down in writing in the technical scheme 23 (below be recited as " the 10th the present invention ") connects cream and is characterised in that, forms by making the adhesive epoxy resin cream of being put down in writing in the technique scheme 14 contain electrically conductive microparticle.

The anisotropic conductive cream of the invention of being put down in writing in the technical scheme 24 (below be recited as " the 11st the present invention ") is characterised in that, connects cream by the conduction of being put down in writing in the technique scheme 23 and forms.

The conductive connection sheet of the invention of being put down in writing in the technical scheme 25 (below be recited as " the 12nd the present invention ") is characterised in that, the conductive connection sheet of forming by adhesive epoxy resin thin slice of being put down in writing in technique scheme 18,19 or 20 and electrically conductive microparticle, and at least a portion of above-mentioned electrically conductive microparticle is exposed from above-mentioned adhesive epoxy resin thin slice.

The conductive connection sheet of the invention of being put down in writing in the technical scheme 26 (below be recited as " the 13rd the present invention ") is characterised in that the electrically conductive microparticle of burying underground less than above-mentioned adhesive epoxy resin sheet thickness in the adhesive epoxy resin thin slice of being put down in writing forms in technique scheme 18,19 or 20.

The anisotropic conducting film of the invention of being put down in writing in the technical scheme 27 (below be recited as " the 14th the present invention ") is characterised in that, is made of the conductive connection sheet of being put down in writing in the technical scheme 26.

The conductive connection sheet of the invention of being put down in writing in the technical scheme 28 (below be recited as " the 15th the present invention ") is characterised in that, it is the conductive connection sheet that forms by resin of binding property thin slice and electrically conductive microparticle, described resin of binding property thin slice is by containing by adding that softening agent has been given fusible resin and being that the adhesive resin composition of the aqueous Resins, epoxy with naphthalene skeleton constitutes at normal temperatures, the crest temperature based on the tan δ of dynamic viscoelastic of above-mentioned resin of binding property thin slice is-20 ℃～40 ℃ scope before curing, be more than 120 ℃ after the curing, simultaneously dispose above-mentioned electrically conductive microparticle on the optional position of above-mentioned resin of binding property thin slice, at least a portion of above-mentioned electrically conductive microparticle is exposed from above-mentioned resin of binding property thin slice.

Non-conductive of the invention of being put down in writing in the technical scheme 29 is characterised in that, in the conductive connection sheet of in technique scheme 28, being put down in writing, be below 5% for the unit elongation of the resin of binding property thin slice after the curing of the resin of binding property thin slice after solidifying after carrying out the pressure kettle test under 120 ℃ of temperature, humidity 85%RH, the condition of 12 hours time.

The flip-chip band (flip chip tape) of the invention of being put down in writing in the technical scheme 30 (below be recited as " the 16th the present invention ") is characterised in that, is made of the conductive connection sheet of being put down in writing in technique scheme 25,28 or 29.

The electronic component joined body of the invention of being put down in writing in the technical scheme 31 (below be recited as " the 17th the present invention ") is characterised in that, utilize technique scheme 1,2,3,4,5,6,7,8,9,10,11, the curable resin composition of being put down in writing in 12 or 13, the adhesive epoxy resin cream of being put down in writing in the technical scheme 14, the nonconductive paste of being put down in writing in the technical scheme 16, filler is lost in filling out of being put down in writing in the technical scheme 17, the conduction of being put down in writing in the technical scheme 23 connects cream, the anisotropic conductive cream of being put down in writing in the technical scheme 24, technical scheme 18, the adhesive epoxy resin thin slice of being put down in writing in 19 or 20, the non-conductive film who is put down in writing in the technical scheme 21, the die attachment film of being put down in writing in the technical scheme 22, technical scheme 25,26, the conductive connection sheet of being put down in writing in 28 or 29, the anisotropic conducting film of being put down in writing in the technical scheme 27, perhaps any in the flip-chip band of being put down in writing in the technical scheme 30 engages the projected electrode of electron device projection (bump) shape and other electrode state with conducting and form.

The electronic component joined body of the invention of being put down in writing in the technical scheme 32 (below be recited as " the 18th the present invention ") is characterised in that, utilize technique scheme 1,2,3,4,5,6,7,8,9,10,11, the curable resin composition of being put down in writing in 12 or 13, the adhesive epoxy resin cream of being put down in writing in the technical scheme 14, the nonconductive paste of being put down in writing in the technical scheme 16, filler is lost in filling out of being put down in writing in the technical scheme 17, the conduction of being put down in writing in the technical scheme 23 connects cream, the anisotropic conductive cream of being put down in writing in the technical scheme 24, technical scheme 18, the adhesive epoxy resin thin slice of being put down in writing in 19 or 20, the non-conductive film who is put down in writing in the technical scheme 21, the die attachment film of being put down in writing in the technical scheme 22, technical scheme 25,26, the conductive connection sheet of being put down in writing in 28 or 29, the anisotropic conducting film of being put down in writing in the technical scheme 27, perhaps any in the flip-chip band of being put down in writing in the technical scheme 30 engages and is selected from die-attach area, ceramic substrate, resin substrate, silicon substrate, at least a circuit substrate of compound semiconductor substrate and glass substrate and forming.

The electronic component joined body of the invention of being put down in writing in the technical scheme 33 is characterised in that in the electronic component joined body of being put down in writing, resin substrate is glass epoxy substrate, Bismaleimide Triazine substrate or polyimide substrate in technique scheme 32.

Embodiment

Specify the present invention below.

The 1st curable resin composition of the present invention be contain have can with the solid polymer of the functional group of epoxy reaction and the curable resin composition of hardener for epoxy resin, when cured article is observed with transmission electron microscope with heavy metal dyeing back, in the matrix of forming by resin, do not observe phase separation structure.

When the 1st curable resin composition dyeing of the present invention back being observed with transmission electron microscope, in the resin matrix of cured article, do not observe phase separation structure with heavy metal.The inside of using transmission electron microscope (Transmission Electron Microscope:TEM) can observe macromolecular material is well-known, after with heavy metals such as perosmic anhydride, ruthenium tetroxide, phospho-wolframic acids macromolecular material being dyed in the method, judge the difference of forming in the resin material by the painted depth.

In addition, in this manual, so-called " cured article " is meant curable resin composition of the present invention heating and make it solidify the material that the back obtains under for example 170 ℃, 30 minutes etc. condition.

Usually, the purpose of adding component of polymer in Resins, epoxy is to give the various performances of resin combination that obtain etc., for example when above-mentioned resin combination is formed lamellar material, above-mentioned component of polymer adds as film forming component, for example when above-mentioned resin combination was formed the paste material, the purpose of adding above-mentioned component of polymer was to improve cured resin intensity and give hyperergy etc.But,,, then immiscible if the intermiscibility of Resins, epoxy after solidifying and the component of polymer that is added is not very approaching with regard to Resins, epoxy with regard to the component of polymer that adds in this Resins, epoxy.

Resin combination with the phase separation structure that forms by interpolation component of polymer in Resins, epoxy, have by the effects such as stress relaxation that component of polymer produced of adding, but being not that component of polymer itself dissolves in the Resins, epoxy self as matrix, is limited so improve the intensity of the cured article of resin combination.

The cured article of the 1st curable resin composition of the present invention does not observe phase separation structure in resin matrix when observing this cured article with above-mentioned transmission electron microscope.That is, can think that resinous principle mixes fully in the 1st curable resin composition of the present invention.

If will make Resins, epoxy and the resin that adds mixes fully in this Resins, epoxy, then the above-mentioned polymkeric substance of Tian Jiaing must have epoxy group(ing) in its structure, perhaps in its structure, have can with the functional group of epoxy reaction.

That is, the 1st curable resin composition of the present invention be contain Resins, epoxy and have can with the composition of the solid polymer of the functional group of epoxy reaction.

Be not particularly limited as above-mentioned Resins, epoxy, be preferably the Resins, epoxy that has the polynuclear hydrocarbon skeleton on the main chain.This is because if contain the Resins, epoxy that main chain has the polynuclear hydrocarbon skeleton, then this cured article can become the material that the strong molecular motion of rigidity is obstructed, can show good physical strength and thermotolerance, the while descends owing to water-absorbent and can show good wet fastness.

As the above-mentioned Resins, epoxy that on main chain, has the polynuclear hydrocarbon skeleton, have no particular limits, can enumerate for example Dicyclopentadiene (DCPD) dioxide, phenol phenolic resin varnish with Dicyclopentadiene (DCPD) skeleton etc. has the Resins, epoxy (below be designated as " dicyclopentadiene-type epoxy resin ") of Dicyclopentadiene (DCPD) skeleton, 1-glycidyl naphthalene, 2-glycidyl naphthalene, 1,2-diglycidyl naphthalene, 1,5-diglycidyl naphthalene, 1,6-diglycidyl naphthalene, 1,7-diglycidyl naphthalene, 2,7-diglycidyl naphthalene, the triglycidyl group naphthalene, 1,2,5,6-four glycidyl group naphthalene etc. has the Resins, epoxy (below be designated as " naphthalene type Resins, epoxy ") of naphthalene skeleton, tetrahydroxy phenyl ethane type Resins, epoxy, four (glycidyl oxygen base phenyl) ethane, 3,4-epoxy-6-methyl cyclohexane ylmethyl-3,4-epoxy-6-methylcyclohexane carbonic ether etc., wherein, preferably use dicyclopentadiene-type epoxy resin or naphthalene type Resins, epoxy.These can use separately at the Resins, epoxy that main chain has the polynuclear hydrocarbon skeleton, also can more than two kinds and use.In addition, above-mentioned dicyclopentadiene-type epoxy resin and naphthalene type Resins, epoxy can be distinguished use separately, also can both and usefulness.

The above-mentioned Resins, epoxy that has the polynuclear hydrocarbon skeleton on main chain has no particular limits, but the preferred lower limit of molecular weight is 500, and preferred upper limit is 1000.If have the molecular weight less than 500 of the Resins, epoxy of polynuclear hydrocarbon skeleton on the main chain, then can not substantially improve physical strength, thermotolerance, wet fastness of the cured article of curable resin composition etc. sometimes, surpass 1000 if having the molecular weight of the Resins, epoxy of polynuclear hydrocarbon skeleton on the opposite main chain, then the rigidity of the cured article of curable resin composition can become strong sometimes, becomes fragile easily.

Have and to have no particular limits with the solid polymer of the functional group of epoxy reaction as above-mentioned, can enumerate the resin that for example has amino, urethane groups, imido grpup, hydroxyl, carboxyl, epoxy group(ing), wherein, also preferably have the high molecular polymer of epoxy group(ing).This is because if contain the high molecular polymer with epoxy group(ing), and then its cured article can show good flexible.Promptly, the cured article of the 1st curable resin composition of the present invention has the good physical strength that comes from the Resins, epoxy that has the polynuclear hydrocarbon skeleton in the above-mentioned main chain, good thermotolerance, good wet fastness etc. simultaneously and comes from the good flexible of above-mentioned high molecular polymer with epoxy group(ing), so formed good materials such as cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability, can show high bonding reliability and high conducting reliability.

As above-mentioned high molecular polymer with epoxy group(ing), so long as endways and/or the high molecular polymer of side chain (pendant position) with epoxy group(ing), just have no particular limits, can enumerate the acrylic rubber that for example contains epoxy group(ing), the divinyl rubber that contains epoxy group(ing), the bisphenol type high molecular expoxy resin, the phenoxy resin that contains epoxy group(ing), the acrylic resin that contains epoxy group(ing), the urethane resin that contains epoxy group(ing), contain the vibrin of epoxy group(ing) etc., wherein, from the physical strength and the stable on heating viewpoint of the cured article that can obtain to contain the high molecular polymer of a large amount of epoxy group(ing) and further improve the 1st curable resin composition of the present invention, the preferred acrylic resin that contains epoxy group(ing) that uses.These high molecular polymers with epoxy group(ing) can use separately, also can more than two kinds and use.

If only use above-mentioned bisphenol type high molecular expoxy resin, then can only contain epoxy group(ing) endways, distance becomes very long between cross-linking set, so the physical strength of the cured article of curable resin composition and thermotolerance can not get substantially improving.

In addition, usually acrylic resin (acrylic acid polymer) often adopts the solution polymerization manufactured of solvent as medium, but when adopting solution polymerization process to generate the high-molecular weight acrylic resin, because the viscosity of solution extremely rises, perhaps sometimes gelation might take place, so be difficult to obtain the high-molecular weight acrylic resin.In addition, in solution polymerization process, the monomer of easy remained unreacted, so residual monomer need be removed with solvent, this can make manufacturing process become complicated.

For example, if use glycidyl methacrylate (GMA) as acrylic monomer with epoxy group(ing), and in other acrylic monomer, add a large amount of GMA and carry out solution polymerization, then because the cohesive force of epoxy group(ing) self, can only obtain the acrylic resin that contains epoxy group(ing) of molecular weight ratio lower (being lower than 10000), if will obtain the acrylic resin that high-molecular weight more contains epoxy group(ing), then cause the extreme rising and the gelation of aforesaid viscosity easily.

On the other hand,, adopt with water or non-solvent and contain the acrylic resin of epoxy group(ing), then can obtain to contain a large amount of epoxy group(ing) and the high acrylic resin that contains epoxy group(ing) of molecular weight as the suspension polymerization manufactured of medium if use above-mentioned GMA.This acrylic resin that contains epoxy group(ing) is the clean resin that does not almost have residual monomer, and is also easy from the lock out operation of polymerization system simultaneously, so manufacturing process is simple.

That is, the high molecular polymer that in the 1st curable resin composition of the present invention, uses, preferably contain the acrylic resin of epoxy group(ing), preferably use the high molecular polymer of suspension polymerization manufactured with epoxy group(ing).By using the acrylic resin that with the high molecular polymer with epoxy group(ing) of suspension polymerization manufactured, preferably contains epoxy group(ing), the cured article of the 1st curable resin composition of the present invention can show better mechanical strength and thermotolerance.

Above-mentionedly have the high molecular polymer of epoxy group(ing), preferably contain the weight-average molecular weight of acrylic resin of epoxy group(ing) preferably more than 10,000.If have the high molecular polymer of epoxy group(ing), preferably contain the weight-average molecular weight less than 10,000 of the acrylic resin of epoxy group(ing), then the film of making of curable resin composition becomes not enough sometimes, and flexible can not get of the cured article of curable resin composition substantially improves.

In addition, above-mentionedly have the high molecular polymer of epoxy group(ing), preferably contain the acrylic resin of epoxy group(ing), its epoxy equivalent (weight) is preferably down and is limited to 200, on be limited to 1000.If have the high molecular polymer of epoxy group(ing), preferably contain the epoxy equivalent (weight) less than 200 of the acrylic resin of epoxy group(ing), then flexible can not get of the cured article of curable resin composition substantially improves sometimes, if the epoxy equivalent (weight) that have the high molecular polymer of epoxy group(ing) on the contrary, preferably contains the acrylic resin of epoxy group(ing) surpasses 1000, then the physical strength of the cured article of curable resin composition or thermotolerance can become abundant inadequately sometimes.

It is composition more than 120 ℃ that the 1st curable resin composition of the present invention is preferably the single and temperature above-mentioned crest of the crest of the tan δ in the visco-elasticity spectral measurement of above-mentioned cured article.

As mentioned above, whether the resin matrix of the resin combination that the interpolation component of polymer forms in Resins, epoxy takes phase separation structure, can confirm by the observation of using transmission electron microscope (TEM), but whether above-mentioned resin matrix reaches phase-separated state, also can learn simply by the visco-elasticity spectrum of measuring cured article.

That is, when the resin matrix of cured article had phase separation structure, this viscoelastic tan δ can not illustrate single crest, for example, two crests can be shown when phase structure is 2 layers, and three crests can be shown when phase structure is 3 layers.

In this manual, so-called " crest of tan δ " is meant and compares the crest that protrudes especially with other parts.

In addition, if 120 ℃ of the crest temperature less thaies of above-mentioned tan δ, can cause that then resin is softening before and after the temperature province of using in reliability test in the past (120 ℃), the result becomes the reason of the interface peel when causing the seeing through of moisture, thermal cycling test sometimes.

The cured article of the 1st curable resin composition of the present invention leaves nothing to be desired in being heated to 120 ℃ dimethyl sulfoxide (DMSO) (DMSO) solution and crosses swelling.Specifically, the swelling capacity measured in being heated to 120 ℃ dimethyl sulfoxide (DMSO) (DMSO) solution of above-mentioned cured article is preferably in 50%.If swelling capacity surpasses 50%, then mean crosslinked loosening under this temperature, water molecules and oxygen molecule are highly susceptible to seeing through.Therefore, if swelling capacity surpasses 50%, then the 1st curable resin composition of the present invention can descend as the reliability of caking agent etc. sometimes.

As mentioned above, the 1st curable resin composition of the present invention is not owing to have phase separation structure in the resin matrix of its cured article, so the swelling capacity of measuring in being heated to 120 ℃ dimethyl sulfoxide (DMSO) (DMSO) solution is in 50%.For example, under the situation of the resin combination of forming by Resins, epoxy with the component of polymer that this Resins, epoxy is separated, the phase structure of this cured article is made of epoxy cross-linking phase (Resins, epoxy phase) and polymer phase.Yet, though the second-order transition temperature of above-mentioned epoxy cross-linking phase (Tg) reaches easily more than 120 ℃ and not and can cause swelling, its amount can be not too many yet even but above-mentioned polymer phase has crosslinking group in its structure, crosslinking structure with comparison pine can present bigger swelling when therefore observing swelling capacity near 120 ℃.

In the 1st curable resin composition of the present invention, above-mentioned Resins, epoxy is the above-mentioned Resins, epoxy that has the polynuclear hydrocarbon skeleton in main chain, it is above-mentioned that to have to be above-mentioned high molecular polymer with epoxy group(ing) with the solid polymer of the functional group of epoxy reaction, and, preferably do not contain mineral filler.

Usually, if will improve the reliability of electronic material, just must add a large amount of mineral fillers with caking agent etc.As everyone knows, add these mineral fillers and can improve absorptivity, spring rate, and can improve moisture resistance properties etc., but in interelectrode crimping engages, sometimes inorganic filler particle can enter between the electrode, in the time of particularly between the narrow electrode in bonding interval, the existence of above-mentioned mineral filler sometimes can cause bonding bad.

In addition, can enumerate spherical silicon dioxide, but this spherical silicon dioxide is the filler with size distribution basically, exists as probability to have the very possibility of the particle of bulk as the above-mentioned mineral filler of preferred use.Especially when adding a large amount of mineral fillers (spherical silicon dioxide), the probability that contains the unusual particle of bulk is very high, is easy to produce aforesaid bad phenomenon.

In view of such circumstances, in the 1st curable resin composition of the present invention, preferably do not contain mineral filler.

In addition, for example, if size distribution in good order and the very little mineral filler of maximum particle diameter, then can produce aforesaid bad phenomenon hardly.Therefore, if such mineral filler then also can be added in the 1st curable resin composition of the present invention.Specifically, the maximum particle diameter of preferred mineral filler is below the 3 μ m, and the addition when the resin total amount is counted 100 weight parts is below 30 weight parts.

If contain the mineral filler that maximum particle diameter surpasses 3 μ m, then be easy to produce aforesaid bad phenomenon, when on needing the substrate of through hole, using the 1st curable resin composition of the present invention simultaneously, the circularity of the communicating pores during laser processing descends, and loses the smoothness of through hole finished surface sometimes because of the existence of above-mentioned mineral filler.

As maximum particle diameter is that the mineral filler that does not contain the bulk particle below the 3 μ m has no particular limits, can enumerate for example silicon-dioxide such as pyrogenic silica, colloidal silica, glass fibre, alumina particulate etc., wherein, the preferred silicon-dioxide that uses, the hydrophobic silica that hydrophobization is handled has been carried out on the especially preferred surface of using.These mineral fillers can be used separately, also can more than two kinds and use.In addition, in the 1st curable resin composition of the present invention, as long as maximum particle diameter below 3 μ m, can also contain the organic filler of being made up of low-molecular-weight microgranular organism.

When to contain above-mentioned maximum particle diameter in the 1st curable resin composition of the present invention be mineral filler below the 3 μ m, if its content surpasses 30 weight parts with respect to above-mentioned Resins, epoxy and above-mentioned total amount 100 weight parts with high molecular polymer of epoxy group(ing) that contain the polynuclear hydrocarbon skeleton in main chain, then have when using the 1st curable resin composition of the present invention on the substrate of through hole at needs, the circularity of the communicating pores during laser processing can descend, lose the smoothness of through hole finished surface sometimes because of the existence of above-mentioned mineral filler, perhaps the concentration of curable resin composition can become too high, thereby influences coating.

In the 1st curable resin composition of the present invention, and the spring rate under preferred 20 ℃ (G ') be 1 * 10 ⁵～1 * 10 ⁸The low elasticity rate material of Pa is separated into island with immiscible form.

By make spring rate under 20 ℃ (G ') in curable resin composition is 1 * 10 ⁵～1 * 10 ⁸The low elasticity rate material of Pa is separated into island with immiscible form, can make the cured article of the 1st curable resin composition of the present invention form sea-island structure, thereby have better mechanical strength or thermotolerance and better flexible concurrently, that is, become the cured article that can show better toughness.

The spring rate of above-mentioned low elasticity rate material under 20 ℃ (G ') if less than 1 * 10 ⁵Pa, then the physical strength of the cured article of curable resin composition or thermotolerance can not get substantially improving sometimes, the spring rate of opposite above-mentioned low elasticity rate material under 20 ℃ (G ') if surpass 1 * 10 ⁸Pa then can not substantially improve cured article flexible of curable resin composition sometimes.In addition,, then in the cured article of curable resin composition, can not form sea-island structure, so can not obtain above-mentioned effect fully sometimes if above-mentioned low elasticity rate material mixes with curable resin composition.

As above-mentioned low elasticity rate material, the following of (G ') is limited to 1 * 10 so long as the spring rate under 20 ℃ ⁵, on be limited to 1 * 10 ⁸Pa and just can use with the immiscible material of curable resin composition has no particular limits, and can enumerate for example various thermoplastic resins, various heat-curing resin, various rubber (various elastomerics) etc.These low elasticity rate materials can use separately, also can more than two kinds and use.

It is below 20 ℃ that the 2nd curable resin composition of the present invention contains the second-order transition temperature that mixes composition epoxy resin that dicyclopentadiene-type epoxy resin, naphthalene type Resins, epoxy and hardener for epoxy resin form and core and the second-order transition temperature of shell portion is the rubber particles of the core shell structure more than 40 ℃.

The Resins, epoxy that the dicyclopentadiene-type epoxy resin that contains in the above-mentioned composition epoxy resin is made up of the Dicyclopentadiene (DCPD) skeleton with epoxy group(ing), this dicyclopentadiene-type epoxy resin is rich in hydrophobicity, so contain dicyclopentadiene-type epoxy resin by making in the above-mentioned composition epoxy resin, can make the 2nd curable resin composition hydrophobization of the present invention, even it is lower and also can show high hydrophobic cured article under the hot and humid environment that with the pressure kettle test is representative to form water-intake rate.

Above-mentioned dicyclopentadiene-type epoxy resin preferably has the lower polymerization degree and/or softening temperature.By using such dicyclopentadiene-type epoxy resin, when with the 2nd curable resin composition of the present invention during as adhesive epoxy resin cream for example, can improve the flowability of cream, in addition, when with the 2nd curable resin composition of the present invention during as adhesive epoxy resin thin slice for example, can give the suitable flexibility of thin slice before solidifying, thereby make it to be difficult for breaking.

Have no particular limits as above-mentioned dicyclopentadiene-type epoxy resin, for example can enumerate the Dicyclopentadiene (DCPD) dioxide or have phenol phenolic resin varnish of Dicyclopentadiene (DCPD) skeleton etc.These dicyclopentadiene-type epoxy resin can be used separately, also can more than two kinds and use.

The Resins, epoxy that the naphthalene type Resins, epoxy that contains in above-mentioned composition epoxy resin is made up of the naphthalene skeleton with epoxy group(ing), in the 2nd the present invention, the preferred use is aqueous naphthalene type Resins, epoxy at normal temperatures.Naphthalene type Resins, epoxy has inflexible naphthalene skeleton, so when with the 2nd curable resin composition of the present invention during as adhesive epoxy resin thin slice for example, even the thin slice after the curing also can obtain high shape-holding property down hot and humid, can show high moisture-proof cementability.

When with the 2nd curable resin composition of the present invention during as adhesive epoxy resin cream for example, the viscosity of above-mentioned naphthalene type Resins, epoxy is preferably lower.In addition, with the 2nd curable resin composition of the present invention during as adhesive epoxy resin thin slice for example, because above-mentioned naphthalene type Resins, epoxy contains isomer, fusing point is usually below normal temperature, so also can improve the flexibility of thin slice at normal temperatures, can make the thin slice before solidifying be difficult for breaking, also can improve curing speed simultaneously.

Be aqueous naphthalene type Resins, epoxy down as above-mentioned normal temperature, have no particular limits, can enumerate for example 1-glycidyl naphthalene, 2-glycidyl naphthalene, 1,2-diglycidyl naphthalene, 1,5-diglycidyl naphthalene, 1,6-diglycidyl naphthalene, 1,7-diglycidyl naphthalene, 2,7-diglycidyl naphthalene, triglycidyl group naphthalene, 1,2,5,6-four glycidyl group naphthalene etc.These naphthalene type Resins, epoxy can use separately, also can more than two kinds and use.

The quantity of the epoxy group(ing) that is contained in above-mentioned dicyclopentadiene-type epoxy resin and naphthalene type Resins, epoxy has no particular limits, and preferably each molecule on average contains more than one, and more preferably each molecule on average contains more than two.Wherein, the quantity of the epoxy group(ing) in each molecule method that can remove the sum of the sum of the epoxy group(ing) in the dicyclopentadiene-type epoxy resin or the epoxy group(ing) in the naphthalene type Resins, epoxy with the molecule sum of the molecule sum of dicyclopentadiene-type epoxy resin or naphthalene type Resins, epoxy is obtained.

In above-mentioned composition epoxy resin, also can contain the Resins, epoxy beyond dicyclopentadiene-type epoxy resin and the naphthalene type Resins, epoxy as required or contain the compound of epoxy group(ing).

The the 1st and the 2nd curable resin composition of the present invention contains the epoxy group(ing) that acts in the Resins, epoxy that has the polynuclear hydrocarbon skeleton in the above-mentioned main chain, epoxy group(ing) in the above-mentioned high molecular polymer with epoxy group(ing), epoxy group(ing) in epoxy group(ing) in the dicyclopentadiene-type epoxy resin that contains in the above-mentioned composition epoxy resin or the naphthalene type Resins, epoxy and make the Resins, epoxy that in main chain, has the polynuclear hydrocarbon skeleton, high molecular polymer with epoxy group(ing), the hardener for epoxy resin of dicyclopentadiene-type epoxy resin or naphthalene type epoxy resin cure (following also abbreviate as sometimes " solidifying agent ").

Because the composition epoxy resin in the 1st curable resin composition of the present invention and the 2nd curable resin composition of the present invention contains above-mentioned hardener for epoxy resin, so have the Resins, epoxy of polynuclear hydrocarbon skeleton in the main chain, high molecular polymer with epoxy group(ing), dicyclopentadiene-type epoxy resin or naphthalene type Resins, epoxy can indurate under heating and promptly solidify, and then the cured article of the 1st and the 2nd curable resin composition of the present invention can possess good physical strength, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., and show high bonding reliability or the high conducting reliability during as conductive material.

As above-mentioned hardener for epoxy resin, have no particular limits, for example can enumerating, heat-curing type acid anhydrides such as trialkyl tetrahydrochysene anhydride phthalic acid is that solidifying agent, phenol are that solidifying agent, amine are potentiality solidifying agent such as solidifying agent, Dyhard RU 100, positively charged ion series catalysts type solidifying agent etc.These hardener for epoxy resin can use separately, also can more than two kinds and use.

Among the above-mentioned hardener for epoxy resin, the preferred use is aqueous heat-curing type solidifying agent or the potentiality solidifying agent such as Dyhard RU 100 that have a plurality of functional groups and can play a role with less equivalent addition at normal temperatures.By using such solidifying agent, when using the 1st and the 2nd curable resin composition of the present invention for example to make the adhesive epoxy resin thin slice, softness and the good thin slice of operability at normal temperatures before can obtaining to solidify.In contrast, be that solid and the more phenol of equivalent addition are solidifying agent because the second-order transition temperature (Tg) before the curing of thin slice self rises quite a lot ofly at normal temperatures, be easy to the thin slice of the operability difference that the initial stage that becomes cracks, so not ideal.

As above-mentioned be the representative substances of aqueous heat-curing type solidifying agent at normal temperatures, for example can enumerating, acid anhydrides such as methyl tetrahydrochysene anhydride phthalic acid, methyl six hydrogen anhydride phthalic acids, the naked acid anhydrides of methyl, trialkyl tetrahydrochysene anhydride phthalic acid are solidifying agent, wherein, from the viewpoint of hydrophobization, preferably use naked acid anhydrides of methyl or trialkyl tetrahydrochysene anhydride phthalic acid.Relative therewith, methyl tetrahydrochysene anhydride phthalic acid and methyl six hydrogen anhydride phthalic acids are owing to poor water resistance, so not ideal.These acid anhydrides are that solidifying agent can use separately, also can more than two kinds and use.

In the 1st and the 2nd curable resin composition of the present invention,, also can be used in combination curing catalyst with above-mentioned hardener for epoxy resin for rerum natura of adjusting curing speed or cured article etc.

As above-mentioned curing catalyst, have no particular limits, for example can enumerate that imidazoles is that curing catalyst, tertiary amine are curing catalyst etc., wherein, from being easy to control the viewpoint of the reaction system that is used to adjust curing speed or cured article rerum natura etc., preferably using imidazoles is curing catalyst.These curing catalysts can use separately, also can more than two kinds and use.

As above-mentioned imidazoles is curing catalyst; have no particular limits, for example can enumerate with cyanoethyl protected imidazoles 1 1-cyanoethyl-2-phenylimidazole, protected alkaline commodity to be called product of " 2MA-OK " (four countries change into industrial society system) etc. with tricarbimide.These imidazoles are that curing catalyst can use separately, also can more than two kinds and use.

When being used in combination acid anhydrides is solidifying agent and for example imidazoles when being curing catalysts such as curing catalyst, preferably is that the addition of solidifying agent is located at below the theoretic required equivalent with respect to epoxy group(ing) with acid anhydrides.If it is excessive to aequum that acid anhydrides is the addition of solidifying agent, might be easy to then that elution goes out chlorion from the cured article of the 1st and the 2nd curable resin composition of the present invention because of the existence of moisture.For example, extract from the cured article of the 1st and the 2nd curable resin composition of the present invention with hot water and to be stripped to timesharing, the pH of extraction water can reduce to about 4-5, washes out the chlorion of being sloughed by Resins, epoxy sometimes in a large number.

In addition, be that solidifying agent and for example imidazoles are under the situation of curing catalyst such as curing catalyst being used in combination amine, amine is that the addition of solidifying agent is with respect to below the also preferred required equivalent in theory of epoxy group(ing).If it is excessive to aequum that amine is the addition of solidifying agent, might be easy to then that elution goes out chlorion from the cured article of the 1st and the 2nd curable resin composition of the present invention because of the existence of moisture.For example, extract from the cured article of the 1st and the 2nd curable resin composition of the present invention with hot water and to be stripped to timesharing, the pH of extraction water can become alkalescence, still can wash out the chlorion of being sloughed by Resins, epoxy in a large number.

The 2nd curable resin composition of the present invention is, the second-order transition temperature that contains core (core) in above-mentioned composition epoxy resin is below 20 ℃ and the second-order transition temperature of shell portion (skin) is that the rubber particles of the core shell structure more than 40 ℃ forms.By making it contain such rubber particles, in the cured article of the 2nd curable resin composition of the present invention, can form the stable phase separation structure of rubber constituent with respect to Resins, epoxy as matrix resin, show soft and good stress relaxation.

It is that core and second-order transition temperature below 20 ℃ is the core shell structure that the shell portion more than 40 ℃ forms that above-mentioned rubber particles has by second-order transition temperature.In addition, above-mentioned rubber particles is so long as the particle of the core shell structure of being made up of the multilayered structure more than two layers gets final product, and when the particle of the core shell structure of being made up of the multilayered structure more than three layers, shell portion means outermost layer.

If the second-order transition temperature of above-mentioned rubber particles core surpasses 20 ℃, then the stress relaxation of the cured article of the 2nd curable resin composition of the present invention can not get substantially improving.In addition, if 40 ℃ of the second-order transition temperature deficiencies of above-mentioned rubber particles shell portion, then rubber particles welding each other (cohesion), perhaps in composition epoxy resin, produce disperse bad.In addition, the choosing of the shell quality award from the ministry of above-mentioned rubber particles is immiscible with Resins, epoxy, perhaps, reaches gelation by insignificant, thereby forms the state that is not dissolved in the Resins, epoxy.

As the resinous principle that constitutes such rubber particles, so long as can obtain that the second-order transition temperature of core is below 20 ℃, the second-order transition temperature of shell portion is the structure more than 40 ℃, any resinous principle all can use, have no particular limits, but from the wide viewpoint of the scope of design of second-order transition temperature, the suitable usually acrylic resin that uses.These resinous principles can use separately, also can more than two kinds and use.

In addition, the shell portion of rubber particles also can have with Resins, epoxy in the functional group of epoxy reaction.As with the functional group of epoxy reaction, have no particular limits, can enumerate for example amino, urethane groups, imido grpup, hydroxyl, carboxyl, epoxy group(ing) etc., wherein, not with epoxy reaction and can not cause the decline of wettability of the 2nd curable resin composition of the present invention and the viewpoint of the decline of storage stability, preferably use hydroxyl or epoxy group(ing) from normal temperatures.The functional group of these and epoxy reaction can use separately, also can more than two kinds and use.

Have no particular limits for above-mentioned rubber particles, but median size is preferably below 30 μ m.If the median size of rubber particles surpasses 30 μ m, then the stress relaxation of the cured article of the 2nd curable resin composition of the present invention can not get substantially improving sometimes.In addition, when with the 2nd curable resin composition of the present invention during as adhesive epoxy resin cream for example, sometimes illiquidity, thereby can influence coating and to the fillibility of gap portion, and, when with the 2nd curable resin composition of the present invention during as adhesive epoxy resin thin slice for example, the difficulty that becomes of the sheet-like formed meeting of film sometimes.

Commercially available product as this rubber particles, have no particular limits, can enumerate " パ ラ Network ロ Application " series of commodity " パ ラ Network ロ Application RP-101 ", " パ ラ Network ロ Application RP-103 " by name, " the パ ラ Network ロ Application RP-412 " etc. of industrial society system on the root for example; ガ Application ッ changes into the commodity " ス Off ィ ロ ィ De IM-101 " by name of society's system, " ス Off ィ ロ ィ De IM-203 ", " ス Off ィ ロ ィ De IM-301 ", " ス Off ィ ロ ィ De IM-401 ", " ス Off ィ ロ ィ De IM-601 ", " ス Off ィ ロ ィ De AC-3355 ", " ス Off ィ ロ ィ De AC-3364 ", " ス Off ィ ロ ィ De AC-3816 ", " ス Off ィ ロ ィ De AC-3832 ", " the ス Off ィ ロ ィ De " series of " ス Off ィ ロ ィ De AC-4030 " etc.; ゼ ォ Application changes into " ゼ ォ Application " series of the commodity by name " ゼ ォ Application F35 1 " of society's system etc.; The commodity of the レ of Mitsubishi one ョ Application society system are called " メ Block レ Application C-140A ", " メ Block レ Application C-201A ", " メ Block レ Application C-215A ", " メ Block レ Application C-223A ", " メ Block レ Application C-303A ", " メ Block レ Application C-323A ", " メ Block レ Application C-102 ", " メ Block レ Application C-132 ", " メ Block レ Application C-202 ", " メ Block レ Application E-901 ", " メ Block レ Application W-341 ", " メ Block レ Application W-300A ", " メ Block レ Application W-450A ", " メ Block レ Application S-2001 ", " メ Block レ Application SX-005 ", " メ Block レ Application SX-006 ", " the メ Block レ Application " series of " メ Block レ Application SRK200 " etc. etc.In addition, commercially available product as the Resins, epoxy that has disperseed rubber particles in advance, have no particular limits, can enumerate " ェ Port セ ッ ト " series etc. of the commodity " ェ Port セ ッ ト BPA-828 " by name, " ェ Port セ ッ ト BPF-807 " etc. of for example Japanese catalyst society system.These rubber particles and disperseed the Resins, epoxy of rubber particles to use separately in advance also can more than two kinds and be used.

In the 2nd curable resin composition of the present invention, also can contain thermoplastic resin or heat-curing resin as required.

As above-mentioned thermoplastic resin, have no particular limits, for example can enumerate vinyl acetate and be polyvinyl acetals such as resin, ethylene-vinyl acetate based copolymer, acrylic resin, polyvinyl butyral resin and be resin, phenylethylene resin series, saturated polyester and be resin, thermal plastic urethane and be resin, polyamide-based resin, thermoplastic polyimide is that resin, ketone are resin, norbornene resin, styrene butadiene based block copolymer etc.These thermoplastic resins can use separately, also can more than two kinds and use.

As above-mentioned heat-curing resin, have no particular limits, for example can enumerating, amino such as urea resin, melamine resin is that resin, phenolic aldehyde are that resin, unsaturated polyester are that resin, Thermocurable urethane are that resin, above-mentioned pentadiene type Resins, epoxy and naphthalene type Resins, epoxy epoxy in addition is that resin, Thermocurable polyimide are that resin, amino-alkyd resin are resin etc.These heat-curing resins can use separately, also can more than two kinds and use.In addition, above-mentioned thermoplastic resin and heat-curing resin can be distinguished use separately, also can the two also use.

When with the 2nd curable resin composition of the present invention during as the adhesive epoxy resin cream of paste for example, above-mentioned thermoplastic resin or heat-curing resin can be brought into play the effect of thickening material.At this moment, as long as the viscosity of cream does not become very high, the weight-average molecular weight of above-mentioned thermoplastic resin or heat-curing resin just is not particularly limited.In addition, also can add the viscosity that solvent is adjusted cream as required.

When with the 2nd curable resin composition of the present invention when on barrier sheet (release sheet or release paper), being configured as laminar adhesive epoxy resin thin slice, in order to ensure good laminar shape, above-mentioned thermoplastic resin or heat-curing resin are preferably the high-molecular weight polymer that has than high glass transition.At this moment, have no particular limits, but weight-average molecular weight is preferably more than 10,000, more preferably more than 100,000 for above-mentioned thermoplastic resin or heat-curing resin.If the weight-average molecular weight less than 10,000 of thermoplastic resin or heat-curing resin, the cohesive force deficiency of thin slice self is sometimes then repelled coating things such as the caking agent that is coated on the thin slice or coating easily, causes easily when peeling off barrier sheet that the cohesion of thin slice self destroys.

Above-mentioned thermoplastic resin or heat-curing resin preferably have can with the functional group of epoxy reaction.By make thermoplastic resin or heat-curing resin have can with the functional group of epoxy reaction, the cured article of the 2nd curable resin composition of the present invention can show better mechanical strength and thermotolerance.

As above-mentioned can with the functional group of epoxy reaction, have no particular limits, can enumerate for example amino, urethane groups, imido grpup, hydroxyl, carboxyl, epoxy group(ing) etc.These can use separately with the functional group of epoxy reaction, also can more than two kinds and use.

When the adhesive epoxy resin cream of the 2nd curable resin composition of the present invention having been adjusted viscosity with the effect solvent, when perhaps using the adhesive epoxy resin thin slice of effect solvent casting method shaping, above-mentioned can with the functional group of epoxy reaction among, also preferred the use in the hydroxyl or the epoxy group(ing) that are used under about 110 ℃ temperature of dry solvent not with epoxy reaction under about 150-230 ℃ temperature with epoxy reaction.Resin as having hydroxyl or epoxy group(ing) has no particular limits, and for example can enumerate polyvinyl butyral resin or contain acrylic resin of epoxy group(ing) etc.

If as using amino or carboxyl with the functional group of epoxy reaction, then when the adhesive epoxy resin cream of the 2nd curable resin composition of the present invention having been adjusted viscosity with the effect solvent, when perhaps using the adhesive epoxy resin thin slice of effect solvent casting method shaping, owing to react with epoxy group(ing) under about 110 ℃ temperature of dry solvent being used for, cream or thin slice can become semi-cured state (B step state) when dry or when being shaped, thereby can influence the coating of cream, perhaps can reduce cream or thin slice with respect to the adhesivity of adherend or moisture-proof cementability etc.

In addition, can have no particular limits with the equivalent of the functional group of epoxy reaction for a kind of thermoplastic resin or heat-curing resin has, but preferred below 10,000, more preferably below 1000.By use have above-mentioned normal can with the thermoplastic resin or the heat-curing resin of the functional group of epoxy reaction, the cured article of the 2nd curable resin composition of the present invention can form high netted of cross-linking density.In addition, above-mentioned what is called can be with the equivalent of the functional group of epoxy reaction be used in exist in a kind of thermoplastic resin or the heat-curing resin can remove the weight-average molecular weight of thermoplastic resin or heat-curing resin with the sum of the functional group of epoxy reaction and the value that obtains.

In the 1st curable resin composition of the present invention, the second-order transition temperature that also can contain the above-mentioned core that contains as required in the 2nd curable resin composition of the present invention is below 20 ℃, the second-order transition temperature of shell portion is the rubber particles of the core shell structure more than 40 ℃, or the above-mentioned thermoplastic resin or the heat-curing resin that can contain in the 2nd curable resin composition of the present invention.

In the 2nd curable resin composition of the present invention, also can contain the above-mentioned high molecular polymer that in the 1st curable resin composition of the present invention, contains as required with epoxy group(ing).In addition, the 2nd curable resin composition of the present invention does not preferably contain the filler that median size surpasses 3 μ m.

In the 1st and the 2nd curable resin composition of the present invention, also can add a kind of in the various additives such as adhesivity activator, pH regulator agent, ion trap agent, viscosity modifier, thixotropy imparting agent, antioxidant, thermo-stabilizer, photostabilizer, UV light absorber, tinting material, dewatering agent, fire retardant, static inhibitor, mould inhibitor, sanitas, solvent for example as required or more than two kinds.

As above-mentioned adhesivity activator, have no particular limits, can enumerate for example silane coupling agent, titanium coupling agent, aluminium coupler etc., wherein, preferably use silane coupling agent.These adhesivity activators can use separately, also can more than two kinds and use.

As above-mentioned silane coupling agent, have no particular limits, can enumerate for example aminosilane coupling agent, epoxy radicals silicone hydride coupler, urea groups silane coupling agent, isocynate silane coupler, vinyl silanes coupler, propenyl silane coupling agent, ketoimine silane coupling agent etc., wherein, from curing speed or and the viewpoint of the affinity of Resins, epoxy, preferably use aminosilane coupling agent.These silane coupling agents can use separately, also can more than two kinds and use.

Addition for above-mentioned adhesivity activator has no particular limits, and preferably with respect to the 1st or the 2nd curable resin composition 100 weight parts of the present invention, the adhesivity activator is below 20 weight parts.If the adhesivity activator surpasses 20 weight parts with respect to the addition of the 1st or the 2nd curable resin composition 100 weight parts of the present invention, then when with curable resin composition during as adhesive epoxy resin thin slice for example, a little less than the intensity of film or cohesive force can become before solidifying sometimes.

As above-mentioned pH regulator agent, have no particular limits, for example can enumerate basic fillers such as acid filler such as silicon-dioxide or lime carbonate etc.These pH regulator agent can be used separately, also can more than two kinds and use.

As above-mentioned ion trap agent, can use so long as can reduce the amount of ionic impurity, have no particular limits, can enumerate aluminium for example for the characteristic good under silicate, oxidizing aqueous titanium, oxidizing aqueous bismuth, zirconium phosphate, titanium phosphate, hydrotalcite, ammonium phosphomolybdate, six zinc cyanides, organic system ion exchange resin etc. or the high temperature as the series of the commodity " IXE " by name of the commercially available synthetic society in the East Asia system of ion trap agent etc.These ion trap agent can be used separately, also can more than two kinds and use.

Addition to above-mentioned ion trap agent has no particular limits, but with respect to the 1st or the 2nd curable resin composition 100 weight parts of the present invention, the content of ion trap agent is preferably below 10 weight parts.If the ion trap agent surpasses 10 weight parts with respect to the addition of the 1st or the 2nd curable resin composition 100 weight parts of the present invention, then the curing speed of curable resin composition can become very slow sometimes.

Manufacture method to the 1st and the 2nd curable resin composition of the present invention has no particular limits, can be by using or also use for example homodisperse device separately, omnipotent mixing tank, Banbury mixer, kneader, 2 roller rolling machines, 3 roller rolling machines, known various mixing rolls such as extrusion machine, required separately composition with each specified amount, a kind of or the various additives that can add more than two kinds of the various compositions that can contain of each specified amount and each specified amount, at normal temperatures or heating down, under normal pressure, decompression down, add depress or condition such as inert gas under uniform mixing, make required curable resin composition.In addition, when hardener for epoxy resin is heat-curing type solidifying agent or potentiality solidifying agent, though also can adopt above-mentioned manufacture method, but when hardener for epoxy resin is the normal temperature cured type solidifying agent, preferably before being about to use curable resin composition or using its finished product, add hardener for epoxy resin.

The pH of the extraction water that is stripped to timesharing of cured article the 1st and the 2nd curable resin composition of the present invention that so obtains, go out curable resin composition with 110 ℃ water hot extractions is preferably more than 5.0, is lower than 8.5.

The timesharing that is stripped to the cured article of 110 ℃ water hot extractions the 1st and the 2nd curable resin composition of the present invention, if the pH of extraction water is lower than 5.0 or more than 8.5, then sometimes on cured article surface with can flow out acidic substance or alkaline matter on every side, thereby cause the corrosion of electrode metals such as aluminium or copper, perhaps cause with the acid by generations such as hydrolysis in the cured article to be that the dechlorination reaction of catalyzer flows out chlorion, thus movie star's reliability.

The timesharing extraction electrical conductivity of water that is stripped to the cured article of 110 ℃ water hot extractions the 1st and the 2nd curable resin composition of the present invention is preferably below the 100 μ S/cm.The so-called 100 μ S/cm that surpass mean that the electroconductibility in the resin increases when placing under special wet condition, might cause electric leakage or insulation breakdown when being connected when use the 1st and the 2nd curable resin composition of the present invention conduct electricity between electrode.

In addition, the preferred the 1st and the specific inductivity of the cured article of the 2nd curable resin composition of the present invention be below 3.5, dielectric dissipation factor is below 0.02.If specific inductivity surpasses 3.5, and dielectric dissipation factor then causes the decline of transport property sometimes above 0.02 under present high frequency.

Purposes to the 1st and the 2nd curable resin composition of the present invention has no particular limits, and for example being fit to be processed into, adhesive epoxy resin cream, adhesive epoxy resin thin slice, conduction are used for fixing of electronic material etc. after connecting cream, conductive connection sheet etc.In addition, also above-mentioned curable resin composition precision work can be the lacquer shape, and with coating processes such as spin-coating method make its after forming film on the silicone wafer etc. as caking agent.

Also can in the 1st and the 2nd curable resin composition of the present invention, add flux (flux).Above-mentioned flux is preferably inertia flux.Because above-mentioned curable resin composition does not contain the big filler of median size, so in fact can be as no extender paste and no packing thin film, and because the pH of cured article also is set as neutral region, so be suitable as the thin slice use that conduction connects the cream that contains flux of usefulness or contains flux.

If the 1st and the 2nd curable resin composition of the present invention is a particulate state, then can be as semiconductor-sealing-purpose sealing agent for example, QFN with sealing agent, integrally formed type CSP with sealing agents such as sealing agents.In addition, if above-mentioned curable resin composition is essentially no extender paste, then also can directly be coated on and have again distribution and be connected with external electric, by grinding, on wafer, seal wiring circuit more then with on the wafer of metal column and make its curing with silk screen print method or spin-coating method.In addition, also can be by directly being coated on the wafer with silk screen print method, and use as the outer coating agent on the wafer.

In addition, laminar if the 1st and the 2nd curable resin composition of the present invention is configured as, then can be used as the fixedly adhesive sheet of usefulness of semi-conductor chip.

The 3rd adhesive epoxy resin cream of the present invention is made up of the 1st or the 2nd curable resin composition of the present invention.The the 1st and the 2nd curable resin composition of the present invention is owing to itself just having cementability, so can easily form the 3rd adhesive epoxy resin cream of the present invention.By when making the 1st or the 2nd curable resin composition of the present invention, use viscosity modifier or thixotropy imparting agent etc. that curable resin composition is processed as paste as required, can easily obtain the 3rd adhesive epoxy resin cream of the present invention.

The 4th interlayer caking agent of the present invention, the 5th nonconductive paste of the present invention and the 6th of the present invention filling out are lost the material that filler is made up of the 3rd adhesive epoxy resin cream of the present invention.

The 7th adhesive epoxy resin thin slice of the present invention is, by the 1st or the 2nd curable resin composition of the present invention being configured as laminar formation.

As the 1st or the 2nd curable resin composition of the present invention is configured as laminar method, have no particular limits, for example can enumerate with the extruding formation method of extrusion machine and with curable resin composition and modulate with solvent cut behind the curable resin composition solution this solution-cast on barrier sheet and make solution casting method of solvent seasoning etc., wherein, never need the pyritous viewpoint to set out, preferably use solution casting method.

The storage spring rate that the 7th adhesive epoxy resin thin slice of the present invention shows when the adhesive epoxy resin thin slice is heated up with 45 ℃/minute heat-up rate (G ') preferably surpass 1 * 10 ³Pa.The above-mentioned storage spring rate of adhesive epoxy resin thin slice (G ') if be 1 * 10 ³Below the pa, then sometimes in the process that is heating and curing of adhesive epoxy resin thin slice, on the bonding interface of adhesive epoxy resin thin slice and adherend, can produce the space.

The 7th adhesive epoxy resin thin slice of the present invention based on the crest temperature preferred consolidation of the tan δ of dynamic viscoelastic before in-20 ℃～40 ℃ scopes, be more than 120 ℃ after the curing, in 0 ℃～35 ℃ scope, be more than 160 ℃ after the curing before more preferably solidifying.Wherein, so-called tan δ uses by dynamic viscoelastic to measure the value that mechanics loss tangent that (survey frequency: 10Hz, heat-up rate: 3 ℃/minute) obtain is represented.In addition, wherein, it is above and carry out state before the thermofixation to be meant before so-called the curing that the adhesive epoxy resin thin slice is heated to specified temperature, is meant the state after the adhesive epoxy resin thin slice generation thermofixation after the so-called curing.In addition, the 4th adhesive epoxy resin thin slice of the present invention carries out thermofixation usually in 20-230 ℃ temperature range.

Owing to have the crest temperature of above-mentioned tan δ, the 7th adhesive epoxy resin thin slice of the present invention is a softish in the normal temperature zone, and operability is good, and has binding property at normal temperatures, therefore can not carry out that adherend is fitted each other in the normal temperature zone, by be heating and curing (back maintenances) such as oven heats, can show high bonding reliability simultaneously.Promptly, before solidifying, the 7th adhesive epoxy resin thin slice of the present invention has binding property at normal temperatures, and can show good rerum natura after being heating and curing, so can fusible thin slice be pasted with having, location and working fastening, can show good rerum naturas such as bonding force by heating simultaneously, show sufficient bonding reliability as the cementability thin slice.

If the crest temperature of the tan δ before the curing of adhesive epoxy resin thin slice is lower than-20 ℃, then therefore the cohesive force deficiency of adhesive epoxy resin thin slice is difficult to peel off from barrier sheet.In addition, in the adhesive epoxy resin thin slice, contain electrically conductive microparticle described later and when making conductive connection sheet, Resins, epoxy can flow in the communicating pores that is provided with in order to dispose electrically conductive microparticle sometimes, thereby buries the slam through hole.On the contrary, if the crest temperature of the tan δ before the curing of adhesive epoxy resin thin slice is above 40 ℃, then in the adhesive epoxy resin thin slice, contain electrically conductive microparticle and when making conductive connection sheet, sometimes under the normal temperature for the binding property deficiency of electrically conductive microparticle, be difficult to keep electrically conductive microparticle.

In addition, if the crest temperature of the tan δ after the curing of adhesive epoxy resin thin slice is lower than 120 ℃, be under the hot and humid environment of representative with pressure kettle test etc. then, the adhesive epoxy resin thin slice after the curing is softening sometimes, causes the decline of bonding reliability.

The preferred lower limit of the linear expansivity after the curing of the 7th adhesive epoxy resin thin slice of the present invention is 10ppm/ ℃, be limited to 200ppm/ ℃ on preferred, be limited to 20ppm/ ℃ under preferred, be limited to 150ppm/ ℃ on preferred, further preferably be limited to 30ppm/ ℃ down, further be limited to 100ppm/ ℃ on preferably.

If the linear expansivity after the curing of adhesive epoxy resin thin slice is lower than 10ppm/ ℃, then in the adhesive epoxy resin thin slice, contain electrically conductive microparticle and when making conductive connection sheet, sometimes the polar expansion missionary society of adhesive epoxy resin thin slice and electrically conductive microparticle becomes big, when electroconductibility being connected thin slice and implements thermal cycling etc., can not follow the polar expansion of electrically conductive microparticle, be difficult to the conducting reliability that keeps high, if the linear expansivity after the curing of opposite adhesive epoxy resin thin slice is above 200ppm/ ℃, then in the adhesive epoxy resin thin slice, contain electrically conductive microparticle and when making conductive connection sheet, implementing under the situation of thermal cycling etc., because of the wide electrically conductive microparticle that makes of opposed interelectrode distance leaves electrode, become the reason of poor flow sometimes.

The 8th non-conductive film of the present invention and the 9th die attachment film of the present invention are made up of the 7th adhesive epoxy resin thin slice of the present invention.

The 10th conduction of the present invention connects cream and forms by making the 3rd adhesive epoxy resin cream of the present invention contain electrically conductive microparticle.

The 11st anisotropic conductive cream of the present invention connects cream by the 10th conduction of the present invention and forms.

The 12nd conductive connection sheet of the present invention contains electrically conductive microparticle in the 7th adhesive epoxy resin thin slice of the present invention and forms by making, and at least a portion of above-mentioned electrically conductive microparticle is exposed from the adhesive epoxy resin thin slice.

The 13rd conductive connection sheet of the present invention is to form by the electrically conductive microparticle of burying underground less than sheet thickness in the 7th adhesive epoxy resin thin slice of the present invention.

As connecting the electrically conductive microparticle that uses in cream, the 11st anisotropic conductive cream of the present invention and the 12nd and the 13rd conductive connection sheet of the present invention in the 10th conduction of the present invention, get final product so long as have the particulate of electroconductibility, have no particular limits, can enumerate the particulate of for example forming by electroconductibility inorganics, electroconductive polymers such as metal, carbon blacks; On the outermost layer of the high-molecular weight polymer of forming by resin, non-conductive inorganics or non-conductive polymer etc., be provided with the particulate of conduction mulch film with methods such as plating processing; At the outermost layer of electroconductibility inorganics or electroconductive polymer etc. at the particulate that further is provided with the conduction mulch film etc., wherein, have the viewpoint of restorative etc. the globular particulate of elasticity, flexibility, the shape of appropriateness from easy acquisition, preferably use on the core of forming by high-molecular weight polymer (core) surface, to form and conduct electricity the electrically conductive microparticle that mulch film forms.These electrically conductive microparticles can use separately, also can more than two kinds and use.

Above-mentioned conduction mulch film has no particular limits, preferably the film of being made up of metal.Metal as conduction mulch film formation usefulness has no particular limits, and can enumerate for example nickel, gold and silver, aluminium, copper, tin, scolding tin etc.Consider with the contact resistance of electrode, electroconductibility and can oxidative degradation etc. characteristics, this conduction mulch film is preferably at outermost layer and has used golden conduction mulch film.In addition, the conduction mulch film preferably has the blocking layer that is used for multiple stratification or is used to improve the adhering nickel dam of core and metal.

With regard to the thickness of above-mentioned conduction mulch film, if can obtain enough conductions and the degree that can not peel off by film toughness, have no particular limits, be preferably more than the 0.4 μ m, more preferably more than the 1 μ m, further more than the preferred 2 μ m.In addition, with regard to the diameter of core, get final product, have no particular limits, be preferably below 1/5 of electrically conductive microparticle diameter so long as can not lose the degree of core characteristic.

High-molecular weight polymer as the core that can become above-mentioned electrically conductive microparticle, have no particular limits, can enumerate for example urea resin, amino such as melamine resin are resin, phenolic aldehyde is a resin, acrylic resin, the ethylene-vinyl acetate based copolymer, the styrene butadiene based block copolymer, polyester based resin, alkyd is resin, polyimide is a resin, urethane is a resin, epoxy is thermoplastic resin or heat-curing resins such as resin, cross-linked resin, organic-inorganic mixed polymer etc., wherein, from the viewpoint of excellent heat resistance, preferably use cross-linked resin.Also can contain weighting material as required in these high molecular polymers.In addition, these high molecular polymers can use separately, also can more than two kinds and use.

Have no particular limits for above-mentioned electrically conductive microparticle, but the shape (aspect) of preferred median size, particle diameter than CV value (coefficient of variation), resistance value, compression recovery, linear expansivity and the K value of, particle diameter respectively in scope as described below.

As the median size of above-mentioned electrically conductive microparticle, when above-mentioned electrically conductive microparticle being sneaked into when using in the resin, be limited to 1 μ m under preferred.Be limited to 5 μ m on preferred.Be limited to 2 μ m under preferred.

In addition,,, also can determine, preferably be limited to 10 μ m down, be limited to 800 μ m on preferably according to the thickness of thin slice as the median size of above-mentioned electrically conductive microparticle when above-mentioned electrically conductive microparticle is used for when thin slice exposes the structure of electrically conductive microparticle.If less than 10 μ m, then sometimes because of the precision problem of the smoothness of electrode or substrate, can cause electrically conductive microparticle and electrode to be difficult to contact and cause poor flow, and if surpass 800 μ m, then be short-circuited because of the electrode that can not be adapted to tiny interval makes adjacent electrode sometimes.Be limited to 15 μ m under preferred, be limited to 300 μ m on preferred, further preferably be limited to 20 μ m down, further be limited to 150 μ m on preferably, be limited to 40 μ m under particularly preferred, be limited to 80 μ m on particularly preferred.

In addition, the median size of above-mentioned electrically conductive microparticle can be by measuring with any 100 electrically conductive microparticles of microscopic examination.

The shape of the particle diameter of above-mentioned electrically conductive microparticle is lower than 1.3 than preferably, more preferably less than 1.1, further preferably is lower than 1.05.In addition, the shape of the particle diameter of so-called electrically conductive microparticle is removed the average major diameter of electrically conductive microparticle and the value obtained than being meant with average minor axis.

The shape of above-mentioned electrically conductive microparticle particle diameter is more than 1.3 such as fruit, and then sometimes because electrically conductive microparticle is irregular, minor axis partly is difficult to contacts electrode, thereby can cause poor flow.The shape of the particle diameter of common most of electrically conductive microparticles is more higher than all, so the electrically conductive microparticle of Shi Yonging is preferably under the state that can be out of shape and carries out spheroidization by the method for utilizing surface tension etc. and handle and form the globular particulate in the present invention.

The CV value (coefficient of variation) of the particle diameter of above-mentioned electrically conductive microparticle is preferably below 5%, more preferably below 2%, more preferably below 1%.In addition, shown in following calculating formula, the CV value of the particle diameter of electrically conductive microparticle is to remove with median size to take advantage of 100 and the value obtained behind the standard deviation of particle diameter.

The CV value (%) of particle diameter=(standard deviation/median size of particle diameter) * 100

If the CV value of the particle diameter of above-mentioned electrically conductive microparticle surpasses 5%, then sometimes because particle diameter is irregular, little electrically conductive microparticle is difficult to contacts electrode, thereby can cause poor flow.The CV value of common its particle diameter of electrically conductive microparticle is bigger, so the electrically conductive microparticle of Shi Yonging preferably makes the neat particulate of particle diameter by classification etc. in the present invention.Particularly particle diameter is that the following particulate of 200 μ m is difficult to carry out classification with good accuracy, so modes such as preferably combination screen sizing, air classification, wet classification are carried out classification.

Median size is being compressed at 10% o'clock, the resistance value of above-mentioned electrically conductive microparticle is preferably below 1 Ω, more preferably below 0.3 Ω, more preferably below 0.05 Ω, is preferably especially below 0.01 Ω.

If the resistance value of above-mentioned electrically conductive microparticle surpasses 1 Ω, then sometimes owing to be difficult to guarantee enough current values, perhaps be difficult to anti-in high-voltage, so the element cisco unity malfunction.In addition, if the resistance value of electrically conductive microparticle is below 0.05 Ω, even then the element of current drive-type also can use under the state of the high conducting reliability of maintenance, effect is more remarkable.

The compression recovery of above-mentioned electrically conductive microparticle is preferably more than 5%, and is more preferably more than 20%, more preferably more than 50%, preferred especially more than 80%.In addition, wherein the compression recovery of so-called electrically conductive microparticle is meant the shape recovery ratio under 10% compression set state in 20 ℃ environment, can be according to the method for putting down in writing in the fair 7-95165 communique of spy, (for example use the slight compression tester, the trade(brand)name " PCT-200 " of society of Shimadzu Seisakusho Ltd. system), on the level and smooth end face of the cylinder of adamantine diameter 50 μ m, behind the condition lower compression electrically conductive microparticle of compression speed 0.28mN/ second, initial point load value 1.0mN, reverse load value 10mN, value from % to the ratio of the displacement difference of reversal point that will represent with.

If the compression recovery of above-mentioned electrically conductive microparticle is lower than 5%, when then opposed sometimes interelectrode distance was expanded because of moments such as collisions, can not follows this variation, thereby cause the conducting instability of moment.

Be limited to 10ppm/ ℃ under the linear expansivity of above-mentioned electrically conductive microparticle preferred, be limited to 200ppm/ ℃ on preferred, be limited to 20ppm/ ℃ under preferred, be limited to 150ppm/ ℃ on preferred, further preferably be limited to 30ppm/ ℃ down, further be limited to 100ppm/ ℃ on preferably.In addition, the linear expansivity of electrically conductive microparticle can be measured with known method.

If the linear expansivity of above-mentioned electrically conductive microparticle is lower than 10ppm/ ℃, then sometimes when in the 4th adhesive epoxy resin thin slice of the present invention, containing electrically conductive microparticle and form the 6th or the 7th conductive connection sheet of the present invention, because it is big that the polar expansion difference of electrically conductive microparticle and adhesive epoxy resin thin slice becomes, so be difficult to follow the extension of adhesive epoxy resin thin slice when carrying out thermal cycling etc., thereby cause the conducting instability, if the linear expansivity of opposite conductivities particulate is above 200ppm/ ℃, then under the situation by bonding next bonding conductive connection sheet on the substrate, interelectrode distance can become wide when carrying out thermal cycling etc., cause breaking of the bonding portion that forms by this adhesion, and make the connection portion of stress concentration, thereby cause poor flow etc. at electrode.

Be limited to 400N/mm under the K value of above-mentioned electrically conductive microparticle is preferred ², be limited to 15000N/mm on preferred ², be limited to 1000N/mm under preferred ², be limited to 10000N/mm on preferred ², be limited to 2000N/mm under further preferred ², be limited to 8000N/mm on further preferred ², be limited to 3000N/mm under particularly preferred ², be limited to 6000N/mm on particularly preferred ²In addition, such as in the fair 7-95165 communique of spy record, the K value of electrically conductive microparticle is with (3/ √ 2) FS ^-3/2R ^-1/2(unit is N/mm ²) definition the value of generally and quantitatively representing spheroid hardness.Specifically, according to the method for putting down in writing in the above-mentioned communique, (for example use the slight compression tester, the trade(brand)name " PCT-200 " of society of Shimadzu Seisakusho Ltd. system), be on the level and smooth end face of cylinder of 50 μ m at adamantine diameter, at the condition lower compression electrically conductive microparticle of compressive hardness 0.27g/ second, maximum load of the test 10g and the value of calculating.Wherein, F represents the load value (N) under 10% compression set, and S represents the compression displacement (mm) under 10% compression set, and R represents radius (mm).

If the K value of above-mentioned electrically conductive microparticle is lower than 400N/mm ², then electrically conductive microparticle can not fully immerse between the opposed electrode sometimes, can not realize conducting under the oxidized situation of electrode surface, and perhaps contact electricity resistive is big, causes the decline of conducting reliability, if the K value of opposite conductivities particulate surpasses 15000N/mm ²When then using the opposite electrode clamping sometimes, part that can counter electrode applies the pressure of transition and causes element fracture, and perhaps only by the interval between the big electrically conductive microparticle determining electrode of particle diameter, the little electrically conductive microparticle of particle diameter can not contacts electrode and become the reason of poor flow.

The 10th conduction of the present invention connects cream can be by carrying out evenly mixing the making behind the above-mentioned electrically conductive microparticle that adds specified amount in the 3rd adhesive epoxy resin cream of the present invention.

The the 12nd and the 13rd conductive connection sheet of the present invention can be configured or bury underground and make after make the above-mentioned electrically conductive microparticle that contains specified amount in the 7th adhesive epoxy resin thin slice of the present invention.

The thickness of the adhesive epoxy resin thin slice that uses in the making of above-mentioned conductive connection sheet is preferably 1/2～2 times of electrically conductive microparticle median size, and more preferably 2/3～1.5 times, further preferred 3/4～1.3 times, preferred especially 4/5～1.2 times.

In addition, in above-mentioned conductive connection sheet, when forming the structure of in thin slice, exposing electrically conductive microparticle, if the thickness of adhesive epoxy resin thin slice is less than 1/2 times of the electrically conductive microparticle median size, then the adhesive epoxy resin thin slice is difficult to the support electrode substrate sometimes, if the thickness of opposite adhesive epoxy resin thin slice surpasses 2 times of the electrically conductive microparticle median size, then electrically conductive microparticle can not contacts electrode and become the factor of poor flow sometimes.When especially on the electrode of element and substrate, projection being arranged, the thickness of adhesive epoxy resin thin slice is preferably more than 1 times of electrically conductive microparticle median size, when not having projection on the contrary on the electrode of element and substrate, the thickness of adhesive epoxy resin thin slice is preferably below 1 times of electrically conductive microparticle median size.

On the adhesive epoxy resin thin slice that in the making of above-mentioned conductive connection sheet, uses, preferably be provided with the communicating pores that is used to dispose electrically conductive microparticle.The position that above-mentioned communicating pores is set has no particular limits, and can suitably select according to substrate or chip as the conducting object, can be arranged on arbitrarily on the position identical with the electrode of the counter substrate that needs conducting.

Above-mentioned communicating pores has no particular limits, and the shape ratio in preferred mean pore size, aperture and the CV value in aperture are respectively in scope as described below.

The mean pore size of communicating pores is preferably 1/2～2 times of electrically conductive microparticle median size, and more preferably 2/3～1.3 times, further preferred 4/5～1.2 times, preferred especially 9/10～1.1 times.If the mean pore size of communicating pores less than 1/2 of the electrically conductive microparticle median size, perhaps surpasses 2 times, the electrically conductive microparticle of then burying underground sometimes is easy to depart from communicating pores.

The shape in communicating pores aperture is lower than 2 than preferably, and is more preferably below 1.5, further preferred below 1.3, preferred especially below 1.1.The shape in communicating pores aperture is more than 2 such as fruit, and then the electrically conductive microparticle that is provided with sometimes is easy to depart from communicating pores.The shape in so-called communicating pores aperture is than being the value of obtaining except that the average major diameter in aperture with average minor axis.

The CV value in communicating pores aperture is preferably below 10%, and is more preferably below 5%, further preferred below 2%, preferred especially below 1%.If the CV value in communicating pores aperture surpasses 10%, then the aperture becomes inconsistent sometimes, and the electrically conductive microparticle of configuration is easy to depart from communicating pores.Shown in following calculating formula, the CV value in so-called communicating pores aperture is to take advantage of 100 values of obtaining after removing the standard deviation in aperture with mean pore size.

The CV value (%) in aperture=(standard deviation/mean pore size in aperture) * 100

When communicating pores being set on the adhesive epoxy resin thin slice that uses in the making of above-mentioned conductive connection sheet and on this communicating pores, disposing electrically conductive microparticle, when the adhesive epoxy resin thin slice itself has been endowed under the fusible situation, the cementability of this communicating pores binding property acquisition on every side can be utilized, thereby the retentivity of high electrically conductive microparticle can be near room temperature region, guaranteed for electrically conductive microparticle.

In addition, as the method for configuration electrically conductive microparticle on the communicating pores that is arranged on the adhesive epoxy resin thin slice, can enumerate the method for for example passing communicating pores attraction electrically conductive microparticle, the method for on communicating pores, pushing electrically conductive microparticle etc.

The 12nd conductive connection sheet of the present invention is, electrically conductive microparticle forms by containing in the 7th adhesive epoxy resin thin slice of the present invention, promptly, optional position in the 7th adhesive epoxy resin thin slice of the present invention disposes a plurality of electrically conductive microparticles and forms, and at least a portion of electrically conductive microparticle is exposed from the adhesive epoxy resin thin slice.

By forming the conductive connection sheet of said structure, when making fine opposed electrode conduction, can not leak electricity between adjacent electrode, can easily carry out the high conducting of reliability at short notice.

In addition, the allocation position of electrically conductive microparticle can be as follows: at least a portion of electrically conductive microparticle only is exposed on the single face of adhesive epoxy resin thin slice, at least a portion of electrically conductive microparticle is exposed on the two sides of adhesive epoxy resin thin slice.

The conductive connection sheet of the 13rd invention is to form by the electrically conductive microparticle of burying underground less than sheet thickness in the 7th adhesive epoxy resin thin slice of the present invention.In the 7th conductive connection sheet of the present invention, electrically conductive microparticle at least a portion also littler than sheet thickness can be exposed to the single face or the two sides of adhesive epoxy resin thin slice, also can not expose.

When on the adhesive epoxy resin thin slice, communicating pores not being set, also can bury underground by the electrically conductive microparticle that the extrusion ratio sheet thickness is also little on the adhesive epoxy resin thin slice.At this moment, when self being endowed under the fusible situation, can utilize this binding property under the state of stable maintenance electrically conductive microparticle, to bury underground at the adhesive epoxy resin thin slice.In addition, when the binding property of adhesive epoxy resin thin slice is more weak, can be heated to not solidified degree of adhesive epoxy resin thin slice, to improve the binding property of adhesive epoxy resin thin slice.In addition, by the center of gravity of the electrically conductive microparticle buried underground preferably in the inside of adhesive epoxy resin thin slice.Thus, can under stable status, bury electrically conductive microparticle underground.

The 14th anisotropic conducting film of the present invention is made up of the 13rd conductive connection sheet of the present invention.

The 15th conductive connection sheet of the present invention is the conductive connection sheet that is formed by resin of binding property thin slice and electrically conductive microparticle, described resin of binding property thin slice is by containing by adding that softening agent has been given fusible resin and being that the adhesive resin composition of the aqueous Resins, epoxy with naphthalene skeleton constitutes at normal temperatures, the crest temperature based on the tan δ of dynamic viscoelastic of above-mentioned resin of binding property thin slice is-20 ℃～40 ℃ scope before curing, be more than 120 ℃ after the curing, simultaneously dispose above-mentioned electrically conductive microparticle on the optional position of above-mentioned resin of binding property thin slice, at least a portion of above-mentioned electrically conductive microparticle is exposed from above-mentioned resin of binding property thin slice.

Given fusible resin as the interpolation softening agent that passes through that in above-mentioned adhesive resin composition, contains, have no particular limits, for example can enumerate vinyl acetate and be polyvinyl acetals such as resin, ethylene-vinyl acetate based copolymer, acrylic resin, polyvinyl butyral resin and be resin, phenylethylene resin series, saturated polyester and be resin, thermal plastic urethane and be resin, polyamide-based resin, thermoplastic polyimide is that resin, ketone are resin, norbornene resin, styrene butadiene based block copolymer etc.These resins are owing to have a high thermotolerance, and give binding property by adding softening agent, so be preferably the high-molecular weight polymer that has than high glass transition.In addition, these resins can use separately, also can more than two kinds and use.

As the softening agent that in above-mentioned adhesive resin composition, contains, can use to be aqueous naphthalene type Resins, epoxy at normal temperatures.The Resins, epoxy that above-mentioned so-called naphthalene type Resins, epoxy is made up of the naphthalene skeleton with epoxy group(ing).Above-mentioned naphthalene type Resins, epoxy is owing to having inflexible naphthalene skeleton, so even the 8th conductive connection sheet of the present invention also can obtain high shape-holding property at its thin slice after the curing under hot and humid environment.

Above-mentioned naphthalene type Resins, epoxy is owing to contain isomer, and fusing point is generally below the normal temperature, so can have binding property even the 8th conductive connection sheet of the present invention is handled also at low temperatures.Promptly, when having when giving binding property than the high-molecular weight polymer of high glass transition to above-mentioned, by using is aqueous naphthalene type Resins, epoxy at normal temperatures, can bring into play good plasticizing effect, even handle the resin of binding property thin slice and the conductive connection sheet that also can obtain to possess simultaneously at low temperatures with respect to the binding property and the shape-holding property under the hot and humid environment of electrically conductive microparticle.

As above-mentioned be aqueous naphthalene type Resins, epoxy at normal temperatures, have no particular limits, can enumerate for example 1-glycidyl naphthalene, 2-glycidyl naphthalene, 1,2-diglycidyl naphthalene, 1,5-diglycidyl naphthalene, 1,6-diglycidyl naphthalene, 1,7-diglycidyl naphthalene, 2,7-diglycidyl naphthalene, triglycidyl group naphthalene, 1,2,5,6-four glycidyl group naphthalene etc.These naphthalene type Resins, epoxy may be used alone, used in two or more.

Quantity for the epoxy group(ing) that contains in the aqueous naphthalene type Resins, epoxy under above-mentioned normal temperature has no particular limits, and preferably each molecule on average contains more than one, and more preferably each molecule on average contains more than two.

In above-mentioned adhesive resin composition, preferably contain and be useful on the hardener for epoxy resin that makes at normal temperatures to aqueous naphthalene type epoxy resin cure.

As above-mentioned hardener for epoxy resin, can use with in the above-mentioned the 1st and the 2nd curable resin composition of the present invention as the identical solidifying agent of solidifying agent that must composition contains, have no particular limits, for example can enumerate acid anhydrides such as trialkyl tetrahydrochysene anhydride phthalic acid is that solidifying agent, phenol are that solidifying agent, amine are potentiality solidifying agent such as solidifying agent, Dyhard RU 100, positively charged ion series catalysts type solidifying agent etc., and wherein preferred to use above-mentioned be the potentiality solidifying agent such as Dyhard RU 100 that aqueous heat-curing type solidifying agent or multifunctional and equivalent addition can be less at normal temperatures.These hardener for epoxy resin can use separately, also can more than two kinds and use.

In addition, in above-mentioned adhesive resin composition,, also can and use curing catalyst with above-mentioned hardener for epoxy resin in order to adjust the rerum natura of curing speed or cured article.

As above-mentioned curing catalyst, the identical curing catalyst of curing catalyst that can use and in the above-mentioned the 1st and the 2nd curable resin composition of the present invention, can be used in combination, have no particular limits, can enumerate imidazoles is that curing catalyst, tertiary amine are curing catalyst etc., wherein, from being easy to control the viewpoint of the reaction system that is used to adjust curing speed or cured article rerum natura etc., preferably using above-mentioned imidazoles is curing catalyst.These curing catalysts can use separately, also can more than two kinds and use.

In above-mentioned adhesive resin composition, add the compound that softening agent (naphthalene type Resins, epoxy) can not given the Resins, epoxy beyond the naphthalene type Resins, epoxy such as fusible high-molecular weight polymer, for example dicyclopentadiene-type epoxy resin yet or contain epoxy group(ing) even also can contain as required.

In addition, in above-mentioned adhesive resin composition, can add as required also that adhesivity activator for example, pH are adjusted a kind of in the various additives such as agent, ion trap agent, viscosity modifier, thixotropy imparting agent, antioxidant, thermo-stabilizer, photostabilizer, UV light absorber, tinting material, dewatering agent, fire retardant, static inhibitor, mould inhibitor, sanitas, solvent or more than two kinds.

The method that make the resin of binding property thin slice as above-mentioned adhesive resin composition being configured as laminar, have no particular limits, for example can enumerate with the extruding formation method of extrusion machine and with adhesive resin composition and modulate behind the adhesive resin composition solution this solution-cast on barrier sheet and make solution casting method of solvent seasoning etc. with solvent cut, wherein, never need the pyritous viewpoint to set out, preferably use solution casting method.

The resin of binding property thin slice that so obtains, use by above-mentioned dynamic viscoelastic and measure (survey frequency: 10Hz, heat-up rate: 3 ℃/minute) the crest temperature of the tan δ that represents of the mechanics loss tangent of obtaining, need in-20 ℃～40 ℃ scopes before solidifying, solidify the back more than 120 ℃, in 0 ℃～35 ℃ scopes, solidify the back before the preferred consolidation more than 160 ℃.

Owing to have the crest temperature of such tan δ, the 15th conductive connection sheet of the present invention that uses above-mentioned resin of binding property thin slice to make is a softish in the normal temperature zone, and operability is good, and has binding property at normal temperatures, can not have in the normal temperature zone adherend to be fitted each other under the hot pressed condition, by be heating and curing (back maintenances) such as oven heats, can show high bonding reliability or high conducting reliability simultaneously.Promptly, the 15th conductive connection sheet of the present invention that uses above-mentioned resin of binding property thin slice to make has binding property at normal temperatures before solidifying, and can show good rerum natura after being heating and curing, so can carry out bonding, location and working fastening with having fusible thin slice, can show good bonding force or good rerum naturas such as conduction by heating simultaneously, show sufficient bonding reliability and conducting reliability as conductive connection sheet.

If the crest temperature of the tan δ before the curing of resin of binding property thin slice is lower than-20 ℃, the cohesive force deficiency of resin of binding property thin slice then, therefore be difficult to peel off the 15th conductive connection sheet of the present invention from barrier sheet, perhaps adhesive resin composition can flow into for the above-mentioned electrically conductive microparticle of configuration on the resin of binding property thin slice in the above-mentioned communicating pores that is provided with and buries the slam through hole, if the crest temperature of the tan δ before the curing of opposite resin of binding property thin slice is above 40 ℃, then in the resin of binding property thin slice, contain electrically conductive microparticle and when making conductive connection sheet, binding property deficiency with respect to the electrically conductive microparticle under the normal temperature is difficult to keep electrically conductive microparticle.

In addition, above-mentioned resin of binding property thin slice is below 5% with respect to the unit elongation of the resin of binding property thin slice after the curing of the resin of binding property thin slice after solidifying after carrying out the pressure kettle test under 120 ℃ of temperature, humidity 85%RH, the condition of 12 hours time preferably.

Surpass 5% if carry out the unit elongation of the resin of binding property thin slice behind the after fixing of above-mentioned pressure kettle test back, then use the bonding reliability or the conducting reliability deficiency of the 15th conductive connection sheet of the present invention of above-mentioned resin of binding property thin slice making sometimes.

As the electrically conductive microparticle that in the 15th conductive connection sheet of the present invention, uses, the identical electrically conductive microparticle of particulate that can be and in the 10th conduction connection cream of the present invention, the 11st anisotropic conductive cream of the present invention, the 12nd and the 13rd conductive connection sheet of the present invention, contain, have no particular limits, can enumerate the particulate of for example forming by electroconductibility inorganics, electroconductive polymers such as metal, carbon blacks; Outermost layer at the high-molecular weight polymer of being made up of resin, non-conductive inorganics or non-conductive polymer etc. is provided with the particulate that conduction covers mould with methods such as plating processing; Further be provided with the particulate of conduction mulch film etc. at the outermost layer of electroconductibility inorganics or electroconductive polymer etc., wherein, from the viewpoint of restorative etc. the globular particulate of the elasticity, flexibility, the shape that are easy to obtain to have appropriateness, preferably use and on the core of forming by high-molecular weight polymer (core) surface, form the electrically conductive microparticle that conducts electricity mulch film and form.These electrically conductive microparticles can use separately, also can more than two kinds and use.

The 15th conductive connection sheet of the present invention forms by contain above-mentioned electrically conductive microparticle in above-mentioned resin of binding property thin slice, promptly, disposing a plurality of electrically conductive microparticles by the optional position at the resin of binding property thin slice forms, and at least a portion of electrically conductive microparticle is exposed from the resin of binding property thin slice.

By forming the conductive connection sheet of said structure, when making fine opposed electrode conduction, can not leak electricity between adjacent electrode, can easily carry out the high conducting of reliability at short notice.

In addition, the position of configuration electrically conductive microparticle can be as follows: make at least a portion of electrically conductive microparticle only be exposed to the single face of resin of binding property thin slice, also can make at least a portion of electrically conductive microparticle be exposed to the two sides of resin of binding property thin slice.

Dispose a plurality of electrically conductive microparticles to make the method for conductive connection sheet can be method identical when making the 12nd conductive connection sheet of the present invention in the optional position of resin of binding property thin slice.

The 3rd adhesive epoxy resin cream of the present invention is connected cream (following also only abbreviate as sometimes " cream ") owing to be paste with the 10th conduction of the present invention, be different from laminar material, need not cut in advance or process according to the size of IC chip and electron device etc., the also device that does not need paste operation to use is so be applicable to the produced in small quantities of many kinds.

In addition, so be different from laminar material, there is not problem of misalignment in above-mentioned cream, even can not produce space with outside part on the concavo-convex big substrate at concavo-convex big substrate of distribution part and distribution owing to be paste yet during stickup.In addition, under laminar situation, thin slice might stretch or disconnect when pasting thin slice, and as paste, does not just have such problem.Therefore, for little IC chip of size and electron device etc. and concavo-convex big substrate, paste used than laminar also being fit to sometimes.

The 3rd adhesive epoxy resin cream of the present invention and the 10th conductive connection sheet of the present invention, so long as viscosity be adjusted to can enough decollators etc. the state that is coated with of apparatus for coating can use, can be with solvent cut, also can be no-solvent type.In addition, above-mentioned cream can be coated on IC chip or the electron device etc., also can be coated on the substrate.That is, being coated on a side who is easy to be coated with upward gets final product.In addition, usually from being easy to regulate the viewpoint of glue spread, preferably be coated on the substrate in advance.

During with the above-mentioned cream of solvent cut, can be coated at least one Fang Shanghou of adherend, carry out maintenance under can not solidified low temperature to make solvent evaporation, carry out the B stepwise by paste, determine the position of IC chip or electron device etc. afterwards, and implement method such as flip-chip connection and carry out bonding.In addition, be under the situation of no-solvent type at above-mentioned cream, equally also can behind the position of determining IC chip or electron device etc., carry out flip-chip and connect.

Above-mentioned cream also can need on the bonding part with only local being coated on such as decollator, cylinder, packer (stamper).In addition,, also can be thermoformed into mobile cream, the heating landfill substrate when utilizing flip-chip to connect thus concavo-convex by adding in order to improve bonding reliability and conducting reliability.

The 3rd adhesive epoxy resin cream of the present invention has no particular limits with the purposes that the 10th conduction of the present invention is connected cream, is connected etc. in electronic material fixing etc. but be suitable for for example bonding or conducting connection, the convex projected electrode of electron device and the conducting of other electrode of circuit substrate.

On the other hand, the 7th adhesive epoxy resin thin slice of the present invention and the 12nd, 13,15 conductive connection sheets of the present invention are owing to be laminar, be different from paste, need not cut in advance, process according to the size of IC chip or electron device etc., the also device that does not need paste operation to use, but can also on production line, carry out high-speed production, so be applicable to the mass production of few kind.

12nd, the purposes of 13,15 conductive connection sheets of the present invention has no particular limits, for example at liquid-crystal display, Personal Computer, carry in the manufacturing processed of electronic products such as communicating machine, be adapted at making minicomponents such as semiconductor element to be electrically connected with substrate or under the situation that makes fine electrode contraposition among the method that substrate is electrically connected to each other and be electrically connected, to use.As actual product, can enumerate for example memory card, IC-card etc.In addition, in the manufacturing processed of glass circuit substrate, be adapted at being provided with on the glass surface that the Lighting Division of automobile grades among the method for turning circuit and use under and the situation about being connected opposed at the electrode surface that makes glass surface and turning circuit.So, can form electronic component joined body.In addition, above-mentioned conductive connection sheet can be used on the single layer substrate, also can be used in simultaneously electrically conductive microparticle as about on the substrate of forming by multilayer of conductive material.

The 16th flip-chip band of the present invention is made up of the 12nd or 15 conductive connection sheets of the present invention.

12nd, 13,15 conductive connection sheets of the present invention are particularly suitable for the joint of bare chip.Usually, using when engaging bare chip under the situation of flip-chip needs to possess protuberance, but when using above-mentioned conductive connection sheet, because electrically conductive microparticle has played the effect of protuberance, so can under the condition of not using protuberance, connect.Therefore, has the very big advantage that to omit miscellaneous operation of making protuberance.In addition, when electrically conductive microparticle has aforesaid preferred K value or CV value etc.,, also can break its oxide film and connect even aluminium electrode etc. are easy to the electrode of oxidation.

As the 12nd, 13,15 conductive connection sheets of the present invention and aforesaid substrate or there is not the method for attachment of the chip of protuberance, can enumerate for example following method.Be formed with on the surface on the substrate or chip of electrode, the mounting conductive connection sheet makes the position of electrically conductive microparticle near electrode, another substrate with electrode surface or chip is set afterwards, and makes electrode position corresponding.By heating or pressurization etc., Jie assistant director of a film or play is electrically connected thin slice and connects under this state.In addition, in heating or pressurization, suitable use has the press-connection machine of well heater or jointing machine (bonding machine) etc.

As above-mentioned engaging condition, preferably carrying out after the conducting really is that electrode contacts after-applied temperature really with electrically conductive microparticle.If do not do like this; can not carry out under the state of contact at electrode and electrically conductive microparticle; resin is flowed through heating; not only can generating electrodes and electrically conductive microparticle between flow into the poor flow of resin; and owing to there is not the power of pushing electrically conductive microparticle; so along with resin flow, electrically conductive microparticle can depart from the position of electrode, thereby can not carry out certain conducting.Specifically, can be at first under the state that does not apply temperature, pressurize with high pressure, the monitoring resistor value confirms on one side whether electrode contacts with each other on one side, heat after pressure being reduced to the disruptive zone that does not have electrically conductive microparticle then, thereby can avoid electrically conductive microparticle with the effect of the frictional force of electrode under move along with resin flow, and resin can not enter between electrode and the electrically conductive microparticle yet, can carry out conducting with high accuracy and connect.Therefore, pressure condition is divided into two stages from the high pressure to low pressure.

In addition, if heat up with ceramic heater this moment quickly, then can produce emptying aperture (space) in resin or on the bonding interface sometimes.It is bonding bad that this volatile component such as for example moisture that are (about 200 ℃) produce owing at high temperature foams and causes.In order to prevent the problems referred to above, can adopt the method that suppresses volatile component self in the resin.But, when using organic substrate, reduce volatile amount in the resin in any case as adherend, all can become the factor of foaming from the volatile component of adherend.Therefore, considered that the spring rate by the resin when applying heat remains certain more than certain spring rate, suppressed the method for this foamed phenomenon self.

As this method, the method that has normally used B step (semicure) to change.Resin flow can be suppressed thus, and foaming can be suppressed.But this moment, resin was difficult to Clearance Flow, and then can bring detrimentally affect to cementability, and particularly the water capacity is easily local on the interface exists, thereby causes detrimentally affect can for the moisture-proof cementability.Therefore, when considering the balance of each performance, the method for B stepwise is very not desirable.

Another method is that mobile decline spring rate less, that make resin keeps to a certain degree above method.Suitablely in this method use small mineral filler, for example usually as the silicon-dioxide of the fine powder (particle diameter is below the 1 μ m, nano level) of thickening material etc.Especially do not use above-mentioned B stepwise method by adopting the method that improves spring rate, can suppress the generation in space.More than explanation is that electrically conductive microparticle fixed point is configured on the optional position of thin slice and the conductive connection sheet that forms, even but electrically conductive microparticle is embedded in the conductive connection sheet that forms in the thin slice, also can use the same method is used for the conductive connecting material purposes.

In the conduction connecting structure body that uses the 12nd, 13,15 conductive connection sheets of the present invention to connect and form, also can around thin slice, seal, to prevent immersing moisture etc. and the bad phenomenon that produces takes place by the connection end face of thin slice.Sealing agent as being used to seal has no particular limits, for example Resins, epoxy, silicone resin, resol, polyimide resin, the inorganic materials etc. enumerated of the use that suits.

The 17th electronic component joined body of the present invention is, utilize the 1st or the 2nd curable resin composition of the present invention, the 3rd adhesive epoxy resin cream of the present invention, the 4th interlayer caking agent of the present invention, the 5th nonconductive paste of the present invention, the 6th filler thanks to of filling out of the present invention, the 7th adhesive epoxy resin thin slice of the present invention, the 8th non-conductive film of the present invention, the 9th die attachment film of the present invention, the 10th conduction of the present invention connects cream, the 11st anisotropic conductive cream of the present invention, the 12nd, 13 or 15 conductive connection sheets of the present invention, the 14th anisotropic conducting film of the present invention, perhaps any in the 16th flip-chip band of the present invention engages projected electrode and other electrode of the overshooting shape of electron device and forms under conducting state.

In addition, the 18th electronic component joined body of the present invention, be to utilize the 1st or the 2nd curable resin composition of the present invention, the 3rd adhesive epoxy resin cream of the present invention, the 4th interlayer caking agent of the present invention, the 5th nonconductive paste of the present invention, the 6th filler thanks to of filling out of the present invention, the 7th adhesive epoxy resin thin slice of the present invention, the 8th non-conductive film of the present invention, the 9th die attachment film of the present invention, the 10th conduction of the present invention connects cream, the 11st anisotropic conductive cream of the present invention, the 12nd, 13 or 15 conductive connection sheets of the present invention, the 14th anisotropic conducting film of the present invention, perhaps any in the 16th flip-chip band of the present invention engages and is selected from die-attach area, ceramic substrate, resin substrate, silicon substrate, at least a circuit substrate in compound semiconductor substrate and the glass substrate and forming.

Above-mentioned resin substrate is preferably glass epoxy substrate, Bismaleimide Triazine substrate or polyimide substrate.

The 1st curable resin composition of the present invention because contain Resins, epoxy, have can with the polymkeric substance and the hardener for epoxy resin of the functional group of epoxy reaction, in the resin matrix of the cured article of observing with transmission electron microscope with heavy metal dyeing back, do not observe phase separation structure, so the physical strength after solidifying, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc. are good, the high conducting reliability in the time of showing high bonding reliability and make conductive material.

The 2nd curable resin composition of the present invention is because in the composition epoxy resin that mixing dicyclopentadiene-type epoxy resin, naphthalene type Resins, epoxy and hardener for epoxy resin form, the second-order transition temperature that contains core is below 20 ℃, the second-order transition temperature of shell portion is the rubber particles of the core shell structure more than 40 ℃, so it is good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., the high conducting reliability in the time of showing high bonding reliability and make conductive material.

The 3rd adhesive epoxy resin cream of the present invention and the 7th adhesive epoxy resin thin slice of the present invention are owing to be made up of the above-mentioned the 1st or the 2nd curable resin composition of the present invention, so it is good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., high conducting reliability in the time of showing high bonding reliability and make conductive material.

The 4th interlayer caking agent of the present invention, the 5th nonconductive paste of the present invention and the 6th filler of filling out thanks to of the present invention are made up of the 3rd adhesive epoxy resin cream of the present invention, the 8th non-conductive film of the present invention and the 9th die attachment film of the present invention are made up of the 7th adhesive epoxy resin thin slice of the present invention, so it is good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., can show high bonding reliability and high conducting reliability.

The 10th conduction of the present invention connects cream and contains electrically conductive microparticle in the above-mentioned the 3rd adhesive epoxy resin cream of the present invention and form by making, in addition, the 12nd and 13 conductive connection sheets of the present invention form by disposing or bury electrically conductive microparticle underground in the above-mentioned the 7th adhesive epoxy resin thin slice of the present invention, so it is all good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., can show high bonding reliability and high conducting reliability.

The 11st anisotropic conductive cream of the present invention is owing to be made up of the 10th conduction connection cream of the present invention, so it is good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., can show high bonding reliability and high conducting reliability.

The 14th anisotropic conducting film of the present invention is owing to be made up of the 13rd conductive connection sheet of the present invention, physical strength, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc. are good altogether so solidify the back, can show high bonding reliability and high conducting reliability.

The 15th conductive connection sheet of the present invention is owing to be the conductive connection sheet that is formed by resin of binding property thin slice and electrically conductive microparticle, and described resin of binding property thin slice is by containing by adding that softening agent has been given fusible resin and being that the adhesive resin composition of aqueous naphthalene type Resins, epoxy is formed at normal temperatures, above-mentioned resin of binding property thin slice is-20 ℃～40 ℃ scope before curing based on the crest temperature of the tan δ of dynamic viscoelastic, be more than 120 ℃ after the curing, simultaneously be provided with above-mentioned electrically conductive microparticle in the optional position of resin of binding property thin slice, so solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stabilitys etc. are good, can show high bonding reliability and high conducting reliability.

The 16th flip-chip band of the present invention is owing to be made up of the 12nd or the 15th conductive connection sheet of the present invention, so it is good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., can show high bonding reliability and high conducting reliability.

The the 17th and the 18th electronic component joined body of the present invention is owing to be to utilize the 1st or the 2nd curable resin composition of the present invention, the 3rd adhesive epoxy resin cream of the present invention, the 4th interlayer caking agent of the present invention, the 5th nonconductive paste of the present invention, the 6th filler thanks to of filling out of the present invention, the 7th adhesive epoxy resin thin slice of the present invention, the 8th non-conductive film of the present invention, the 9th die attachment film of the present invention, the 10th conduction of the present invention connects cream, the 11st anisotropic conductive cream of the present invention, the 12nd, 13 or 15 conductive connection sheets of the present invention, the 14th anisotropic conducting film of the present invention, the perhaps any making in the 16th flip-chip band of the present invention is so can show high bonding reliability and high conducting reliability.

Embodiment

Below by embodiment the present invention is described in further detail, but the present invention is not limited in these embodiment.

In the present invention, except that situation about specifying, following starting material have been used.

1. Resins, epoxy

(1) dicyclopentadiene-type solid epoxy (trade(brand)name " EXA-7200HH ", big Japanese ink chemical industry society system)

(2) naphthalene type liquid epoxy resin (trade(brand)name " HP-4032D ", big Japanese ink chemical industry society system)

(3) bisphenol A-type liquid epoxy resin (trade(brand)name " EP828 ", japan epoxy resin society system)

2. the polymer that has epoxy group(ing)

(1) contains the acrylic resin-a (trade(brand)name " マ one プ Le one Off G-2050M ", suspension polymerization, epoxy equivalent (weight): 340, weight-average molecular weight: 200,000, second-order transition temperature: 80 ℃, Japanese grease society system) of epoxy group(ing)

(2) contain the acrylic resin-b (trade(brand)name " Block レ Application マ-CP-15 ", suspension polymerization, epoxy equivalent (weight): 500, weight-average molecular weight: 10,000, second-order transition temperature: 80 ℃, Japanese grease society system) of epoxy group(ing)

(3) acrylic rubber-c that contains epoxy group(ing) (makes ethyl propenoate 99 weight parts and glycidyl methacrylate 1 weight part carry out the material that solution polymerization obtains by the hot radical method in vinyl acetic monomer, epoxy equivalent (weight): 8000, weight-average molecular weight: 200,000, second-order transition temperature: 10 ℃)

(4) contain the acrylic rubber-d (trade(brand)name " Nippol AR-42W ", Japanese ゼ ォ Application society system) of epoxy group(ing)

3. high-molecular weight polymer

(1) polyvinyl butyral resin (trade(brand)name " BX-5Z ", ponding chemical industry society system)

4. hardener for epoxy resin

(1) trialkyl tetrahydrochysene anhydride phthalic acid (trade(brand)name " YH-307 ", japan epoxy resin society system)

(2) Dyhard RU 100 (trade(brand)name " EH-3636AS " Xu Dianhuagongyeshe system)

(3) guanidine compound (trade(brand)name " DX147 " japan epoxy resin society system)

5. curing catalyst

(1) tricarbimide modified solid decentralized imidazoles (trade(brand)name " 2MAOK-PW ", four countries change into society's system)

(2) 1-cyano ethyl-2-phenylimidazole

(3) 2-ethyl-4-methylimidazole

6. cementability imparting agent

(1) imidazoles silane coupling agent (trade(brand)name " SP-1000 " day ore deposit マ テ リ ァ Le ズ)

(2) aminosilane coupling agent (trade(brand)name " S320 ", チ ッ ソ society system)

7. filler

(1) surface-hydrophobicized pyrogenic silica (trade(brand)name " レ ォ ロ シ-Le MT-10 ", median size: below the 1 μ m, ト Network ャ マ society system)

(2) spherical silicon dioxide (median size: 5 μ m)

8. stress relaxation imparting agent

(1) contains the core-shell-type acrylic rubber particle (trade(brand)name " ス Off ィ ロ ィ De AC-4030 ", ガ Application ッ changes into society's system) of hydroxyl

(2) contain the core-shell-type acrylic rubber particle (trade(brand)name " ゼ ォ Application F451 ", Japanese ゼ ォ Application society system) of carboxyl

(3) terminal epoxy groups modified silicone oil (trade(brand)name " KF-105 ", chemical industry society of SHIN-ETSU HANTOTAI system)

9. solvent

(1) vinyl acetic monomer

(embodiment 1)

Use the homodisperse device, acrylic resin-a, trialkyl tetrahydrochysene anhydride phthalic acid 60 weight parts, tricarbimide modified solid decentralized imidazoles 8 weight parts and imidazoles silane coupling agent 2 weight parts that dicyclopentadiene-type solid epoxy 76 weight parts, naphthalene type liquid epoxy resin 20 weight parts, 4 weight parts are contained epoxy group(ing) are evenly mixing, modulation adhesive epoxy resin cream.

(embodiment 2-4 and comparative example 1-2)

Except the combined group with adhesive epoxy resin cream becomes to be defined as the composition shown in the table 1, modulate adhesive epoxy resin cream in the same manner with embodiment 1.

The performance of the adhesive epoxy resin cream that obtains by embodiment 1-4 and comparative example 1,2 with following method evaluation (1. gelation rate, 2. initial stage bonding force-A, the foamed state under 3.200 ℃).The results are shown in the table 1.

1. gelation rate

Adhesive epoxy resin cream is heating and curing under 170 ℃ of-1 minute and 170 ℃ of two conditions of-2 minutes in baking oven.Then, cured article was flooded 24 hours in the vinyl acetic monomer of normal temperature, filter not solvent components then, thorough drying, obtain the weight ratio (weight before the weight/dipping behind the dipping) of the cured article of vinyl acetic monomer dipping front and back then, calculate gelation rate (weight %).

2. initial stage bonding force-A

The 1 adhesive epoxy resin cream that drips on the glass epoxy substrate of FR-4 is provided with the square spacer plate that the length of side is 5mm around it, bonding thereon have a SiO ₂The length of side of passive film (passivation) is the quadrate silicon chip of 10mm, is heating and curing under 170 ℃ 30 minutes then, makes conjugant.Then, at the sectional fixture up and down of the conjugant that obtains,, obtain maximum breaking tenacity (N/25mm according to the draw speed up-down stretch of 5mm/min ²), and be defined as initial stage bonding force-A.

3.200 the foamed state under ℃

Adhesive epoxy resin cream is put into 200 ℃ baking oven, take out after 1 minute, the foamed state that detects by an unaided eye, the foamed state under estimating 200 ℃ according to following criterion.

[criterion]

Zero ... do not observe foaming.

* ... seen foaming.

Table 1

			Embodiment				Comparative example
									1	2	3	4	1	2
			Form (weight ratio)	The dicyclopentadiene-type solid epoxy		76	78	76							48	76	48
Naphthalene type liquid epoxy resin		20							20	20	50	20	50
				Acrylic resin-a that contains epoxy group(ing)		4	2	-						-	-	-
Acrylic resin-the b that contains epoxy group(ing)		-							-	4	2	-	-
				Trialkyl tetrahydrochysene anhydride phthalic acid		60	60	60						52	60	52
Tricarbimide modified solid decentralized imidazoles		8							8	8	8	8	8
				The imidazoles silane coupling agent		2	2	2						0.5	2	0.5
Surface-hydrophobicized pyrogenic silica		-							4	4	4	4	4
				The core-shell-type acrylic rubber particle that contains hydroxyl		-	-	5						5	5	5
Estimate	Gelation rate (weight %)	170 ℃ of curing in-1 minute							100	100	58	55	35				15
			170 ℃ of curing in-2 minutes	100	100	100	100	100						100
		Initial stage bonding force-A (N/25mm 2)							412	441	588	568	304		343
	Foamed state under 200 ℃			○	○	○	○	×						×

As shown in Table 1, the gelation rate of the adhesive epoxy resin cream that is obtained by embodiment 1-4 is all high and solidified nature is all good or good, and the initial stage, bonding force-A was good, does not see foaming simultaneously under 200 ℃, thereby can suppress the generation in space.

In contrast, the gelation rate of the adhesive epoxy resin cream that is obtained by the comparative example 1,2 that does not contain the high molecular polymer (acrylic resin that contains epoxy group(ing)) with epoxy group(ing) when 170 ℃ solidified in-1 minute is all low and solidified nature is all poor, and, initial stage, bonding force-A was poor, simultaneously under 200 ℃, see foaming, thereby can not suppress the generation in space.

(embodiment 5)

Acrylic resin-a, trialkyl tetrahydrochysene anhydride phthalic acid 50 weight parts, tricarbimide modified solid decentralized imidazoles 8 weight parts, aminosilane coupling agent 2 weight parts and surface-hydrophobicized pyrogenic silica 4 weight parts that dicyclopentadiene-type solid epoxy 76 weight parts, naphthalene type liquid epoxy resin 20 weight parts, 10 weight parts are contained epoxy group(ing) are dissolved in the vinyl acetic monomer, use the homodisperse type to stir instrument, low whipping speed is evenly to mix under the condition of 3000rpm, thereby the modulation solids component is the vinyl acetic monomer solution of the curable resin composition of 50 weight %.

Then, to use rod to be coated with machine by the vinyl acetic monomer solution of the above-mentioned curable resin composition that obtains and be coated on the surface on the demoulding treated side of thick polyethylene terephthalate (PET) thin slice of 50 μ m of demoulding processing, and make dried thickness reach 50 μ m, descended dry 3 minutes at 110 ℃ then, thereby make the adhesive epoxy resin thin slice.

(embodiment 6 and comparative example 3)

Except the combined group of adhesive epoxy resin thin slice (curable resin composition) being become to be defined as the composition shown in the table 2, make the vinyl acetic monomer solution (solids component is 50 weight %) and the adhesive epoxy resin thin slice of curable resin composition in the same manner with embodiment 5.

The performance of the adhesive epoxy resin thin slice that is obtained by embodiment 5, embodiment 6 and comparative example 3 with following method evaluation (4. observe by transmission electron microscope, 5. the second-order transition temperature of cured article, 6. initial stage bonding force-B, the bonding force after 7.PCT100 hour).The results are shown in the table 2.

4. transmission electron microscope (TEM) is observed

To in baking oven, carry out maintenance solidified adhesive epoxy resin thin slice with 30 minutes at 170 ℃ and be cut into film, and use perosmic anhydride that it is dyeed with slicing machine (microtome).Observe this sample (multiplying power is 100,000 times) with transmission electron microscope, observe the phase separation structure that forms by above-mentioned dyeing.

5. the second-order transition temperature of cured article

The adhesive epoxy resin thin slice was heating and curing 30 minutes at 170 ℃, was the visco-elasticity of measuring cured article under 3 ℃/minute the stretch mode condition at heat-up rate then, according to the crest temperature of tan δ set second-order transition temperature (℃).

6. initial stage bonding force-B

Stickup is cut into the quadrate adhesive epoxy resin thin slice that the length of side is 5mm on the glass epoxy substrate of FR-4, pastes thereon to have SiO ₂The silicon chip of passive film, the adhesion back of exerting pressure was heating and curing under 170 ℃ 30 minutes, made conjugant.Then, at the sectional fixture up and down of the conjugant that obtains,, obtain maximum breaking tenacity (N/25mm according to the draw speed up-down stretch of 5mm/min ²), and be defined as initial stage bonding force-B.

7.PCT100 the bonding force after hour

Under the condition of 120 ℃-85%RH, carry out the pressure kettle test (PCT) 100 hours of the conjugant made in the same manner when measuring initial stage bonding force-B, take out conjugant then, obtain maximum breaking tenacity (N/25mm in the same manner with 5. situation ²), and be defined as bonding force after PCT100 hour.

Table 2

		Embodiment		Comparative example
					5	6	3
		Form (weight ratio)	The dicyclopentadiene-type solid epoxy	76				50	50
Naphthalene type liquid epoxy resin	20				20	20
			Acrylic resin-a that contains epoxy group(ing)	10			-	-
Acrylic resin-the b that contains epoxy group(ing)	-				30	-
			Acrylic rubber-the c that contains epoxy group(ing)	-			-	30
Trialkyl tetrahydrochysene anhydride phthalic acid	50				45	40
			Tricarbimide modified solid decentralized imidazoles	8			8	8
Aminosilane coupling agent	2				2	2
			Surface-hydrophobicized pyrogenic silica	4			4	4
Estimate	Transmission electron microscope is observed				Mix	Mix			Be separated
		The second-order transition temperature of cured article (℃)	178	180			25173
	Initial stage bonding force-B (N/25mm 2)				441	510		225
		Bonding force after PCT100 hour	392	451			20

As shown in Table 2, the second-order transition temperature of the cured article of the adhesive epoxy resin thin slice that is obtained by embodiment 5,6 is all higher, do not demonstrate phase separation structure at resin in mutually, so initial stage bonding force-B is good, even simultaneously after PCT100 hour the decline of bonding force also less.

In contrast, the second-order transition temperature of cured article that has been replaced containing the adhesive epoxy resin thin slice that the comparative example 3 of the acrylic resin of epoxy group(ing) obtains by the acrylic rubber-c that contains epoxy group(ing) that makes of solution polymerization process is low, demonstrate the crest of tan δ at low temperatures, and phase separation structure has appearred, and initial stage bonding force-B is poor, simultaneously the decline highly significant of the bonding force after PCT100 hour.

(embodiment 7)

Acrylic resin-a, trialkyl tetrahydrochysene anhydride phthalic acid 50 weight parts, 1-cyano ethyl-2-phenylimidazole 4 weight parts, aminosilane coupling agent 2 weight parts, surface-hydrophobicized pyrogenic silica 4 weight parts that dicyclopentadiene-type solid epoxy 45 weight parts, naphthalene type liquid epoxy resin 45 weight parts, 10 weight parts are contained epoxy group(ing) are dissolved in vinyl acetic monomer, use the homodisperse type to stir instrument, low whipping speed be evenly stir under the condition of 3000rpm mixing, thereby the modulation solids component is the vinyl acetic monomer solution of the curable resin composition of 60 weight %.

Then, to use rod to be coated with device by the vinyl acetic monomer solution of the above-mentioned curable resin composition that obtains and be coated on the surface on the demoulding treated side of thick polyethylene terephthalate (PET) thin slice of 50 μ m of demoulding processing, and make dried thickness reach 40 μ m, descended dry 3 minutes at 110 ℃ then, form the adhesive epoxy resin layer.

(embodiment 8-12 and comparative example 4-7)

Except the combined group of adhesive epoxy resin thin slice (curable resin composition) being become to be defined as the composition shown in the table 3, make the vinyl acetic monomer solution (solids component is 40 weight %) and the adhesive epoxy resin thin slice of curable resin composition in the same manner with the situation of embodiment 7.

Performance (the observation (transmission electron microscope observation) of phase separation structure during 7.TEM dyeing of the adhesive epoxy resin thin slice that obtains by embodiment 7-12 and comparative example 4-7 with following method evaluation, 8. the observation of visco-elasticity tan δ crest temperature, 9.120 the measurement of ℃ dimethyl sulfoxide (DMSO) swelling ratio, 10. the measurement of extraction water pH, 11. the measurement of ionic conductivity, 12. the measurement of extraction chlorion impurity, 13. DIELECTRIC CONSTANT ' measurement, 14. the measurement of dielectric dissipation factor, 15. laser processing, 16. the measurement of minimum storage spring rate G ' during fusion, 17. defining tight produces, 18. the conducting of conjugant PCT is measured, the conducting of 19. conjugant TCT is measured).The results are shown in the table 3.

7. transmission electron microscope is observed

To in baking oven, carry out maintenance solidified adhesive epoxy resin thin slice with 30 minutes at 170 ℃ and be cut into film, and use perosmic anhydride that it is dyeed with slicing machine.Observe this sample (multiplying power is 100,000 times) with transmission electron microscope, observe the phase separation structure that forms by above-mentioned dyeing.

8. the observation of visco-elasticity tan δ crest temperature

With the viscoelasticity measurement device of stretch mode, be 3 ℃/minute at heat-up rate, measure in the scope of temperature-100 ℃～290 ℃, measure in baking oven, having carried out maintenance solidified adhesive epoxy resin thin slice with 30 minutes at 170 ℃.Observable graphic representation has the situation of the crest value temperature of two above tan δ also not miss, and has all carried out record.

9.120 the measurement of ℃ dimethyl sulfoxide (DMSO) swelling ratio

Weighing at 170 ℃ with the weight of carrying out the solidified adhesive sheet in 30 minutes, and with its dipping 5 minutes in being heated to 120 ℃ dimethyl sulfoxide (DMSO) (DMSO).Take out this thin slice after 5 minutes, carefully wipe solvent after, weigh once more with balance.

The DMSO swelling is than (%)=(dipping back weight-initial stage weight) * 100/ (initial stage weight)

Can represent with above-mentioned formula.

10. the measurement of extraction water pH

The adhesive epoxy resin thin slice was heating and curing in 170 ℃ baking oven 30 minutes, takes by weighing the about 1g of cured article of adhesive epoxy resin thin slice then.Then, this cured article is cut into tiny size and drops in the developmental tube of glass interpolation 10g distilled water, usefulness blowtorch (burner) seal test pipe, add extraction heat 12 hours when in 110 ℃ baking oven, shaking often, use pH meter to measure the pH of extraction water then.

11. the measurement of ionic conductivity

Use the ionic conductivity survey meter to measure the ionic conductivity (μ S/cm) of above-mentioned extraction water.

12. extract the measurement of chlorion impurity

Use ion chromatography, measure by the chlorion impurity level (ppm) in the above-mentioned extraction water that obtains.

13. DIELECTRIC CONSTANT ' measurement, the measurement of 14. dielectric dissipation factors

To Measuring Dielectric Constant and dielectric dissipation factor under the condition that is 1GHz in frequency at 170 ℃ of samples after solidifying 30 minutes.

15. laser processing

Use carbon dioxide laser, the microscopic examination hole shape is used in the circular hole (diameter is about 100 μ m) of processing then on the adhesive epoxy resin thin slice that attaches the PET thin slice up and down, estimates laser processing according to following criterion.

[criterion]

Zero ... the smoothness of hole shape and communicating pores is all good.

* ... hole shape is imperfect.

16. the measurement of minimum storage spring rate G ' during fusion

With adhesive epoxy resin thin slice (solidify before) stacked with the heat lamination device be the thickness of about 600 μ m, with 45 ℃/minute heat-up rate it is warming up to 200 ℃ by 25 ℃ then, the spring rate of measurement when frequency is the condition down cut of 100rad/s (G ').At this moment, the fusing of adhesive epoxy resin thin slice and solidifying simultaneously takes place, and the spring rate of expression Schwellenwert is at this moment pronounced be minimum spring rate { (G ') Pa}.

17. defining tight produces

Clip the adhesive epoxy resin thin slice with glass epoxy substrate and silicon chip (length of side is the square of 1cm), carried out bondingly 200 ℃ of following thermo-compressed in 30 seconds, use ultrasonic wave to peel off failure detector and confirm to have this moment tight to produce.

18. the conducting of conjugant PCT is measured

It is on the FR-4 substrate that above-mentioned epoxy laminate is sticked on the thick glass/epoxy of 20mm * 20mm * 1.0mm, and (nickel plating 5 μ m, gold-plated 0.3 μ m on the thick Copper Foil of 18 μ m) is as follows for described FR-4 substrate distribution: when being electrically connected by the IC chip and the metal wiring in the IC chip form daisy chain (daisy chain).Be situated between then help this thin slice with IC chip (size: 10mm * 10mm is equipped with 172 principal column (stud) projections of making by terminal conjunction method in advance (big or small 100 μ m, high about 50 μ m) along outer periphery) and electrode base board at 78N/cm ²Load under heat and engage according to 190 ℃ of-15 seconds, 230 ℃ orders of-15 seconds, then 125 ℃ of following maintenances 1 hour, thereby make the conducting conjugant.

With respect to the conducting conjugant that obtains, after confirming that all electrodes have high conducting resistance stability at normal temperatures, the conducting conjugant is moved in pressure kettle test (PCT) environment (120 ℃, 85%RH), and all conduction resistance values changed for 10% required time under the measurement PCT testing circumstance.

19. the conducting of conjugant TCT is measured

Adopt the method identical to make the conducting conjugant with above-mentioned situation, be placed on thermal cycling test machine (125 ℃ of 40 ℃ of , each is 10 minutes) carry out thermal cycling test (TCT), under suitable cycle number, take out and confirm the variation of conduction resistance value, measure the cycle number of conduction resistance value variation more than 10%.

Table 3

		Embodiment						Comparative example
												7	8	9	10	11	12	4	5	6	7
		Form (weight part)	Naphthalene type liquid epoxy resin	45	45	45	45	45	45	45	45											45	45
Dicyclopentadiene-type epoxy resin	45											45	45	45	45	45	45	45	45	45
			Acrylic resin-a that contains epoxy group(ing)	10	10	10	10	10	10	-	10										10	-
Acrylic rubber-the d that contains epoxy group(ing)	-											-	-	-	-	-	5	5	30	-
			Polyvinyl butyral resin	-	-	-	-	-	-	-	-										-	10
Trialkyl tetrahydrochysene anhydride phthalic acid	50											50	50	50	50	58	50	50	50	-
			Dyhard RU 100	-	-	-	-	-	-	-	-										-	5
2-ethyl-4-methylimidazole	-											-	-	-	-	6	-	-	-	-
			1-cyano ethyl-2-phenylimidazole	4	4	6	4	6	-	4	4										4	1.5
Aminosilane coupling agent	2											2	2	2	2	2	2	2	2	2
			Surface-hydrophobicized pyrogenic silica (median size is 10nm, and maximum particle diameter is 12nm)	-	4	4	4	-	4	-	4										4	-
Spherical silicon dioxide (median size 5 μ m, maximum＜15 μ m)	-											-	-	-		-	100	-	-	-
			The core-shell-type acrylic rubber particle that contains hydroxyl	-	5	-	-		-	-	-										-	-
The core-shell-type acrylic rubber particle that contains carboxyl	-											-	10	-		-	-	-	-	-
			Estimate	Phase separation structure during TEM dyeing	Mix	-	-	Mix	Mix	Mix	Be separated										Be separated	Be separated	Be separated
Visco-elasticity tan δ crest temperature	178	178										182	178	185	172	-20175	-25173	-25170	92220
				120 ℃ of dimethyl sulfoxide (DMSO) swelling ratios (%)	28	30	25	-	-	-	55									50	85	-
Extraction water pH	7	7.2										7.9	8	7.4	4.7	-	7.5	7	9.1
				Ionic conductivity (μ S/cm)	40	35	42	40	55	140	75									72	80	350
Extraction chlorion impurity (ppm)	5	3										5	3	6	146	-	19	25	173
				DIELECTRIC CONSTANT '	3.1	3.1	3.1	-	-	-	-									-	-	3.5
Dielectric dissipation factor tan δ	0.015	0.015										0.016	-	-	-	-	-	-	0.02
				Laser processing	○	○	○	○	○	○	×									○	○	○
Minimum storage spring rate G ' (10 during fusion 3/Pa)	3	5										-	-	-	-	0.5	-	-	-
				Have or not and produce the space	Do not have	Do not have	Do not have	Do not have	Do not have	Do not have	Have									Do not have	Do not have	Do not have
PCT conducting (h)	＞400	＞400										350	＞400	＞400	-	＜100	＜200	＜100	300
				TCT conducting (circulation)	900	＞1000	＞1000	＞1000	＞1000	-	＞1000									＞1000	500	＞1000

As shown in Table 3, the adhesive epoxy resin thin slice with regard to being obtained by embodiment 7-11 does not demonstrate phase separation structure, so the DMSO swelling is lower than very during high temperature.On the other hand, in showing the comparative example 4-6 of phase separation structure, also can observe the crest value of two tan δ, and the DMSO swelling is quite higher than also.Therefore, the PCT performance is compared also relatively poor with embodiment obviously.With regard to by the extraction water pH adhesive epoxy resin thin slice that obtains of near the embodiment 12 neutral and comparative example 7 not, ionic conductivity is than higher in addition, and this explanation has free ions and washes out.Hence one can see that, and generally be considered to have the chlorion impurity level of bigger relation very many with electrical insulating property and electrode corrosion this moment.In addition, with regard to the adhesive epoxy resin thin slice that is obtained by comparative example 7, specific inductivity, dielectric dissipation factor all show higher value, have obtained the relatively poor result of physics value.

Minimum storage spring rate during for fusion, the value of the adhesive epoxy resin thin slice that is obtained by comparative example 4 is very low, and hence one can see that has formed the conjugant that adhering resin enters the space in mutually under not suppressing the foamy condition that is produced by volatile component.In addition, during the adhesive epoxy resin thin slice that obtains when the adhesive epoxy resin thin slice that relatively obtains by embodiment 7 with by embodiment 8, though not obvious, the adhesive epoxy resin thin slice that is obtained by the embodiment 8 that has added the core-shell-type rubber particles has higher TCT cycle performance.This may be to be solidified by the stress relaxation of rubber particles to produce.

In addition, by the vinyl acetic monomer solution of the synthetic curable resin composition of embodiment 7-9 as the interlayer caking agent, use 8 inches wafers to make the semiconductor packages of estimating usefulness of following method.

At first, will on 8 inches wafers of the external copper projection that disposes 110 μ m * 110 μ m, high 20 μ m,, and make the thickness after the curing reach 25 μ m with caking agent between the spin coater coating layer.After the coating, wafer was placed in the warm braw drying oven 110 ℃ * 5 minutes+120 ℃ * 60 minutes, the interlayer caking agent is solidified.Then, use shredder to grind the top layer part of solidified interlayer caking agent, expose the copper projection.

Use known photolithography, form distribution copper circuit pattern again, be configured to planar so that be equipped with the copper post position of the solder ball of encapsulation.After forming again the wiring circuit pattern, use known photolithography to form the copper post, use known wafer level solder ball support, make the wafer-level packaging that is equipped with solder ball (diameter is 300 μ m).Then, cutting is equipped with the wafer of solder ball, makes one IC (size: 10mm * 10mm is provided with 172 juts with planar), thereby forms the semiconductor packages of estimating usefulness.

The semiconductor packages evaluation scolding tin thermotolerance of the evaluation usefulness that use obtains, the conducting reliability under the PCT environment and the conducting reliability under the TCT environment, it is more than 5 times that results verification goes out the scolding tin thermotolerance, the PCT reliability is 400 hours, and the TCT reliability is 1000 more than the circulation.

Can confirm also to can be used as the interlayer caking agent by above by the vinyl acetic monomer solution of the synthetic curable resin composition of embodiment 7-9.

In addition, made semiconductor crystal wafer distribution base plate for packaging again as semiconductor packages of estimating usefulness at this, and like this too under the situation of modular printing wiring board etc.

(embodiment 13)

Use the homodisperse type to stir instrument, with dicyclopentadiene-type solid epoxy 45 weight parts, naphthalene type liquid epoxy resin 45 weight parts, contain the acrylic resin (molecular-weight average 10,000 of epoxy group(ing), epoxy equivalent (weight) 500) 4 weight parts, trialkyl tetrahydrochysene anhydride phthalic acid 50 weight parts, 1-cyano ethyl-2-phenylimidazole 4 weight parts, aminosilane coupling agent 2 weight parts are evenly mixing, thereby obtain the cementability epoxy paste, and it is used as nonconductive paste.

(embodiment 14-21 and comparative example 8,9)

Except the combined group with cream becomes to be defined as the composition shown in the table 4, make nonconductive paste (embodiment 14-16) or anisotropic conductive cream (embodiment 17-21, comparative example 8,9) in the same manner with the situation of embodiment 13.

The nonconductive paste that obtains by embodiment 13-21 and comparative example 8,9 with above-mentioned method evaluation or the performance of anisotropic conductive cream (pH of extraction water, chlorion impurity level, the crest temperature of tan δ in phase separation structure, the viscoelasticity measurement when utilizing tem observation dyeing, ionic conductivity, specific inductivity (ε ') and dielectric dissipation factor (tan δ)).

In addition, use the anisotropic conductive cream and IC chip and the substrate that obtain by embodiment 17-21, comparative example 8,9, made the semiconductor packages of estimating usefulness in order to the below method.

As IC chip (size: 10mm * 10mm), use sets in advance 172 principal column projection (big or small 100 μ m that make by terminal conjunction method along the periphery, high about 50 μ m) chip, as substrate, when using distribution to become to help the IC chip to be electrically connected by Jie and the metal wiring in the IC chip form the thick substrate (glass/epoxy is FR-4) of 20mm * 20mm * 1.0mm of daisy chain (nickel plating 5 μ m, gold-plated 0.3 μ m on the thick Copper Foil of 18 μ m).

At first, substrate was carried out in the warm braw drying oven air-dry 120 ℃ * 6 hours, remove the moisture in the substrate.

Then, will be filled in by the anisotropic conductive cream that embodiment 17-21, comparative example 8,9 obtain in the syringe (Musashi engineering society system).At the front end of this syringe accurate nozzle (Musashi engineering society system, spray nozzle front end diameter 0.3mm) is installed, is used diverting device (Musashi engineering society system), coating anisotropic conductive cream in the IC chip bonding area on the substrate of drying, glue spread is 40mg.

(Shibuya industry society system DB100), is partly carried out flip-chip to the electrode part of the substrate through being coated with the electrode of IC chip and is connected to use flip-chip bonder.Condition of contact is 78N/cm ², 190 ℃ * 15 seconds+230 ℃ * 15 seconds.In 120 ℃ of warm braw drying ovens, made the resin completely solidified then, thereby make the semiconductor packages of estimating usefulness through 1 hour.

The semiconductor packages of the evaluation usefulness of use is estimated the thermotolerance of 20. scolding tin and is estimated the conducting reliability under the PCT environment, the conducting reliability under the TCT environment with above-mentioned method with following method.The results are shown in the table 4.In addition, in the table 4, the position of using "-" to represent shows fails to measure.

20. the thermotolerance of scolding tin

With the semiconductor package of estimating usefulness be contained in drying conditions be 125 ℃ * 6hr, wet condition be handle under the condition of 30 ℃/80% * 48hr after, under the imposing a condition of 250 ℃ * 30s, carry out the scolding tin reflow treatment, the conducting of electrode and peeling off of resistance change and interlayer after confirming to handle.Under wet condition is the condition of 30 ℃/80% * 48hr, handle sample once more after the backflow, under the imposing a condition of 250 ℃ * 30s, carry out the scolding tin reflow treatment then, confirm conducting of reflow treatment rear electrode for the second time and peeling off of resistance change and interlayer.Carry out this processing always, reach 5 times, thereby estimate the scolding tin thermotolerance up to the backflow number of times.In addition,, change more than 10%, then be judged as bad if resistance change is compared with the resistance value at initial stage even having under the situation of conducting.Peeling off of interlayer is to use ultrasonic fault detection image device (Hitachi builds machine Off ァ ィ Application テ ッ Network society system, mi-scope hyperII) to confirm.

Table 4

		Embodiment									Comparative example
													13	14	15	16	17	18	19	20	21	8	9
		Form (weight ratio)	Naphthalene type liquid epoxy resin	45	65	45	45	45	45	45	45	45												45	65
Dicyclopentadiene-type epoxy resin	45												25	45	45	45	45	45	45	45	45	25
			Acrylic resin-the b that contains epoxy group(ing)	4	4	2	4	4	4	4	4	4											-	-
Trialkyl tetrahydrochysene anhydride phthalic acid	50												55	50	50	50	50	50	50	50	50	55
			Acrylic rubber-the d that contains epoxy group(ing)	-	-	-	-	-	-	-	-	-											4	4
1-cyano ethyl-2-phenylimidazole	4												4	4	6	4	4	4	4	4	4	4
			Aminosilane coupling agent	2	2	2	2	2	2	2	2	2											2	2
Spherical silicon dioxide (median size 5 μ m, maximum＜15 μ m)	-												-	-	-	-	-	-	-	-	-	-
			Surface-hydrophobicized pyrogenic silica (median size 10nm, maximum 12nm)	-	-	4	4	-	-	4	4	4											-	-
The core-shell-type acrylic rubber particle that contains hydroxyl	-												-	5	5	-	-	5	5	5	-	-
			Ag particle (median size 7 μ m)	-	-	-	-	20	-	-	-	-											20	20
Ni particle (median size 7 μ m)	-												-	-	-	-	20	20	-	-	-	-
			Resin core plating Au particle (median size 3 μ m)	-	-	-	-	-	-	-	20	-											-	-
Insulation covers process resin core plating Au particle (median size 2 μ m)	-												-	-	-	-	-	-	-	30	-	-
			Estimate	Phase separation structure (only to resin layer) during TEM dyeing	Mix	Mix	-	-	-	-	-	-											-	Be separated	Be separated
Visco-elasticity tan δ crest temperature (℃)	178	185											178	182	178	180	178	178	182	-15178	-15173
				Extraction water pH	7	7.1	7.2	7.9	7	7.1	7.2	7.1										7.9	6.5	4.5
Extraction chlorion impurity (ppm)	5	4											3	5	5	4	3	4	5	14	140
				Ionic conductivity (μ S/cm)	40	30	35	42	40	30	35	32										42	70	95
DIELECTRIC CONSTANT '	3.1	3.1											3.1	3.1	3.1	3.1	3.1	3.1	3.1	3.1	3.1
				Dielectric dissipation factor tan δ	0.015	0.015	0.015	0.016	0.015	0.015	0.015	0.015										0.016	0.015	0.015
PCT conducting (h) (in the resistance change 10%)	300	300											＞400	＞400	300	300	＞400	＞400	＞400	200	300
				TCT conducting (circulation) (in the resistance change 10%)	800	900	＞1000	＞1000	800	900	＞1000	＞1000										＞1000	＞1000	＞1000
Scolding tin thermotolerance (number of times) (in the resistance change 10%)	5	5											5	5	5	5	5	5	5	3	3

As known from Table 4, the chlorion impurity level is few in the anisotropic conductive cream that is obtained by embodiment 17-21.In addition, just show with regard to the anisotropic conductive cream that the embodiment 17 of the acrylic resin that contains epoxy group(ing) of intermiscibility obtains by containing with respect to dicyclopentadiene-type solid epoxy and naphthalene type liquid epoxy resin, during with the tem observation cured article, in epoxy resin-base, do not observe and be separated, in addition, the ionic conductivity of the anisotropic conductive cream that is obtained by embodiment 17-21 is all lower.In addition, use evaluation that the anisotropic conductive cream that obtained by embodiment 17-21 makes with the scolding tin thermotolerance of semiconductor packages, PCT environment down and the conducting reliability under the TCT environment all good.And then, use contains the semiconductor packages that the anisotropic conductive cream that is obtained by embodiment 19-21 of low elasticity particle (core-shell-type acrylic rubber particle) forms to be compared with the semiconductor packages that the anisotropic conductive cream that uses the embodiment 17,18 that does not contain these forms, under the PCT environment with the TCT environment under the conducting better reliability.

In contrast, show with regard to the anisotropic conductive cream that obtains by comparative example 8,9 of the acrylic rubber that contains epoxy group(ing) of immiscible property with regard to containing with respect to naphthalene type liquid epoxy resin and dicyclopentadiene-type solid epoxy, during with the tem observation cured article, observed in epoxy resin-base and be separated, ionic conductivity is also high.

In addition,, adopt following method to connect semi-conductor chip and substrate, thereby made the semiconductor packages of estimating usefulness by the cementability epoxy paste that is obtained by embodiment 13-15 is lost filler as filling out.

Based on glass epoxide base material FR-4 equivalence product, chip at the substrate (4 laminate) of having finished Cu distribution operation, through hole plating and welding resistance operation carries on the part, semi-conductor chip (the size: 10mm * 10mm of 172 subsidiary high-melting-point scolding tin projections is disposed in setting along the periphery, package size 100 μ m, high about 100 μ m) flip-chip bonder, under the prone state of this chip, position to scolding tin jut and opposed base-plate terminal part is adjusted, and carry out this crimping under 230 ℃ of temperature, the 10kg that exerts pressure, the condition of 5 seconds clamping times.At this moment, can confirm to finish simultaneously scolding tin projection and base-plate terminal part joint, and chip surface and substrate is bonding, the scolding tin projection is drawn as column.

Then, with common IR reflow ovens, scolding tin is refluxed.Through after this operation, confirm to adopt the position skew when facing down bonding method to obtain revisal, and kept the shape of column scolding tin projection.

Then, in Musashi engineering (society) system syringe, fill the filler resin thanks to of filling out of the present invention, and the accurate nozzle (spray nozzle front end diameter 0.3mm) of Musashi engineering society system is installed at the front end of this syringe, use diverting device, by the space potting resin of chip fore-end between chip and substrate.

Then, under 125 ℃ * 1 hour condition, in the warm braw drying oven, make the resin completely solidified, afterwards, (Hitachi changes into industrial society system to use sealing material, ェ Port キ シ モ-Le デ ィ Application グ コ Application パ ゥ Application De CEL9200), obtain with common transfer mold (180 ℃ of forming temperatures, compacting pressure 1.5kN/cm ²) covered the sealing prod at the whole back side of chip.Then, use the solder ball forming device, form solder ball with array-like, obtain to estimate the semiconductor packages of usefulness at substrate back.

The evaluation that obtains has been carried out-45 ℃～125 ℃ temperature cycle evaluation test with semiconductor packages,, do not seen breaking of scolding tin projection even also do not occur the unusual of conducting result in the sample of result after 1000 circulations.Evaluation semiconductor packages behind the cutting test is observed around the scolding tin jut, and the result can confirm do not have crack etc. the peripheral portion person of the whole periphery of each scolding tin projection and semi-conductor chip.In addition, under 30 ℃, the condition of 80%RH, make its moisture absorption after 48 hours, with scolding tin dipping (280 ℃, 30 seconds), observe with the ultrasonic fault detection defect-detecting equipment afterwards, but on the interface on sealing resin and chip passivation surface, still do not see and peeling off or fissured existence.In addition, carrying out high temperature and humidity test (120 ℃/80%RH, 500 hours) back conducting result does not have unusually yet, does not see breaking of scolding tin projection yet.The evaluation semiconductor packages of cutting high temperature and humidity test is observed around the scolding tin jut, and the result can confirm crack etc. not occur at the peripheral portion of whole periphery of each scolding tin projection and semi-conductor chip.

Therefore, can confirm that the cementability epoxy paste that is obtained by embodiment 13-15 also is suitable as fills out filler thanks to.

(embodiment 22)

Acrylic resin-a, trialkyl tetrahydrochysene anhydride phthalic acid 50 weight parts, 1-cyano ethyl-2-phenylimidazole 4 weight parts, aminosilane coupling agent 2 weight parts and silver particles (median size 7 μ m) 20 weight parts that dicyclopentadiene-type solid epoxy 45 weight parts, naphthalene type liquid epoxy resin 45 weight parts, 10 weight parts contained epoxy group(ing) are dissolved in vinyl acetic monomer, use the homodisperse type to stir instrument, low whipping speed is evenly to mix under the condition of 3000rpm, thereby the modulation solids component is the vinyl acetic monomer solution of the curable resin composition of 40 weight %.In addition, above-mentioned silver particles is used with the form of varnish.

Then, on the demoulding treated side of polyethylene terephthalate (PET) thin slice that it is 50 μ m that the machine that will be coated with by the vinyl acetic monomer solution use rod of the above-mentioned curable resin composition that obtains is coated on the surperficial thickness of handling through the demoulding, and make dried thickness reach 42 μ m, descended dry 3 minutes at 110 ℃ then, thereby form the adhesive epoxy resin layer.Two PET thin slices that will be formed with this adhesive epoxy resin layer carry out stacked processing and make the adhesive epoxy resin thin slice under 80 ℃, this moment, the adhesive epoxy resin layer faced one another face.The adhesive epoxy resin thin slice that obtains is in the adhesive epoxy resin layer and is sandwiched in two states between the PET thin slice.

(embodiment 23-26 and comparative example 10,11)

Except combined group being become to be defined as the composition shown in the table 5, make the conductive connection sheet (embodiment 22-26, comparative example 10,11) that electrically conductive microparticle do not expose, the conductive connection sheet (embodiment 27) that electrically conductive microparticle exposes in the same manner with the situation of embodiment 22.

In addition, as electrically conductive microparticle, use following material to be mixed in the resin in the table 5 with the varnish form.

Cover with thermoplastic resin

Silver particles: median size 7 μ m

Ni particle: median size 7 μ m

The gold-plated particle of resin core: median size 3 μ m (ponding chemical industry society system " ミ Network ロ パ-Le A ")

The gold-plated particle of insulation covering resin core: median size 2 μ m, ponding chemical industry society system (ミ Network ロ パ-Le A)

Formed material.

(embodiment 27)

On the adhesive epoxy resin thin slice of the long 2cm that obtains, wide 2cm,, use CO in order to be formed on per 1 square centimeter electrode terminal that 172 pins are arranged on square ₂The laser alignment arrangements communicating pores of taper of surface 120 μ m, the back side 85 μ m of multiple row, make it to conform to the electrode position of IC chip.These row be spaced apart about 4mm, the be separated by spacing of 200 μ m of each communicating pores of each row is arranged, the CV value in each communicating pores aperture is 2%, shape is 1.04 than (minor axis in the major diameter/hole in hole).

Rear side to this adhesive epoxy resin thin slice, be covered with the suction inlet of diameter 8mm, and make it to cover all communicating poress and the place of not sewing, under the vacuum tightness of-50kPa, aspirate afterwards, to the electrically conductive microparticle that is positioned at adhesive epoxy resin slice surfaces side (median size 105 μ m, behind top layer plating 0.2 μ m nickel again plating the electrically conductive microparticle of gold of 2.3 μ m) carry out the absorption of several seconds.At this moment, having mesh on suction inlet is the steel sieve of 50 μ m, to be used to the supporting adhesive epoxy resin thin slice,, be attracted to the communicating pores position in addition of adhesive epoxy resin thin slice to avoid electrically conductive microparticle while carry out antistatic the suction on this basis.After burying neither too much nor too little 1 electrically conductive microparticle underground on each communicating pores that is pumped in the adhesive epoxy resin thin slice by electrically conductive microparticle, stop suction, thereby make conductive connection sheet.In addition, after the suction, use the softish brush to remove the lip-deep impurity of conductive connection sheet, to prevent unforeseen circumstances.In addition, the conductive connection sheet in this stage is in its uncured state.

The performance of the conductive connection sheet that obtains by embodiment 23-27 and comparative example 10,11 with above-mentioned method evaluation (pH of extraction water, chlorion impurity level, tan δ crest temperature in phase separation structure, the viscoelasticity measurement when dyeing with tem observation, ionic conductivity, specific inductivity (ε ') and dielectric dissipation factor (tan δ)).In addition, use the conductive connection sheet that obtains by embodiment 23-27 and comparative example 10,11 to make the semiconductor packages of estimating usefulness with aforesaid method, and estimated conducting reliability under scolding tin thermotolerance, the PCT environment and the conducting reliability under the TCT environment for this semiconductor packages.The results are shown in the table 5.

Table 5

Mixture		Embodiment						Comparative example
										22	23	24	25	26	27	10	11
		Adhesive epoxy resin sheet	Naphthalene type liquid epoxy resin	45	45	45	45	45	45									45	45
Dicyclopentadiene-type epoxy resin	45									45	45	45	45	45	45	45
			Acrylic resin-a that contains epoxy group(ing)	10	10	10	10	10	10								-	-
Acrylic rubber-the d that contains epoxy group(ing)	-									-	-	-	-	-	10	10
			Trialkyl tetrahydrochysene anhydride phthalic acid	50	50	50	50	50	50								50	60
1-cyano ethyl-2-phenylimidazole	4									4	4	4	6	4	4	4
			Aminosilane coupling agent	2	2	2	2	2	2								2	2
Surface-hydrophobicized pyrogenic silica (median size 10nm, maximum 12nm)	-									-	4	4	4	4	-	-
			The core-shell-type acrylic rubber particle that contains hydroxyl	-	-	5	5	5	5								-	-
Ag particle (median size 7 μ m)	20									-	-	-	-	-	20	20
			Ni particle (median size 7 μ m)	-	20	20	-	-	-								-	-
Resin core plating Au particle (median size 3 μ m)	-									-	-	20	-	-	-	-
			Insulation covers process resin core plating Au particle (median size 2 μ m)	-	-	-	-	30	-								-	-
Resin core plating Au particle (median size 100 μ m)														Layout type
			Estimate	Phase separation structure (only to resin layer) during TEM dyeing	Mix	Mix	-	-	-								-	Be separated	Be separated
Visco-elasticity tan δ crest temperature (℃)	178	180								178	178	182	178	-20175	-20175
				Extraction water pH	7	7.1	7.2	7.1	7.9							7.2	6.5	4.5
Extraction chlorion impurity (ppm)	5	4								3	4	5	3	14	130
				Ionic conductivity (μ S/cm)	40	30	35	32	42							35	70	75
DIELECTRIC CONSTANT '	3.1	3.1								3.1	3.1	3.1	3.1	3.1	3.1
				Dielectric dissipation factor tan δ	0.015	0.015	0.015	0.015	0.016							0.015	0.015	0.015
PCT conducting (h) (in the resistance change 10%)	300	300								＞400	＞400	＞400	＞400	200	200
				TCT conducting (circulation) (in the resistance change 10%)	800	900	＞1000	＞1000	＞1000							＞1000	＞1000	＞1000
Scolding tin thermotolerance (number of times) (in the resistance change 10%)	5	5								5	5	5	5	3	3

By 5 as can be known, in the conductive connection sheet of making by embodiment 23-27 (particulate is exposed type, particulate exposed type not), also similarly obtained high joint reliability with the juncture that uses the adhesive epoxy resin thin slice of making by embodiment 7-12 of not introducing electrically conductive microparticle.

Industrial utilizability

Curable resin composition of the present invention is good owing to solidifying its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., can show high bonding reliability and the high conducting reliability when forming conductive material, to connect with, conduction that cream uses etc. with, conductive connection sheet with, adhesive epoxy resin thin slice with adhesive epoxy resin cream be the various industrial uses of representative so be suitable for.

In addition, adhesive epoxy resin cream of the present invention and adhesive epoxy resin thin slice are owing to use the curable resin composition of the invention described above to make, so it is good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., can show high bonding reliability, be suitable for the joint of various electron devices.

In addition, conduction connection cream of the present invention and conductive connection sheet are owing to use adhesive epoxy resin cream of the invention described above and adhesive epoxy resin thin slice to make, so it is good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., can show high bonding reliability and high conducting reliability, the conducting that is suitable for various electron devices engages.

Also have, interlayer caking agent of the present invention, nonconductive paste, fill out thanks to filler, non-conductive film and die attachment film owing to use adhesive epoxy resin cream of the invention described above and adhesive epoxy resin thin slice to make, so it is good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., can show high bonding reliability, be suitable for the joint of various electron devices.

In addition, anisotropic conductive cream of the present invention, anisotropic conducting film and flip-chip band are owing to use the conduction of the invention described above to be connected cream and conductive connection sheet making, so it is good to solidify its physical strength of back, thermotolerance, wet fastness, flexible, cold-resistant thermal cycling, anti-scolding tin backflow, dimensional stability etc., can show high bonding reliability and high conducting reliability, the conducting that is suitable for various electron devices engages.

In addition, electronic component joined body of the present invention is owing to the curable resin composition that uses the invention described above, adhesive epoxy resin cream, adhesive epoxy resin thin slice, conduction connect cream, conductive connection sheet, nonconductive paste, fill out any making of losing in filler, non-conductive film, die attachment film, anisotropic conductive cream, anisotropic conducting film or the flip-chip band, so can show high bonding reliability and high conducting reliability.

Claims (21)

1. curable resin composition, it is characterized in that containing: mix second-order transition temperature and be below 20 ℃, the second-order transition temperature of shell portion is the rubber particles of the core shell structure more than 40 ℃ with composition epoxy resin that the Resins, epoxy of Dicyclopentadiene (DCPD) skeleton, the Resins, epoxy with naphthalene skeleton and hardener for epoxy resin form and core.

2. an adhesive epoxy resin cream is characterized in that being made up of the described curable resin composition of claim 1.

3. an interlayer caking agent is characterized in that being made up of the described adhesive epoxy resin cream of claim 2.

4. a nonconductive paste is characterized in that being made up of the described adhesive epoxy resin cream of claim 2.

5. fill out filler thanks to for one kind, it is characterized in that forming by the described adhesive epoxy resin cream of claim 2.

6. an adhesive epoxy resin thin slice is characterized in that by the described curable resin composition of claim 11 is configured as laminar formation.

7. adhesive epoxy resin thin slice as claimed in claim 6 is characterized in that the storage spring rate (G ') of the thing that is heating and curing that is heating and curing by heating up with 45 ℃/minute heat-up rate surpasses 1 * 10 ³Pa.

8. as claim 6 or 7 described adhesive epoxy resin thin slices, it is characterized in that before curing, being-20 ℃～40 ℃ based on the crest temperature of the tan δ of dynamic viscoelastic, be more than 120 ℃ after the curing.

9. a non-conductive film is characterized in that being made of claim 6,7 or 8 described adhesive epoxy resin thin slices.

10. a die attachment film is characterized in that being made of claim 6,7 or 8 described adhesive epoxy resin thin slices.

11. a conduction connects cream, it is characterized in that forming by electrically conductive microparticle is contained in the described adhesive epoxy resin cream of claim 2.

12. an anisotropic conductive cream is characterized in that connecting cream by the described conduction of claim 11 forms.

13. conductive connection sheet, it is characterized in that the conductive connection sheet be made up of claim 6,7 or 8 described adhesive epoxy resin thin slices and electrically conductive microparticle, at least a portion of above-mentioned electrically conductive microparticle is exposed from above-mentioned adhesive epoxy resin thin slice.

14. a conductive connection sheet is characterized in that being embedded with the electrically conductive microparticle less than the thickness of above-mentioned adhesive epoxy resin thin slice in claim 6,7 or 8 described adhesive epoxy resin thin slices.

15. an anisotropic conducting film is characterized in that being made up of the described conductive connection sheet of claim 14.

16. conductive connection sheet, it is the conductive connection sheet that forms by resin of binding property thin slice and electrically conductive microparticle, described resin of binding property thin slice is by containing by adding that softening agent is given fusible resin and being that the adhesive resin composition of the aqueous Resins, epoxy with naphthalene skeleton constitutes at normal temperatures, it is characterized in that, above-mentioned resin of binding property thin slice based on the crest temperature of the tan δ of dynamic viscoelastic before curing in-20 ℃～40 ℃ scope, be more than 120 ℃ after the curing, simultaneously dispose above-mentioned electrically conductive microparticle on the optional position of above-mentioned resin of binding property thin slice, at least a portion of above-mentioned electrically conductive microparticle is exposed from above-mentioned resin of binding property thin slice.

17. conductive connection sheet as claimed in claim 16 is characterized in that the unit elongation for the resin of binding property thin slice after the curing of the resin of binding property thin slice after solidifying after carrying out the pressure kettle test under 120 ℃ of temperature, humidity 85%RH, the condition of 12 hours time is below 5%.

18. a flip-chip band is characterized in that being made of claim 13,16 or 17 described conductive connection sheets.

19. electronic component joined body, it is characterized in that utilizing the described curable resin composition of claim 1, the described adhesive epoxy resin cream of claim 2, the described interlayer caking agent of claim 3, the described nonconductive paste of claim 4, the described filler thanks to of filling out of claim 5, the described conduction of claim 11 connects cream, the described anisotropic conductive cream of claim 12, claim 6,7 or 8 described adhesive epoxy resin thin slices, the described non-conductive film of claim 9, the described die attachment film of claim 10, claim 13,14,16 or 17 described conductive connection sheets, the described anisotropic conducting film of claim 15, perhaps any in the described flip-chip band of claim 18 engages the projected electrode of the overshooting shape of electron device and other electrode state with conducting and form.

20. electronic component joined body, it is characterized in that utilizing the described curable resin composition of claim 1, the described adhesive epoxy resin cream of claim 2, the described interlayer caking agent of claim 3, the described nonconductive paste of claim 4, the described filler thanks to of filling out of claim 5, the described conduction of claim 11 connects cream, the described anisotropic conductive cream of claim 12, claim 6,7 or 8 described adhesive epoxy resin thin slices, the described non-conductive film of claim 9, the described die attachment film of claim 10, claim 13,14,16 or 17 described conductive connection sheets, the described anisotropic conducting film of claim 15, perhaps any in the described flip-chip band of claim 18 engages and is selected from die-attach area, ceramic substrate, resin substrate, silicon substrate, at least a circuit substrate in compound semiconductor substrate and the glass substrate and forming.

21. electronic component joined body as claimed in claim 20 is characterized in that resin substrate is glass epoxy substrate, Bismaleimide Triazine substrate or polyimide substrate.