WO2015033834A1 - Curable composition and connection structure - Google Patents
Curable composition and connection structure Download PDFInfo
- Publication number
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- curable composition
- group
- weight
- particles
- phenoxy resin
- Prior art date
Links
Images
Classifications
-
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明に係る硬化性組成物に含まれるフェノキシ樹脂(以下、フェノキシ樹脂(A)と記載することがある)は、加水分解性基を側鎖に有する。上記フェノキシ樹脂は、加水分解性基を有するので、フェノキシ樹脂(A)の使用により、高温高湿下での接着性が高い硬化物を与える硬化性組成物を得ることができる。特に、導電性粒子を含む硬化性組成物においては、導電性粒子が接着対象物に接触するため、接着性が低くなりやすい傾向がある。さらに、導電性粒子を含む硬化性組成物を用いた接続構造体においては、かなり高いレベルで高温高湿下での接着性が求められる。高温高湿下での接着性が高いと、高い導通信頼性が得られる。本発明では、導電性粒子を含む硬化性組成物において、高温高湿下での接着性を効果的に高めることができる。 (Phenoxy resin)
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. In particular, in the curable composition containing electroconductive particle, since electroconductive particle contacts an adhesion target object, there exists a tendency for adhesiveness to become low easily. Furthermore, in a connection structure using a curable composition containing conductive particles, 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. In this invention, the adhesiveness under high temperature and high humidity can be effectively improved in the curable composition containing electroconductive particle.
本発明に係る硬化性組成物は、加水分解性基を側鎖に有するフェノキシ樹脂(A)と、導電性粒子とを含む。本発明に係る硬化性組成物は、加水分解性基を側鎖に有するフェノキシ樹脂(A)と、該フェノキシ樹脂(A)の湿気硬化を促進させる湿気硬化促進剤とを含むことが好ましい。本発明に係る硬化性組成物は、湿気により硬化可能であることが好ましい。本発明に係る硬化性組成物は、上記湿気硬化促進剤を含んでいなくてもよい。本発明に係る硬化性組成物は、上記湿気硬化促進剤以外の硬化剤又は重合開始剤を含んでいてもよく、使用時に、上記湿気硬化促進剤が添加されてもよい。硬化性組成物は、使用時に硬化させて用いられる組成物である。上記フェノキシ樹脂(A)は1種のみが用いられてもよく、2種以上が併用されてもよい。上記導電性粒子は、1種のみが用いられてもよく、2種以上が併用されてもよい。上記湿気硬化促進剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。 (Curable composition)
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 | stimulates the moisture hardening of this phenoxy resin (A). 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. As for the said phenoxy resin (A), only 1 type may be used and 2 or more types may be used together. As for the said electroconductive particle, only 1 type may be used and 2 or more types may be used together. As for the said moisture hardening accelerator, only 1 type may be used and 2 or more types may be used together.
上述した硬化性組成物を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。 (Connection structure)
A connection structure can be obtained by connecting a connection object member using the curable composition mentioned above.
以下のフェノキシ樹脂(A1),(A2),(A3)を合成した。 (Phenoxy resin (A))
The following phenoxy resins (A1), (A2), and (A3) were synthesized.
(1)ビスフェノールFと1,6-ヘキサンジオールジグリシジルエーテル、及びビスフェノールF型エポキシ樹脂との第1の反応物の合成:
ビスフェノールF(4,4’-メチレンビスフェノールと2,4’-メチレンビスフェノールと2,2’-メチレンビスフェノールとを重量比で2:3:1で含む)72重量部、1,6-ヘキサンジオールジグリシジルエーテル70重量部、ビスフェノールF型エポキシ樹脂(DIC社製「EPICLON EXA-830CRP」)30重量部を、3つ口フラスコに入れ、窒素フロー下にて、150℃で溶解させた。その後、水酸基とエポキシ基との付加反応触媒であるテトラーn-ブチルスルホニウムブロミド0.1重量部を添加し、窒素フロー下にて、150℃で6時間、付加重合反応させることにより第1の反応物を得た。 (Synthesis Example 1)
(1) Synthesis of first reaction product of bisphenol F with 1,6-hexanediol diglycidyl ether and bisphenol F type epoxy resin:
72 parts by weight of bisphenol F (containing 4,4′-methylene bisphenol, 2,4′-methylene bisphenol and 2,2′-methylene bisphenol in a weight ratio of 2: 3: 1), 1,6-hexanediol 70 parts by weight of glycidyl ether and 30 parts by weight of bisphenol F type epoxy resin (“EPICLON EXA-830CRP” manufactured by DIC) were placed in a three-necked flask and dissolved at 150 ° C. under a nitrogen flow. Thereafter, 0.1 part by weight of tetra-n-butylsulfonium bromide, which is an addition reaction catalyst between a hydroxyl group and an epoxy group, was added, and the addition reaction was carried out at 150 ° C. for 6 hours under a nitrogen flow to achieve the first reaction. I got a thing.
合成例1で得られた上記第1の反応物100重量部を、3つ口フラスコに入れ、窒素フロー下にて、120℃で溶解させた。その後、信越シリコーン社製「KBE-9007」(3-イソシアネートプロピルトリエトキシシラン)2重量部を添加し、第1の反応物の側鎖水酸基と3-イソシアネートプロピルトリエトキシシランのイソシアネート基との反応触媒であるジラウリン酸ジブチルすず0.002重量部を添加し、窒素フロー下にて、120℃で4時間反応させた。その後、110℃にて5時間真空乾燥し、未反応のKBE-9007を除去した。 (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.
合成例1で得られた上記第1の反応物100重量部を、3つ口フラスコに入れ、窒素フロー下にて、120℃で溶解させた。その後、信越シリコーン社製「KBE-403」(3-グリシドキシプロピルトリエトキシシラン)3重量部を添加し、第1の反応物の側鎖水酸基と3-グリシドキシプロピルトリエトキシシランのエポキシ基との反応触媒であるテトラーn-ブチルスルホニウムブロミド0.1重量部を添加し、窒素フロー下にて、120℃で4時間反応させた。その後、110℃にて5時間真空乾燥し、未反応のKBE-403を除去した。 (Synthesis Example 3)
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, 3 parts by weight of “KBE-403” (3-glycidoxypropyltriethoxysilane) manufactured by Shin-Etsu Silicone Co., Ltd. was added, and the side chain hydroxyl group of the first reactant and the epoxy of 3-glycidoxypropyltriethoxysilane were added. 0.1 part by weight of tetra-n-butylsulfonium bromide which is a reaction catalyst with the group was added, and the mixture was 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-403.
他のフェノキシ樹脂(新日鐵住金化学社製「YP-50S」) (Phenoxy resin not equivalent to phenoxy resin (A))
Other phenoxy resins (“YP-50S” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
リン酸アクリレート(ダイセル・オルネクス社製「EBECRYL168」、pH=2.8)
リン酸メタクリレート:2-メタクロイロキシエチルアシッドホスフェート(共栄社化学社製「ライトエステルP-1M」、pH=3)
リン酸アクリレート2:2-アクリロイルオキシエチルアシッドフォスフェート(共栄社化学社製「ライトアクリレートP-1A(N)」、pH=3) (Moisture curing accelerator)
Phosphoric acid acrylate ("EBECRYL168" manufactured by Daicel Ornex Co., Ltd., pH = 2.8)
Phosphoric acid methacrylate: 2-methacryloylethyl acid phosphate (“Eye ester P-1M” manufactured by Kyoeisha Chemical Co., pH = 3)
Phosphoric acid acrylate 2: 2-acryloyloxyethyl acid phosphate (“Light acrylate P-1A (N)”, pH = 3, manufactured by Kyoeisha Chemical Co., Ltd.)
ラジカル重合性化合物1(アクリロイルモルフォリン、KOHJIN社製「ACMO」、pH=11.5、上記式(1)で表される化合物、Rは水素原子) (Radically polymerizable compound)
Radical polymerizable compound 1 (acryloylmorpholine, “ACMO” manufactured by KOHJIN, pH = 11.5, compound represented by the above formula (1), R is a hydrogen atom)
熱硬化性化合物(エポキシ樹脂、DIC社製「EPICLON EAX-4850-150」) (Thermosetting compound)
Thermosetting compound (epoxy resin, “EPICLON EAX-4850-150” manufactured by DIC)
有機過酸化物(日油社製「パーオクタO」) (Thermal radical polymerization initiator)
Organic peroxide (“NO-OPERO” manufactured by NOF Corporation)
熱硬化剤(旭化成イーマテリアルズ社製「HXA3922HP」、マイクロカプセル化されたアミン系型硬化剤) (Thermosetting agent)
Thermosetting agent ("HXA3922HP" manufactured by Asahi Kasei E-Materials, microencapsulated amine type curing agent)
はんだ粒子(三井金属社製「DS-10」、平均粒子径10μm) (Conductive particles)
Solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle size 10 μm)
(メタ)アクリル変性フェノキシ樹脂(上記第2の反応物)
カプロラクトン変性エポキシ(メタ)アクリレート1(ダイセル・オルネクス社製「EBECRYL3708」)
脂肪族ウレタンアクリレート(ダイセル・オルネクス社製「EBECRYL8413」)
イミドアクリレート(東亜合成社製「M-140」)
シランカップリング剤(信越シリコーン社製「KBE-9007」、3-イソシアネートプロピルトリエトキシシラン) (Other compounds)
(Meth) acryl-modified phenoxy resin (second reactant described above)
Caprolactone-modified epoxy (meth) acrylate 1 ("EBECRYL3708" manufactured by Daicel Ornex)
Aliphatic urethane acrylate ("EBECRYL8413" manufactured by Daicel Ornex)
Imido acrylate ("M-140" manufactured by Toa Gosei Co., Ltd.)
Silane coupling agent (“KBE-9007” manufactured by Shin-Etsu Silicone, 3-isocyanatopropyltriethoxysilane)
(1)硬化性組成物の調製
下記の表1に示す成分を下記の表1に示す配合量で配合して、遊星式攪拌機を用いて2000rpmにて、ペーストの温度が30℃以下になるように管理し、10分間攪拌することにより、異方性導電ペーストを得た。 (Examples 1 to 11 and Comparative Examples 1 to 3)
(1) Preparation of curable composition The components shown in Table 1 below are blended in the blending amounts shown in Table 1 below, and the temperature of the paste is 30 ° C. or less at 2000 rpm using a planetary stirrer. And anisotropic stirring paste was obtained by stirring for 10 minutes.
L/Sが100μm/100μmの銅電極にNi/Auメッキを行った電極パターン(幅3mm、電極数70本)を上面に有するガラスエポキシ基板(FR-4基板)を用意した。また、L/Sが100μm/100μmの銅電極にNi/Auメッキを行った電極パターン(幅3mm、電極数70本)を下面に有するフレキシブルプリント基板を用意した。 (2) Fabrication of 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 μm / 100 μm plated with Ni / Au Prepared. In addition, 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 μm / 100 μm was prepared.
(1)pH
得られた硬化性組成物のpHを、硬化性組成物1gを純水10gに溶解させた後、pH計(HORIBA社製「D-72」)、電極ToupH 電極 9615-10Dを用いて測定した。 (Evaluation)
(1) pH
The pH of the obtained curable composition was 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. .
硬化性組成物の初期粘度を測定した。さらに、硬化性組成物を23℃にて48時間静置した後、48時間静置後の粘度を測定した。粘度の測定は、E型粘度計 TV-33(東機産業社製)を用いて行い、硬化性組成物の保存安定性を評価した。保存安定性を下記の基準で判定した。 (2) Storage stability The initial viscosity of the curable composition was measured. Furthermore, the curable composition was allowed to stand at 23 ° C. for 48 hours, and then the viscosity after standing for 48 hours was measured. The viscosity was measured using an E-type viscometer TV-33 (manufactured by Toki Sangyo Co., Ltd.) to evaluate the storage stability of the curable composition. Storage stability was determined according to the following criteria.
○○:48時間静置後の粘度/初期粘度が1.2倍未満
○:48時間静置後の粘度/初期粘度が1.2倍以上、1.5倍未満
△:48時間静置後の粘度/初期粘度が1.5倍以上、2倍未満
×:48時間静置後の粘度/初期粘度が2倍以上 [Criteria for storage stability]
○○: 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 Δ: 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
示差走査熱測定装置SII社製「DSC200」を用い、硬化性組成物を2mg採取し、窒素フロー下、昇温速度10℃/分にて、30℃~300℃まで測定し、発熱ピーク面積Aを求めた。 (3) Low temperature curability Using a differential scanning calorimeter “DSC200” manufactured by SII, 2 mg of the curable composition was sampled and measured from 30 ° C. to 300 ° C. under a nitrogen flow at a heating rate of 10 ° C./min. The exothermic peak area A was determined.
○○:130℃で圧着した際の、反応率が80%以上
○:○○に相当せず、かつ140℃で圧着した際の、反応率が80%以上
△:○○及び○に相当せず、かつ150℃で圧着した際の、反応率が80%以上
×:○○及び○に相当せず、かつ150℃で圧着した際の、反応率が80%未満 [Criteria for low-temperature curability]
○○: Reaction rate of 80% or more when crimped at 130 ° C. ○: Not equivalent to ○○ and reaction rate of 80% or more when crimped at 140 ° C. Δ: Corresponding to ○○ and ○ And a reaction rate of 80% or more when crimped at 150 ° C. ×: Not equivalent to ◯◯ and ○, and a reaction rate of less than 80% when crimped at 150 ° C.
得られた接続構造体の上下の電極間の接続抵抗をそれぞれ、4端子法により測定した。2つの接続抵抗の平均値を算出した。なお、電圧=電流×抵抗の関係から、一定の電流を流した時の電圧を測定することにより接続抵抗を求めることができる。上下の電極間の導通性を下記の基準で判定した(得られた抵抗値は、電極面積3mm×100μmの上下電極間の接続抵抗×70本分の合計値)。 (4) Conductivity The connection resistance between the upper and lower electrodes of the obtained connection structure was measured by a four-terminal method. The average value of the two connection resistances was calculated. Note that the connection resistance can be obtained by measuring the voltage when a constant current is passed from the relationship of voltage = current × resistance. 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
○○:接続抵抗の平均値が8.0Ω以下
○:接続抵抗の平均値が8.0Ωを超え、10.0Ω以下
△:接続抵抗の平均値が10.0Ωを超え、15.0Ω以下
×:接続抵抗の平均値が15.0Ωを超える [Conductivity criteria]
○○: Average value of connection resistance is 8.0Ω or less ○: Average value of connection resistance exceeds 8.0Ω and 10.0Ω or less △: Average value of connection resistance exceeds 10.0Ω and 15.0Ω or less × : Average connection resistance exceeds 15.0Ω
得られた接続構造体を用いて、島津製作所社製「マイクロオートグラフMST-I」を用い、90°ピール強度Cを引っ張り速度50mm/分にて23℃雰囲気下で測定した。85℃及び湿度85%雰囲気下で500時間静置した後、同様にして90°ピール強度Dを測定した。高温高湿下での接着性を下記の基準で判定した。 (5) 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.
○○:90°ピール強度D20N/cm以上であり、D/C×100が80%以上
○:90°ピール強度D15N/cm以上、20N/cm未満であり、D/C×100が80%以上
△:90°ピール強度D10N/cm以上、15N/cm未満であり、D/C×100が80%以上
×:90°ピール強度D10N/cm未満 [Criteria for adhesion under high temperature and high humidity]
○○: 90 ° peel strength D20 N / cm or more, D / C × 100 is 80% or more ○: 90 ° peel strength D15 N / cm or more, less than 20 N / cm, D / C × 100 is 80% or more Δ: 90 ° peel strength D10 N / cm or more and less than 15 N / cm, D / C × 100 is 80% or more ×: 90 ° peel strength D10 N / cm or less
2…基材粒子
3…導電層
3A…第2の導電層
3B…はんだ層
3Ba…溶融したはんだ層部分
11…導電性粒子
12…はんだ層
21…導電性粒子
51…接続構造体
52…第1の接続対象部材
52a…第1の電極
53…第2の接続対象部材
53a…第2の電極
54…接続部 DESCRIPTION OF
Claims (12)
- 加水分解性基を側鎖に有するフェノキシ樹脂と、導電性粒子とを含む、硬化性組成物。 A curable composition comprising a phenoxy resin having a hydrolyzable group in the side chain and conductive particles.
- 前記加水分解性基が水酸基と反応性を有する、請求項1に記載の硬化性組成物。 The curable composition according to claim 1, wherein the hydrolyzable group is reactive with a hydroxyl group.
- 前記加水分解性基がアルコキシシリル基である、請求項1又は2に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the hydrolyzable group is an alkoxysilyl group.
- 前記フェノキシ樹脂は、シランカップリング剤と反応する反応性官能基を有しかつ加水分解性基を側鎖に有さないフェノキシ樹脂と、シランカップリング剤とを反応させることで、前記シランカップリング剤に由来する加水分解性基を側鎖に導入することで得られる、請求項1~3のいずれか1項に記載の硬化性組成物。 The phenoxy resin has a reactive functional group that reacts with a silane coupling agent, and a phenoxy resin that does not have a hydrolyzable group in the side chain and the silane coupling agent, thereby reacting the silane coupling agent. The curable composition according to any one of claims 1 to 3, which is obtained by introducing a hydrolyzable group derived from an agent into a side chain.
- 前記フェノキシ樹脂は、エポキシ基又は(メタ)アクリロイル基を末端に有する、請求項1~4のいずれか1項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 4, wherein the phenoxy resin has an epoxy group or a (meth) acryloyl group at a terminal.
- 前記フェノキシ樹脂の湿気硬化を促進させる湿気硬化促進剤を含む、請求項1~5のいずれか1項に記載の硬化性組成物。 6. The curable composition according to any one of claims 1 to 5, comprising a moisture curing accelerator that accelerates moisture curing of the phenoxy resin.
- 前記湿気硬化促進剤のpHが4以下であり、前記湿気硬化促進剤が、前記フェノキシ樹脂における前記加水分解性基と反応性を有する、請求項6に記載の硬化性組成物。 The curable composition according to claim 6, wherein 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.
- ラジカル重合性化合物と、熱ラジカル重合開始剤とを含む、請求項1~7のいずれか1項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 7, comprising a radical polymerizable compound and a thermal radical polymerization initiator.
- 電子部品の接続に用いられる、請求項1~8のいずれか1項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 8, which is used for connecting electronic components.
- 前記導電性粒子が、少なくとも外表面がはんだである導電性粒子である、請求項1~9のいずれか1項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 9, wherein the conductive particles are conductive particles having at least an outer surface made of solder.
- 導電材料であり、電極間の電気的な接続に用いられる、請求項1~10のいずれか1項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 10, which is a conductive material and is used for electrical connection between electrodes.
- 第1の電極を表面に有する第1の接続対象部材と、
第2の電極を表面に有する第2の接続対象部材と、
前記第1の接続対象部材と、前記第2の接続対象部材を接続している接続部とを備え、
前記接続部が、請求項1~11のいずれか1項に記載の硬化性組成物を硬化させることにより形成されており、
前記第1の電極と前記第2の電極とが、前記導電性粒子により電気的に接続されている、接続構造体。 A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
The first connection target member, and a connection portion connecting the second connection target member,
The connecting portion is formed by curing the curable composition according to any one of claims 1 to 11,
A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201480025623.2A CN105189655B (en) | 2013-09-05 | 2014-08-27 | Solidification compound and connection structural bodies |
JP2014543031A JP5820536B2 (en) | 2013-09-05 | 2014-08-27 | Curable composition and connection structure |
KR1020157024483A KR102167312B1 (en) | 2013-09-05 | 2014-08-27 | Curable composition and connection structure |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013184418 | 2013-09-05 | ||
JP2013-184418 | 2013-09-05 | ||
JP2013184417 | 2013-09-05 | ||
JP2013-184417 | 2013-09-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015033834A1 true WO2015033834A1 (en) | 2015-03-12 |
Family
ID=52628309
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/072422 WO2015033834A1 (en) | 2013-09-05 | 2014-08-27 | Curable composition and connection structure |
PCT/JP2014/072421 WO2015033833A1 (en) | 2013-09-05 | 2014-08-27 | Curable composition and connection structure |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/072421 WO2015033833A1 (en) | 2013-09-05 | 2014-08-27 | Curable composition and connection structure |
Country Status (5)
Country | Link |
---|---|
JP (3) | JP5746797B1 (en) |
KR (2) | KR102167312B1 (en) |
CN (2) | CN105189655B (en) |
TW (2) | TWI596150B (en) |
WO (2) | WO2015033834A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017530227A (en) * | 2014-09-25 | 2017-10-12 | ヘキシオン・インコーポレイテッド | Silane functionalized compounds and compositions thereof |
WO2021044631A1 (en) * | 2019-09-06 | 2021-03-11 | 昭和電工マテリアルズ株式会社 | Resin paste composition, semiconductor device, and semiconductor device manufacturing method |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102605942B1 (en) * | 2015-08-24 | 2023-11-27 | 세키스이가가쿠 고교가부시키가이샤 | Conductive materials and connection structures |
JPWO2017033932A1 (en) * | 2015-08-24 | 2018-06-07 | 積水化学工業株式会社 | Conductive material and connection structure |
JP6551794B2 (en) * | 2016-05-30 | 2019-07-31 | パナソニックIpマネジメント株式会社 | Conductive particle, connecting material for circuit member, connecting structure, and connecting method |
KR102428039B1 (en) * | 2016-10-06 | 2022-08-03 | 세키스이가가쿠 고교가부시키가이샤 | Conductive material, bonded structure, and manufacturing method of bonded structure |
JP7070552B2 (en) * | 2017-03-29 | 2022-05-18 | 味の素株式会社 | Curable compositions and structures |
KR102064379B1 (en) * | 2018-05-08 | 2020-01-10 | 한국생산기술연구원 | Preparing Method of Epoxy Resin Having Alkoxysilyl Group |
JP2020132716A (en) * | 2019-02-15 | 2020-08-31 | 旭化成株式会社 | Polyphenylene ether-containing resin composition |
JP2022019451A (en) * | 2020-07-17 | 2022-01-27 | 京都エレックス株式会社 | Conductive adhesive composition |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000239539A (en) * | 1999-02-18 | 2000-09-05 | Chuo Rika Kogyo Corp | Resin composition and its production |
JP2001089420A (en) * | 1999-09-16 | 2001-04-03 | Idemitsu Kosan Co Ltd | Acrylate compound and adhesive and liquid crystal element using the same |
JP2002212262A (en) * | 2001-01-17 | 2002-07-31 | Arakawa Chem Ind Co Ltd | Resin composition for electric insulation, insulating material and manufacturing method thereof |
JP2002226549A (en) * | 2001-02-05 | 2002-08-14 | Nippon Steel Chem Co Ltd | Siloxane-modified acrylic resin, photosensitive resin composition and hardened product |
JP2002244327A (en) * | 2001-02-14 | 2002-08-30 | Konica Corp | Electrophotographic photoreceptor, method for manufacturing electrophotographic photoreceptor, image forming method, image forming device and process cartridge |
JP2003055435A (en) * | 2001-08-16 | 2003-02-26 | Arakawa Chem Ind Co Ltd | Electrical insulating resin composition, insulating material for electronic material and process for producing it |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4289319B2 (en) | 1997-03-31 | 2009-07-01 | 日立化成工業株式会社 | Circuit connection material, circuit terminal connection structure and connection method |
JP5002876B2 (en) * | 2001-09-18 | 2012-08-15 | 日立化成工業株式会社 | Anisotropic conductive film, connector and semiconductor device |
JP5821355B2 (en) | 2011-07-15 | 2015-11-24 | 住友ベークライト株式会社 | Metal base circuit board, laminated board, inverter device and power semiconductor device |
JP5727325B2 (en) * | 2011-08-01 | 2015-06-03 | 積水化学工業株式会社 | Thermosetting resin material and multilayer substrate |
KR102152474B1 (en) * | 2011-12-16 | 2020-09-04 | 히타치가세이가부시끼가이샤 | Adhesive composition, film-like adhesive, adhesive sheet, connection structure and method for producing connection structure |
-
2014
- 2014-08-27 JP JP2014543030A patent/JP5746797B1/en not_active Expired - Fee Related
- 2014-08-27 KR KR1020157024483A patent/KR102167312B1/en active IP Right Grant
- 2014-08-27 JP JP2014543031A patent/JP5820536B2/en active Active
- 2014-08-27 WO PCT/JP2014/072422 patent/WO2015033834A1/en active Application Filing
- 2014-08-27 CN CN201480025623.2A patent/CN105189655B/en active Active
- 2014-08-27 CN CN201480027694.6A patent/CN105209515B/en not_active Expired - Fee Related
- 2014-08-27 WO PCT/JP2014/072421 patent/WO2015033833A1/en active Application Filing
- 2014-08-27 KR KR1020157022403A patent/KR101596655B1/en active IP Right Grant
- 2014-09-05 TW TW103130886A patent/TWI596150B/en not_active IP Right Cessation
- 2014-09-05 TW TW103130883A patent/TWI598890B/en active
-
2015
- 2015-06-25 JP JP2015127668A patent/JP5897189B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000239539A (en) * | 1999-02-18 | 2000-09-05 | Chuo Rika Kogyo Corp | Resin composition and its production |
JP2001089420A (en) * | 1999-09-16 | 2001-04-03 | Idemitsu Kosan Co Ltd | Acrylate compound and adhesive and liquid crystal element using the same |
JP2002212262A (en) * | 2001-01-17 | 2002-07-31 | Arakawa Chem Ind Co Ltd | Resin composition for electric insulation, insulating material and manufacturing method thereof |
JP2002226549A (en) * | 2001-02-05 | 2002-08-14 | Nippon Steel Chem Co Ltd | Siloxane-modified acrylic resin, photosensitive resin composition and hardened product |
JP2002244327A (en) * | 2001-02-14 | 2002-08-30 | Konica Corp | Electrophotographic photoreceptor, method for manufacturing electrophotographic photoreceptor, image forming method, image forming device and process cartridge |
JP2003055435A (en) * | 2001-08-16 | 2003-02-26 | Arakawa Chem Ind Co Ltd | Electrical insulating resin composition, insulating material for electronic material and process for producing it |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017530227A (en) * | 2014-09-25 | 2017-10-12 | ヘキシオン・インコーポレイテッド | Silane functionalized compounds and compositions thereof |
WO2021044631A1 (en) * | 2019-09-06 | 2021-03-11 | 昭和電工マテリアルズ株式会社 | Resin paste composition, semiconductor device, and semiconductor device manufacturing method |
Also Published As
Publication number | Publication date |
---|---|
JP5820536B2 (en) | 2015-11-24 |
CN105209515B (en) | 2017-03-08 |
KR20150103300A (en) | 2015-09-09 |
CN105189655B (en) | 2017-03-08 |
KR101596655B1 (en) | 2016-02-22 |
JPWO2015033834A1 (en) | 2017-03-02 |
JP5897189B2 (en) | 2016-03-30 |
CN105189655A (en) | 2015-12-23 |
KR102167312B1 (en) | 2020-10-19 |
JP2015180749A (en) | 2015-10-15 |
TW201515014A (en) | 2015-04-16 |
WO2015033833A1 (en) | 2015-03-12 |
TW201514241A (en) | 2015-04-16 |
JPWO2015033833A1 (en) | 2017-03-02 |
KR20160053841A (en) | 2016-05-13 |
TWI596150B (en) | 2017-08-21 |
TWI598890B (en) | 2017-09-11 |
CN105209515A (en) | 2015-12-30 |
JP5746797B1 (en) | 2015-07-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5897189B2 (en) | Curable composition and connection structure | |
JP7425824B2 (en) | Conductive material, connected structure, and method for manufacturing connected structure | |
JP6630284B2 (en) | Conductive material and connection structure | |
JP2014017248A (en) | Conductive material, production method of conductive material, and connection structure | |
JP6049879B2 (en) | Curable composition, conductive material and connection structure | |
JP6581434B2 (en) | Conductive material and connection structure | |
JP2018006084A (en) | Conductive material, connection structure and method for producing connection structure | |
JP2017224602A (en) | Conductive material, connection structure and method for producing connection structure | |
JP2017045607A (en) | Conducive material, connection structure, and manufacturing method of connection structure | |
WO2017033931A1 (en) | Conductive material and connection structure | |
WO2017033933A1 (en) | Electroconductive material and connection structure | |
JP2017045606A (en) | Conducive material, connection structure and manufacturing method of connection structure | |
KR102605910B1 (en) | Conductive materials and connection structures | |
JP2017188327A (en) | Conductive material, connection structure and method for producing connection structure | |
JP6533369B2 (en) | Conductive material and connection structure | |
JP2017191685A (en) | Conductive material and connection structure | |
JP2020170592A (en) | Conductive material and connection structure | |
JP2017045543A (en) | Conducive material and connection structure | |
JP2017045542A (en) | Conducive material and connection structure |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480025623.2 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2014543031 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14841474 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20157024483 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14841474 Country of ref document: EP Kind code of ref document: A1 |