WO2015033834A1 - 硬化性組成物及び接続構造体 - Google Patents

硬化性組成物及び接続構造体 Download PDF

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WO2015033834A1
WO2015033834A1 PCT/JP2014/072422 JP2014072422W WO2015033834A1 WO 2015033834 A1 WO2015033834 A1 WO 2015033834A1 JP 2014072422 W JP2014072422 W JP 2014072422W WO 2015033834 A1 WO2015033834 A1 WO 2015033834A1
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Prior art keywords
curable composition
group
weight
particles
phenoxy resin
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PCT/JP2014/072422
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English (en)
French (fr)
Japanese (ja)
Inventor
石澤　英亮
敬士 久保田
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積水化学工業株式会社
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Priority to CN201480025623.2A priority Critical patent/CN105189655B/zh
Priority to JP2014543031A priority patent/JP5820536B2/ja
Priority to KR1020157024483A priority patent/KR102167312B1/ko
Publication of WO2015033834A1 publication Critical patent/WO2015033834A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • the present invention relates to a curable composition and a connection structure using a phenoxy resin.
  • a curable composition containing a curable compound is widely used in various applications such as electricity, electronics, architecture, and vehicles.
  • Patent Document 1 includes (A) a phenoxy resin having a structure represented by the following general formula (X), (B) an inorganic filler, and (C) a silane cup.
  • a curable composition comprising a ring agent is disclosed.
  • the content of the (C) silane coupling agent is 1% by mass or more and 10% by mass or less with respect to the entire curable composition.
  • n and m are integers of 1 or more and 20 or less independent of each other.
  • R1 to R19 are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and may be the same or different.
  • X is a single bond, a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO 2 — or —CO—.
  • conductive particles may be blended with the curable composition.
  • a curable composition containing conductive particles is called an anisotropic conductive material.
  • the anisotropic conductive material may be connected between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), or connected between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.
  • FOG Glass
  • COF Chip on Film
  • Patent Document 2 discloses a curing agent that generates free radicals by heating, a hydroxyl group-containing resin having a molecular weight of 10,000 or more, a phosphate ester, a radical polymerizable substance, a conductive material.
  • An anisotropic conductive material (curable composition) containing conductive particles is disclosed.
  • Specific examples of the hydroxyl group-containing resin include polymers such as polyvinyl butyral resin, polyvinyl formal, polyamide, polyester, phenol resin, epoxy resin, and phenoxy resin.
  • An object of the present invention is to provide a curable composition that gives a cured product having high adhesion under high temperature and high humidity. Moreover, the objective of this invention is providing the connection structure using the said curable composition.
  • a curable composition containing a phenoxy resin having a hydrolyzable group in the side chain and conductive particles.
  • the hydrolyzable group has reactivity with a hydroxyl group.
  • the hydrolyzable group is an alkoxysilyl group.
  • the phenoxy resin has a reactive functional group that reacts with a silane coupling agent and does not have a hydrolyzable group in a side chain; It can be obtained by introducing a hydrolyzable group derived from the silane coupling agent into the side chain by reacting with the silane coupling agent.
  • the phenoxy resin has an epoxy group or a (meth) acryloyl group at the terminal.
  • the curable composition includes a moisture curing accelerator that promotes moisture curing of the phenoxy resin.
  • the moisture curing accelerator has a pH of 4 or less, and the moisture curing accelerator has reactivity with the hydrolyzable group in the phenoxy resin.
  • the curable composition includes a radical polymerizable compound and a thermal radical polymerization initiator.
  • the curable composition is used for connection of an electronic component.
  • the conductive particles are conductive particles having at least an outer surface of solder.
  • the curable composition is a conductive material and is used for electrical connection between electrodes.
  • a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, A connection portion connecting the second connection target member, the connection portion being formed by curing the curable composition described above, the first electrode and the second electrode are connected electrically by the conductive particles.
  • the curable composition containing the phenoxy resin and conductive particles has an adhesive property under high temperature and high humidity. Gives a high cured product.
  • FIG. 1 is a front cross-sectional view schematically showing a connection structure using a curable composition according to an embodiment of the present invention.
  • FIG. 2 is a front cross-sectional view schematically showing an enlarged connection portion between conductive particles and electrodes in the connection structure shown in FIG. 1.
  • FIG. 3 is a cross-sectional view showing an example of conductive particles that can be used in the curable composition according to an embodiment of the present invention.
  • FIG. 4 is a cross-sectional view showing a modification of the conductive particles.
  • FIG. 5 is a cross-sectional view showing another modified example of conductive particles.
  • the phenoxy resin (hereinafter sometimes referred to as phenoxy resin (A)) contained in the curable composition according to the present invention has a hydrolyzable group in the side chain. Since the phenoxy resin has a hydrolyzable group, the use of the phenoxy resin (A) makes it possible to obtain a curable composition that gives a cured product having high adhesion under high temperature and high humidity.
  • the curable composition containing electroconductive particle since electroconductive particle contacts an adhesion target object, there exists a tendency for adhesiveness to become low easily.
  • adhesion at high temperature and high humidity is required at a considerably high level. High adhesion reliability under high temperature and high humidity can provide high conduction reliability.
  • the adhesiveness under high temperature and high humidity can be effectively improved in the curable composition containing electroconductive particle.
  • phenoxy resin includes both a phenoxy resin obtained by a one-step method and a phenoxy resin obtained by a multi-step method.
  • examples of the phenoxy resin (A) include polyhydroxy ethers synthesized from bisphenols and epichlorohydrin, and polyhydroxy ethers synthesized from an epoxy compound and a diol.
  • examples of the phenoxy resin (A) include a resin obtained by reacting epichlorohydrin with a divalent phenol compound, and a resin obtained by reacting a divalent epoxy compound with a divalent phenol compound.
  • the hydrolyzable group is preferably reactive with a hydroxyl group.
  • Specific examples of the hydrolyzable group include an alkoxysilyl group and an alkoxy titanate group. From the viewpoint of effectively increasing the adhesiveness under high temperature and high humidity, the hydrolyzable group is preferably an alkoxysilyl group.
  • the alkoxysilyl group is preferably a group represented by the following formula (11).
  • R1 and R2 each represent an alkyl group having 1 to 5 carbon atoms, n represents 2 or 3, m represents 0 or 1, and m + n represents 3.
  • R1 and R2 are each preferably a methyl group or an ethyl group.
  • the phenoxy resin (A) preferably has an epoxy group or a (meth) acryloyl group at the terminal.
  • high temperature and high humidity resistance can be expressed by reacting the functional groups at the ends or reacting with the reactive compound added to the phenoxy resin (A).
  • the phenoxy resin (A) preferably has an epoxy group at the end, and preferably has a (meth) acryloyl group at the end.
  • the phenoxy resin (A) has a reactive functional group that reacts with a silane coupling agent and does not have a hydrolyzable group in the side chain (hereinafter, referred to as a phenoxy resin (a)).
  • a silane coupling agent are preferably obtained by introducing a hydrolyzable group derived from the silane coupling agent into the side chain.
  • the reactive functional group in the phenoxy resin (a) include an epoxy group and a hydroxyl group.
  • the reactive functional group is preferably a hydroxyl group.
  • silane coupling agent examples include silane coupling agents having an isocyanate group, silane coupling agents having an epoxy group, and silane coupling agents having an amino group. Among these, a silane coupling agent having an isocyanate group is preferable.
  • the weight average molecular weight of the phenoxy resin (A) is preferably 5000 or more, more preferably 8000 or more, preferably 150,000 or less, more preferably 50,000 or less,
  • the number average molecular weight of the phenoxy resin (A) is preferably 2000 or more, more preferably 3000 or more, preferably 50,000 or less, more preferably 20,000 or less.
  • the phenoxy resin (A) preferably has a skeleton derived from an aliphatic diol such as 1,6-hexanediol. Thereby, peeling adhesive force can be improved further.
  • the content of the phenoxy resin (A) is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably 45% by weight or less. Preferably it is 35 weight% or less.
  • the content of the phenoxy resin (A) is not less than the above lower limit and not more than the above upper limit, the balance between moisture curing and heat curing of the curable composition is further improved.
  • the curable composition concerning this invention contains the phenoxy resin (A) which has a hydrolysable group in a side chain, and electroconductive particle. It is preferable that the curable composition concerning this invention contains the phenoxy resin (A) which has a hydrolysable group in a side chain, and the moisture hardening accelerator which accelerates
  • the curable composition according to the present invention is preferably curable by moisture.
  • the curable composition concerning this invention does not need to contain the said moisture hardening accelerator.
  • the curable composition according to the present invention may contain a curing agent or a polymerization initiator other than the moisture curing accelerator, and the moisture curing accelerator may be added at the time of use.
  • the curable composition is a composition used by being cured at the time of use.
  • the said phenoxy resin (A) only 1 type may be used and 2 or more types may be used together.
  • the said electroconductive particle only 1 type may be used and 2 or more types may be used together.
  • the said moisture hardening accelerator only 1 type may be used and 2 or more types may be used together.
  • the moisture curing accelerator is not particularly limited as long as it can promote moisture curing of the phenoxy resin (A).
  • the moisture curing accelerator preferably promotes the moisture curing of the phenoxy resin (A) by promoting the hydrolysis of the phenoxy resin (A).
  • the moisture curing accelerator preferably has reactivity with the hydrolyzable group in the phenoxy resin (A).
  • the moisture curing accelerator preferably has a polymerizable functional group. Examples of the polymerizable functional group include a (meth) acryloyl group and an epoxy group.
  • the pH of the moisture curing accelerator is preferably less than 7, more preferably 5 or less, still more preferably 4 or less, and still more preferably 3 or less.
  • the pH of the moisture curing accelerator is not more than the above upper limit, the low temperature curability of the curable composition can be further improved, and the radical reaction during storage (before thermal curing) of the curable composition. And the storage stability of the curable composition can be further enhanced.
  • moisture hardening of the said curable composition can be accelerated
  • the lower limit of the pH of the moisture curing accelerator is not particularly limited, but the pH of the moisture curing accelerator is preferably 1 or more, more preferably 2 or more.
  • the moisture curing accelerator can also be used as a pH adjuster.
  • the pH of the moisture curing accelerator is preferably lower than the pH of the radical polymerizable compound described later, more preferably 1 or more, and even more preferably 3 or more.
  • the pH of the moisture curing accelerator is measured using a pH meter (“D-72” manufactured by HORIBA) and an electrode TopH electrode 9615-10D after dissolving 1 g of the moisture curing accelerator in 10 g of pure water. Can do.
  • the moisture curing accelerator is preferably a phosphoric acid compound, and preferably has a (meth) acryloyl group.
  • the phosphoric acid compound examples include phosphoric acid (meth) acrylate, phosphoric acid ester compound, and phosphorous acid ester compound.
  • Phosphoric acid (meth) acrylate is preferable from the viewpoint of effectively promoting moisture curing and from the viewpoint of further rapidly curing at low temperature and further enhancing the storage stability of the curable composition.
  • the moisture curing accelerator examples include “EBECRYL168” manufactured by Daicel Ornex, and “Light Acrylate P-1A (N)”, “Light Ester P-1M”, and “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd. Or the like.
  • the content of the moisture curing accelerator is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 15 parts by weight or less, more preferably 10 parts by weight with respect to 100 parts by weight of the phenoxy resin (A). Less than parts by weight.
  • the content of the moisture curing accelerator is not less than the lower limit and not more than the upper limit, the curable composition is effectively moisture cured.
  • the content of the moisture curing accelerator is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 10 parts by weight or less, more preferably 100 parts by weight of the radical polymerizable compound described later. Is 5 parts by weight or less.
  • the content of the moisture curing accelerator is not less than the above lower limit and not more than the above upper limit, the low temperature curability and the storage stability of the curable composition are further improved.
  • the hard composition preferably contains a radical polymerizable compound and a thermal radical polymerization initiator.
  • a curable composition that can be cured by both moisture and heat is obtained.
  • the adhesiveness of the curable composition under high temperature and high humidity can be further enhanced by using the radical polymerizable compound and the thermal radical polymerization initiator.
  • the said radically polymerizable compound only 1 type may be used and 2 or more types may be used together.
  • the said thermal radical polymerization initiator only 1 type may be used and 2 or more types may be used together.
  • the pH of the said moisture hardening accelerator becomes like this.
  • it is less than 7, More preferably, it is 5 or less, More preferably, it is 4 or less, More preferably, it is 3
  • it is preferably 2 or more.
  • the above radical polymerizable compound can be addition-polymerized by radicals and has a radical polymerizable group.
  • the radical polymerizable compound is a thermosetting compound.
  • radical polymerizable group examples include a group containing an unsaturated double bond.
  • Specific examples of the radical polymerizable group include allyl group, isopropenyl group, maleoyl group, styryl group, vinylbenzyl group, (meth) acryloyl group and vinyl group.
  • the (meth) acryloyl group means an acryloyl group and a methacryloyl group.
  • the radical polymerizable group preferably has a vinyl group, and more preferably a (meth) acryloyl group.
  • the radical polymerizable group is a (meth) acryloyl group
  • the radical polymerizable group has a vinyl group.
  • radical polymerizable compound examples include a compound having a (meth) acryloyl group, a compound having a vinyl group, and a compound having an allyl group. From the viewpoint of increasing the crosslink density in the cured product and further improving the adhesiveness of the cured product, a radical polymerizable compound having a (meth) acryloyl group is preferred.
  • the radical polymerizable compound may be a radical polymerizable compound having a radical polymerizable group and a morpholine group.
  • a radical polymerizable compound having a (meth) acryloyl group and a morpholine group is preferable.
  • the morpholine group is a group represented by the following formula (1a).
  • the radical polymerizable compound is preferably a radical polymerizable compound represented by the following formula (1). .
  • R represents a hydrogen atom or a methyl group.
  • the pH of the radical polymerizable compound is preferably 9 or more, more preferably 10 or more, preferably 13 or less, more preferably 12 or less.
  • the pH of the radical polymerizable compound is measured using a pH meter (“D-72” manufactured by HORIBA) and an electrode TopH electrode 9615-10D after dissolving 1 g of the radical polymerizable compound in 10 g of pure water. Can do.
  • the pH of the curable composition is preferably 5 or more, more preferably 6 or more, preferably 9 or less, more preferably less than 9, and still more preferably 8 or less.
  • the pH of the curable composition is not less than the above lower limit and not more than the above upper limit, the low temperature curability and storage stability of the curable composition are further improved.
  • the pH of the curable composition is measured by dissolving 1 g of the curable composition in 10 g of pure water and then using a pH meter (“D-72” manufactured by HORIBA) and an electrode TopH electrode 9615-10D. Can do.
  • the content of the radical polymerizable compound is preferably 10 parts by weight or more, more preferably 30 parts by weight or more, preferably 200 parts by weight or less, and more preferably 150 parts by weight with respect to 100 parts by weight of the phenoxy resin (A). It is as follows. When the content of the radical polymerizable compound is not less than the above lower limit and not more than the above upper limit, the balance between moisture curing and heat curing of the curable composition is further improved.
  • the content of the radical polymerizable compound having the radical polymerizable group and the morpholine group and the content of the radical polymerizable compound represented by the formula (1) with respect to 100 parts by weight of the phenoxy resin (A). Is preferably 20 parts by weight or more, more preferably 50 parts by weight or more, preferably 300 parts by weight or less, more preferably 200 parts by weight or less.
  • the content of these radically polymerizable compounds is not less than the above lower limit and not more than the above upper limit, the low temperature curability and storage stability of the curable composition are further improved.
  • the thermal radical polymerization initiator is not particularly limited, and examples thereof include azo compounds and organic peroxides.
  • examples thereof include azo compounds and organic peroxides.
  • the said azo compound and the said organic peroxide only 1 type may respectively be used and 2 or more types may be used together.
  • Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1 , 1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, dimethyl-2,2′-azobis (2-methylpropionate), dimethyl-1,1′-azobis (1-cyclohexanecarboxylate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2-tert-butylazo-2-cyanopropane, 2 2,2′-azobis (2-methylpropionamide) dihydrate, 2,2′-azobis (2,4,4-trimethylpentane), and the like.
  • the thermal radical polymerization initiator is preferably an organic peroxide.
  • the curable compound includes a radical polymerizable compound having a radical polymerizable group and a morpholine group and an organic peroxide. It preferably contains an oxide, and more preferably contains a radical polymerizable compound represented by the above formula (1) and an organic peroxide.
  • organic peroxide examples include diacyl peroxide compounds, peroxy ester compounds, hydroperoxide compounds, peroxydicarbonate compounds, peroxyketal compounds, dialkyl peroxide compounds, and ketone peroxide compounds.
  • diacyl peroxide compound examples include benzoyl peroxide, diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, and disuccinic acid peroxide.
  • peroxyester compounds include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, tert-hexylperoxyneodecanoate, and tert-butylperoxyneo.
  • hydroperoxide compound examples include cumene hydroperoxide and p-menthane hydroperoxide.
  • peroxydicarbonate compound examples include di-sec-butyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, and di- (2-ethylhexyl) peroxycarbonate and the like.
  • Other examples of the peroxide include methyl ethyl ketone peroxide, potassium persulfate, and 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane.
  • the decomposition temperature for obtaining the 10-hour half-life of the thermal radical polymerization initiator is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, preferably 90 ° C. or lower, more preferably 80 ° C. or lower.
  • the decomposition temperature is 30 ° C. or higher, the storage stability of the curable composition is further enhanced.
  • the decomposition temperature is not more than the upper limit, the curable composition is effectively thermally cured.
  • the content of the thermal radical polymerization initiator is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight with respect to 100 parts by weight of the radical polymerizable compound. Less than parts by weight.
  • the content of the thermal radical polymerization initiator is not less than the lower limit and not more than the upper limit, the curable composition is effectively thermally cured.
  • the content of the organic peroxide is preferably 100 parts by weight of the radically polymerizable compound having the radically polymerizable group and the morpholine group and 100 parts by weight of the radically polymerizable compound represented by the formula (1). It is 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less. When the content of the organic peroxide is not less than the above lower limit and not more than the above upper limit, the low temperature curability and storage stability of the curable composition are further improved.
  • the curable composition includes an imide (meth) acrylate, a phenoxy resin having a (meth) acryloyl group, a caprolactone-modified epoxy (meth) acrylate, and an aliphatic urethane (meth). It is preferable to include at least one selected from the group consisting of acrylates, and at least one selected from the group consisting of imide (meth) acrylates, phenoxy resins having (meth) acryloyl groups and caprolactone-modified epoxy (meth) acrylates It is more preferable to contain. These are included in the radical polymerizable compound.
  • the total content of the imide (meth) acrylate, the phenoxy resin having the (meth) acryloyl group, and the caprolactone-modified epoxy (meth) acrylate is preferably 5 parts by weight or more.
  • the amount is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, preferably 80 parts by weight or less, more preferably 60 parts by weight or less.
  • a phenoxy resin having a (meth) acryloyl group and a caprolactone-modified epoxy (meth) acrylate it is preferable to use at least one of a phenoxy resin having a (meth) acryloyl group and a caprolactone-modified epoxy (meth) acrylate.
  • the said curable composition may contain the phenoxy resin which has a (meth) acryloyl group, and may contain the caprolactone modified epoxy (meth) acrylate.
  • the said phenoxy resin which has the said (meth) acryloyl group, and the said caprolactone modified epoxy (meth) acrylate only 1 type may be used, respectively, and 2 or more types may be used together.
  • the content of the phenoxy resin having a (meth) acryloyl group is preferably 0 part by weight (unused) or more, more preferably 10 parts by weight or more, and further preferably 50 parts by weight with respect to 100 parts by weight of the phenoxy resin (A). Part by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight or less.
  • the content of the caprolactone-modified epoxy (meth) acrylate is preferably 0 part by weight (unused) or more, more preferably 10 parts by weight or more, and still more preferably 50 parts by weight with respect to 100 parts by weight of the phenoxy resin (A). Above, preferably 200 parts by weight or less, more preferably 100 parts by weight or less.
  • the adhesiveness of the cured product and the high temperature and high humidity of the cured product is further increased.
  • the above cured product may be adhered to polyimide.
  • the curable composition preferably contains an imide (meth) acrylate.
  • the said imide (meth) acrylate only 1 type may be used and 2 or more types may be used together.
  • the content of the imide (meth) acrylate is preferably 0 part by weight (unused) or more, more preferably 10 parts by weight or more, still more preferably 50 parts by weight or more, with respect to 100 parts by weight of the phenoxy resin (A). Preferably it is 200 weight part or less, More preferably, it is 100 weight part or less.
  • the content of the imide (meth) acrylate is not less than the above lower limit and not more than the above upper limit, the adhesiveness of the cured product and the adhesiveness of the cured product under high temperature and high humidity are further increased, and particularly the cured product against polyimide. The adhesiveness is further increased.
  • the curable composition contains conductive particles.
  • the conductive particles include conductive particles formed entirely of a conductive material, and conductive particles having base material particles and a conductive layer disposed on the surface of the base material particles. It is done.
  • the conductive particles are preferably conductive particles having an outer surface that is solder.
  • the adhesion between the connection part derived from the solder and formed by curing the curable composition and the connection target member connected by the connection part is further enhanced.
  • solder particles particles including a base particle and a solder layer disposed on the surface of the base particle can be used.
  • solder particles it is preferable to use solder particles.
  • FIG. 3 is a cross-sectional view showing an example of conductive particles that can be used in the curable composition according to one embodiment of the present invention.
  • the solder particles are preferably conductive particles 21 that are solder particles.
  • the conductive particles 21 are formed only by solder.
  • the conductive particles 21 do not have base particles in the core and are not core-shell particles.
  • both a center part and an outer surface are formed with the solder.
  • particles including base particles and a solder layer disposed on the surface of the base particles may be used.
  • the conductive particle 1 includes a base particle 2 and a conductive layer 3 disposed on the surface of the base particle 2.
  • the conductive layer 3 covers the surface of the base particle 2.
  • the conductive particle 1 is a coated particle in which the surface of the base particle 2 is coated with the conductive layer 3.
  • the conductive layer 3 has a second conductive layer 3A and a solder layer 3B (first conductive layer) disposed on the surface of the second conductive layer 3A.
  • the conductive particle 1 includes a second conductive layer 3A between the base particle 2 and the solder layer 3B. Therefore, the conductive particles 1 include the base particle 2, the second conductive layer 3A disposed on the surface of the base particle 2, and the solder layer 3B disposed on the surface of the second conductive layer 3A. Is provided.
  • the conductive layer 3 may have a multilayer structure, or may have a laminated structure of two or more layers.
  • the conductive layer 3 in the conductive particle 1 has a two-layer structure.
  • the conductive particles 11 may have a solder layer 12 as a single conductive layer.
  • the conductive particles 11 include base material particles 2 and a solder layer 12 disposed on the surface of the base material particles 2.
  • the solder layer 12 may be disposed on the surface of the base particle 2 so as to contact the base particle 2.
  • the conductive particles 1 and 11 are more preferable among the conductive particles 1, 11 and 21 because the thermal conductivity of the conductive material tends to be further lowered.
  • conductive particles including base particles and a solder layer disposed on the surface of the base particles it is easy to further reduce the thermal conductivity of the conductive material.
  • the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
  • the base particles are preferably base particles excluding metal, and are resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.
  • the substrate particles may be copper particles.
  • the base material particles are preferably resin particles formed of a resin.
  • electroconductive particle is compressed by crimping
  • the substrate particles are resin particles, the conductive particles are easily deformed during the pressure bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction
  • the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Alkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, Polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamide Bromide, polyether ether ketone, polyether sulfone, divinyl benzene polymer, and diviny
  • polyolefin resins such as polyethylene, polypropylene,
  • the divinylbenzene copolymer examples include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer. Since the hardness of the resin particles can be easily controlled within a suitable range, the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.
  • the monomer having the ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer. And a polymer.
  • non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; acids such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate Atom
  • crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure And silane
  • examples of inorganic substances for forming the substrate particles include silica and carbon black.
  • the inorganic substance is preferably not a metal.
  • the particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle
  • examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the substrate particles are metal particles
  • examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
  • the metal particles are preferably copper particles.
  • the substrate particles are preferably not metal particles.
  • the melting point of the substrate particles is preferably higher than the melting point of the solder layer.
  • the melting point of the substrate particles is preferably higher than 160 ° C, more preferably higher than 300 ° C, still more preferably higher than 400 ° C, and particularly preferably higher than 450 ° C.
  • the melting point of the substrate particles may be less than 400 ° C.
  • the melting point of the substrate particles may be 160 ° C. or less.
  • the softening point of the substrate particles is preferably 260 ° C. or higher.
  • the softening point of the substrate particles may be less than 260 ° C.
  • the conductive particles may have a single solder layer.
  • the conductive particles may have a plurality of conductive layers (solder layer, second conductive layer). That is, in the conductive particles, two or more conductive layers may be stacked.
  • the solder particles may be particles formed of a plurality of layers.
  • the solder for forming the solder layer and the solder for forming solder particles are preferably low melting point metals having a melting point of 450 ° C. or lower.
  • the solder layer is preferably a low melting point metal layer having a melting point of 450 ° C. or lower.
  • the low melting point metal layer is a layer containing a low melting point metal.
  • the solder particles are preferably low melting point metal particles having a melting point of 450 ° C. or lower.
  • the low melting point metal particles are particles containing a low melting point metal.
  • the low melting point metal is a metal having a melting point of 450 ° C. or lower.
  • the melting point of the low melting point metal is preferably 300 ° C. or lower, more preferably 160 ° C. or lower.
  • the solder layer and the solder particles preferably contain tin.
  • the tin content is preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 70% by weight. Above, particularly preferably 90% by weight or more.
  • the content of tin in the solder layer and the solder particles is equal to or higher than the lower limit, the connection reliability between the conductive particles and the electrodes is further enhanced.
  • the tin content is determined using a high-frequency inductively coupled plasma emission spectrometer (“ICP-AES” manufactured by Horiba, Ltd.) or a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu). It can be measured.
  • ICP-AES high-frequency inductively coupled plasma emission spectrometer
  • EDX-800HS fluorescent X-ray analyzer
  • solder particles and the conductive particles having the solder on the conductive surface are used, so that the solder is melted and joined to the electrodes, and the solder conducts between the electrodes. For example, since the solder and the electrode are not in point contact but in surface contact, the connection resistance is lowered.
  • the use of conductive particles having solder on the conductive surface increases the bonding strength between the solder and the electrode. As a result, peeling between the solder and the electrode is further less likely to occur, and conduction reliability and connection reliability are improved. Effectively high.
  • the low melting point metal constituting the solder layer and the solder particles is not particularly limited.
  • the low melting point metal is preferably tin or an alloy containing tin.
  • the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, a tin-zinc alloy, and a tin-indium alloy.
  • the low melting point metal is preferably tin, a tin-silver alloy, a tin-silver-copper alloy, a tin-bismuth alloy, or a tin-indium alloy because of its excellent wettability with respect to the electrode. More preferred are a tin-bismuth alloy and a tin-indium alloy.
  • the material constituting the solder is preferably a filler material having a liquidus of 450 ° C. or lower based on JIS Z3001: welding terms.
  • the composition of the solder include a metal composition containing zinc, gold, silver, lead, copper, tin, bismuth, indium and the like. Of these, a tin-indium system (117 ° C. eutectic) or a tin-bismuth system (139 ° C. eutectic) which is low-melting and lead-free is preferable. That is, the solder preferably does not contain lead, and is preferably a solder containing tin and indium or a solder containing tin and bismuth.
  • the solder layer and the solder particles are nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, Metals such as manganese, chromium, molybdenum, and palladium may be included.
  • the solder layer and the solder particles preferably contain nickel, copper, antimony, aluminum, or zinc.
  • the content of these metals for increasing the bonding strength is 100% by weight of solder (100% by weight of solder layer or 100% by weight of solder particles). %), Preferably 0.0001% by weight or more, preferably 1% by weight or less.
  • the melting point of the second conductive layer is preferably higher than the melting point of the solder layer.
  • the melting point of the second conductive layer is preferably above 160 ° C, more preferably above 300 ° C, even more preferably above 400 ° C, even more preferably above 450 ° C, particularly preferably above 500 ° C, most preferably Preferably it exceeds 600 degreeC. Since the solder layer has a low melting point, it melts during conductive connection.
  • the second conductive layer is preferably not melted at the time of conductive connection.
  • the conductive particles are preferably used after melting solder, preferably used after melting the solder layer, and used without melting the second conductive layer while melting the solder layer. It is preferred that Since the melting point of the second conductive layer is higher than the melting point of the solder layer, only the solder layer can be melted without melting the second conductive layer at the time of conductive connection.
  • the absolute value of the difference between the melting point of the solder layer and the melting point of the second conductive layer is preferably more than 0 ° C, more preferably 5 ° C or more, still more preferably 10 ° C or more, and further preferably 30 ° C. Above, particularly preferably 50 ° C. or higher, most preferably 100 ° C. or higher.
  • the second conductive layer preferably contains a metal.
  • the metal constituting the second conductive layer is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, tungsten, molybdenum and cadmium, and alloys thereof. Is mentioned. Further, tin-doped indium oxide (ITO) may be used as the metal. As for the said metal, only 1 type may be used and 2 or more types may be used together.
  • ITO tin-doped indium oxide
  • the second conductive layer is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and even more preferably a copper layer.
  • the conductive particles preferably have a nickel layer, a palladium layer, a copper layer, or a gold layer, more preferably have a nickel layer or a gold layer, and still more preferably have a copper layer.
  • the average particle diameter of the conductive particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, still more preferably 50 ⁇ m or less, and particularly preferably 40 ⁇ m or less.
  • the average particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrode is sufficiently large, and aggregated conductive particles are formed when the conductive layer is formed. It becomes difficult. Moreover, it becomes a size suitable for the conductive particles in the conductive material, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base particle.
  • the particle diameter of the conductive particles indicates a number average particle diameter.
  • the average particle diameter of the conductive particles is determined by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.
  • the thickness of the solder layer is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.3 ⁇ m or less.
  • the thickness of the solder layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes. .
  • the thinner the solder layer is the easier it is to lower the thermal conductivity of the conductive material.
  • the thickness of the solder layer is preferably 4 ⁇ m or less, more preferably 2 ⁇ m or less.
  • the thickness of the second conductive layer is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and still more preferably 0.3 ⁇ m or less.
  • the thickness of the second conductive layer is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes is further reduced.
  • the thinner the second conductive layer is, the easier it is to reduce the thermal conductivity of the conductive material. From the viewpoint of sufficiently reducing the thermal conductivity of the conductive material, the thickness of the second conductive layer is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the thickness of the solder layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the conductive particles have a conductive layer different from the solder layer and the other conductive layer (such as the second conductive layer) as the conductive layer, the solder layer and the other conductive layer different from the solder layer
  • the total thickness is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the curable composition preferably includes a conductive material and includes the conductive particles.
  • the conductive material is preferably an anisotropic conductive material.
  • the conductive material is preferably used for electrical connection of electrodes.
  • the conductive material is preferably a conductive material for circuit connection.
  • the conductive material can be used as a conductive paste and a conductive film.
  • the conductive material is a conductive film
  • a film that does not include conductive particles may be laminated on a conductive film that includes conductive particles.
  • the content of the conductive particles is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 2% by weight or more, and further preferably 10% by weight. More preferably, 20% by weight or more, particularly preferably 25% by weight or more, most preferably 30% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, Particularly preferred is 45% by weight or less, and most preferred is 35% by weight or less.
  • the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, it is easy to arrange many conductive particles between the electrodes, and the conduction reliability is further enhanced. Moreover, since content of a sclerosing
  • the curable composition preferably contains a flux.
  • the flux is not particularly limited.
  • a flux generally used for soldering or the like can be used.
  • the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, phosphoric acid, a derivative of phosphoric acid, an organic halide, hydrazine, an organic acid, and pine resin. Is mentioned.
  • As for the said flux only 1 type may be used and 2 or more types may be used together.
  • Examples of the molten salt include ammonium chloride.
  • Examples of the organic acid include lactic acid, citric acid, stearic acid, glutamic acid, and glutaric acid.
  • Examples of the pine resin include activated pine resin and non-activated pine resin.
  • the flux is preferably an organic acid having two or more carboxyl groups, pine resin.
  • the flux may be an organic acid having two or more carboxyl groups, or pine resin.
  • the above rosins are rosins whose main component is abietic acid.
  • the flux is preferably rosins, and more preferably abietic acid. By using this preferable flux, the conduction reliability between the electrodes is further enhanced.
  • the flux may be dispersed in the curable composition or may adhere to the surface of conductive particles or solder particles.
  • the content of the flux is 0% by weight (unused) or more, preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less.
  • the curable composition may not contain a flux. When the flux content is not less than the above lower limit and not more than the above upper limit, it becomes more difficult to form an oxide film on the surface of the solder and the electrode, and the oxide film formed on the surface of the solder and the electrode is more effective. Can be removed.
  • the curable composition may be, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, and an ultraviolet absorber as necessary.
  • various additives such as a lubricant, an antistatic agent and a flame retardant may be included.
  • connection structure can be obtained by connecting a connection object member using the curable composition mentioned above.
  • connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member, and the connection The part is formed by curing the curable composition described above.
  • FIG. 1 is a front sectional view schematically showing a connection structure using a curable composition according to an embodiment of the present invention.
  • the curable composition used here includes conductive particles 1. Instead of the conductive particles 1, the conductive particles 11 or the conductive particles 21 may be used. Moreover, you may use electroconductive particle other than electroconductive particle 1,11,21.
  • a connection structure 51 shown in FIG. 1 is a connection that connects a first connection target member 52, a second connection target member 53, and the first connection target member 52 and the second connection target member 53. Part 54.
  • the first connection target member 52 has a plurality of first electrodes 52a on the surface (upper surface).
  • the second connection target member 53 has a plurality of second electrodes 53a on the surface (lower surface).
  • the first electrode 52 a and the second electrode 53 a are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.
  • FIG. 2 is an enlarged front sectional view showing a connection portion between the conductive particle 1 and the first and second electrodes 52a and 53a in the connection structure 51 shown in FIG.
  • the connection structure 51 after the solder layer 3 ⁇ / b> B in the conductive particles 1 is melted, the melted solder layer portion 3 ⁇ / b> Ba is in sufficient contact with the first and second electrodes 52 a and 53 a. That is, by using the conductive particles 1 whose surface layer is the solder layer 3B, compared to the case where the conductive particles whose surface layer is a metal such as nickel, gold or copper are used, the conductive particles The contact area between 1 and the first and second electrodes 52a and 53a is increased.
  • electrical_connection reliability and connection reliability of the connection structure 51 can be improved.
  • the flux generally deactivates gradually due to heating. Further, from the viewpoint of further improving the conduction reliability, it is preferable to bring the second conductive layer 3A into contact with the first electrode 52a, and it is preferable to bring the second conductive layer 3A into contact with the second electrode 53a. .
  • the manufacturing method of the connection structure is not particularly limited. As an example of the manufacturing method of this connection structure, after arrange
  • the method of heating and pressurizing is mentioned.
  • the pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
  • the heating temperature is about 120 to 220 ° C.
  • the first and second connection target members are not particularly limited.
  • the first and second connection target members include electronic components such as semiconductor chips, capacitors, and diodes, and circuit boards such as printed boards, flexible printed boards, glass epoxy boards, and glass boards. Examples include parts.
  • the conductive curable composition is preferably a conductive material used for connecting electronic components.
  • the curable composition is preferably a conductive material that is liquid and is applied to the upper surface of the connection target member in a liquid state.
  • the curable composition is preferably used for electrical connection between electrodes.
  • the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, and a tungsten electrode.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode.
  • the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
  • the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element.
  • the trivalent metal element include Sn, Al, and Ga.
  • the first reaction product contains a hydroxyl group derived from bisphenol F, 1,6-hexanediol diglycidyl ether, and an epoxy group of bisphenol F type epoxy resin. It was confirmed that the unit had a bonded structural unit in the main chain and an epoxy group at both ends.
  • the weight average molecular weight of the second reactant obtained by GPC was 15000, and the number average molecular weight was 5000.
  • R represents a group or a hydroxyl group represented by the following formula.
  • the weight average molecular weight of the phenoxy resin (A1) obtained by GPC was 16000, and the number average molecular weight was 5,500.
  • Synthesis Example 2 100 parts by weight of the first reaction product obtained in Synthesis Example 1 was placed in a three-necked flask and dissolved at 120 ° C. under a nitrogen flow. Thereafter, 2 parts by weight of “KBE-9007” (3-isocyanatepropyltriethoxysilane) manufactured by Shin-Etsu Silicone Co., Ltd. was added to react the side chain hydroxyl group of the first reactant with the isocyanate group of 3-isocyanatepropyltriethoxysilane. 0.002 part by weight of dibutyltin dilaurate as a catalyst was added and reacted at 120 ° C. for 4 hours under a nitrogen flow. Thereafter, it was vacuum-dried at 110 ° C. for 5 hours to remove unreacted KBE-9007.
  • KBE-9007 3-isocyanatepropyltriethoxysilane
  • R represents a group or a hydroxyl group represented by the following formula.
  • Thermosetting compound (epoxy resin, “EPICLON EAX-4850-150” manufactured by DIC)
  • Thermosetting agent (Thermosetting agent) Thermosetting agent ("HXA3922HP" manufactured by Asahi Kasei E-Materials, microencapsulated amine type curing agent)
  • Solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle size 10 ⁇ m)
  • connection structure Glass epoxy substrate (FR-4 substrate) having an electrode pattern (width: 3 mm, number of electrodes: 70) on the upper surface of a copper electrode having L / S of 100 ⁇ m / 100 ⁇ m plated with Ni / Au Prepared.
  • a flexible printed circuit board having an electrode pattern (width: 3 mm, number of electrodes: 70) obtained by performing Ni / Au plating on a copper electrode having an L / S of 100 ⁇ m / 100 ⁇ m was prepared.
  • the curable composition was applied on the upper surface of the glass epoxy substrate so as to have a thickness of 150 ⁇ m and a width of 0.8 mm, thereby forming a curable composition layer.
  • the flexible printed circuit board was laminated on the upper surface of the curable composition layer so that the electrodes face each other.
  • the pressure of 1.0 MPa was adjusted by adjusting the temperature of the heater head so that the temperature of the curable composition layer located on the electrode was 140 ° C. by a crimping machine (“BD-03” manufactured by Ohashi Seisakusho). For 10 seconds. As a result, the solder was melted and the curable composition layer was cured to obtain a connection structure.
  • BD-03 manufactured by Ohashi Seisakusho
  • Viscosity after standing for 48 hours / initial viscosity is less than 1.2 times
  • Viscosity after standing for 48 hours / initial viscosity is 1.2 times or more and less than 1.5 times
  • ⁇ After standing for 48 hours Viscosity / initial viscosity is 1.5 times or more and less than 2 times
  • Viscosity after standing for 48 hours / initial viscosity is 2 times or more
  • the conductivity between the upper and lower electrodes was determined according to the following criteria (the obtained resistance value is the total value of connection resistance between upper and lower electrodes of electrode area 3 mm ⁇ 100 ⁇ m ⁇ 70).
  • ⁇ Average value of connection resistance is 8.0 ⁇ or less ⁇ : Average value of connection resistance exceeds 8.0 ⁇ and 10.0 ⁇ or less ⁇ : Average value of connection resistance exceeds 10.0 ⁇ and 15.0 ⁇ or less ⁇ : Average connection resistance exceeds 15.0 ⁇
  • Adhesiveness under high temperature and high humidity Using the obtained connection structure, “Micro Autograph MST-I” manufactured by Shimadzu Corporation was used and a 90 ° peel strength C was obtained at a pulling speed of 50 mm / min. The measurement was performed in an atmosphere of ° C. After leaving it to stand at 85 ° C. and a humidity of 85% for 500 hours, the 90 ° peel strength D was measured in the same manner.
  • the adhesiveness under high temperature and high humidity was determined according to the following criteria.
  • composition and evaluation results of the curable composition are shown in Table 1 below.

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KR102428039B1 (ko) * 2016-10-06 2022-08-03 세키스이가가쿠 고교가부시키가이샤 도전 재료, 접속 구조체 및 접속 구조체의 제조 방법
JP7070552B2 (ja) * 2017-03-29 2022-05-18 味の素株式会社 硬化性組成物および構造物
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