JP5162728B1 - Conductive material and connection structure - Google Patents

Abstract

In spite of using a cation generator, when the electrodes of the connection target member are electrically connected, a conductive material capable of improving the conduction reliability and insulation reliability of the resulting connection structure, and the A connection structure using a conductive material is provided.
The conductive material according to the present invention includes a curable component, a cation exchanger, an anion exchanger, and conductive particles 5. The curable component contains a curable compound and a cation generator. The connection structure 1 according to the present invention includes a connection part that electrically connects the first connection target member 2, the second connection target member 4, and the first and second connection target members 2, 4. 3. The connecting portion 3 is formed by curing the conductive material.
[Selection] Figure 1

Description

  The present invention relates to a conductive material including a plurality of conductive particles, and for example, electrically connects electrodes of various connection target members such as a flexible printed circuit board, a glass substrate, a glass epoxy substrate, a semiconductor chip, and an organic electroluminescence display element substrate. The present invention relates to a conductive material that can be used for connection. The present invention also relates to a connection structure using the conductive material.

  Pasty or film-like anisotropic conductive materials are widely known. In the anisotropic conductive material, a plurality of conductive particles are dispersed in a binder resin or the like.

  In order to obtain various connection structures, the anisotropic conductive material is, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)) or a connection 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.

  As an example of the anisotropic conductive material, the following Patent Document 1 includes a resin component mainly composed of a thermosetting resin, a metal ion scavenger for capturing metal ions dissociated from an electrode, and conductive particles. An anisotropic conductive material containing is disclosed. The metal ion scavenger has a smaller particle size than the conductive particles.

  The following Patent Document 2 discloses an anisotropic conductive material including an insulating adhesive, conductive particles, and an inorganic ion exchanger.

  Patent Document 3 listed below discloses an anisotropic conductive material comprising an alicyclic epoxy resin, a diol, a styrenic thermoplastic elastomer having an epoxy group, an ultraviolet active cationic polymerization catalyst, and conductive particles. A material is disclosed.

  Patent Document 4 below discloses an anisotropic conductive adhesive sheet including a curing agent, a curable insulating resin, conductive particles, and ion scavenger particles. In Patent Document 4, it is described that there are a cation type, an anion type, and a both ion type regarding the types of ions exchanged by the ion scavenger particles. Moreover, in patent document 4, since both the metal ion (positive ion) which causes the ion migration of an electrode terminal directly, and the anion which raises electrical conductivity and produces a metal ion can be exchanged. Both ion types are described as being preferred.

JP 2001-237006 A Japanese Patent Laid-Open No. 10-245528 JP-A-11-060899 JP 2007-16088 A

  For example, when the electrode of the semiconductor chip and the electrode of the glass substrate are electrically connected by the anisotropic conductive material, an anisotropic conductive material containing conductive particles is disposed on the glass substrate. Next, the semiconductor chips are stacked, and heated and pressurized. As a result, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.

  When a connection structure is produced using conventional anisotropic conductive materials as described in Patent Documents 1 to 4, migration occurs when the obtained connection structure is used in a state of being energized under high humidity. Sometimes. For this reason, the insulation reliability of the connection structure may be low.

  In particular, a connection structure using a conventional anisotropic conductive material containing a cation generator as described in Patent Document 3 has a problem that migration is likely to occur due to use in a state of being energized under high humidity. .

  Moreover, as described in Patent Document 4, migration may not be sufficiently suppressed only by using an ion scavenger. Furthermore, in the Example of patent document 4, any one of a cation type ion capture agent particle and an anion type ion capture agent particle is used. In the examples of the cation type ion scavenger particles and the anion type ion scavenger particles used in the examples of Patent Document 4, and the both ion type ion scavenger particles mentioned in Patent Document 4, other formulations are used. Depending on the type of component, migration may not be sufficiently suppressed.

  In recent years, L / S (line / space) which is the electrode width / interelectrode width in the connection structure has been further reduced. As the L / S of the electrode in the connection structure is smaller, there is a problem that an insulation failure is more likely to occur when migration occurs.

  The object of the present invention is to improve the conduction reliability and insulation reliability of the resulting connection structure when the electrodes of the connection target members are electrically connected despite the use of a cation generator. It is to provide a conductive material that can be formed, and a connection structure using the conductive material.

  According to a wide aspect of the present invention, the curable component includes a curable component, a cation exchanger, an anion exchanger, and conductive particles, and the curable component includes a curable compound and a cation generator. A conductive material is provided.

  In a specific aspect of the conductive material according to the present invention, the cation exchanger has a neutral exchange capacity of 2 meq / g or more, and the anion exchanger has a neutral exchange capacity of 1 meq / g or more.

  The cation exchanger preferably contains a zirconium atom. The anion exchanger preferably contains a magnesium atom and an aluminum atom.

  In another specific aspect of the conductive material according to the present invention, the content of the cation exchanger is 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the curable compound, and The content of the anion exchanger is 0.01 parts by weight or more and 5 parts by weight or less.

  In another specific aspect of the conductive material according to the present invention, the conductive particles include resin particles and a conductive layer disposed on the surface of the resin particles, and at least the outer surface of the conductive layer is A low melting point metal layer having a melting point of 450 ° C. or lower.

  In another specific aspect of the conductive material according to the present invention, a flux is further included.

  The conductive material according to the present invention is preferably a conductive material used for connecting a connection target member having a copper electrode.

  The conductive material according to the present invention is preferably an anisotropic conductive material.

  A connection structure according to the present invention includes a first connection target member, a second connection target member, and a connection part that electrically connects the first and second connection target members, The connection part is formed of the conductive material described above.

  In a specific aspect of the connection structure according to the present invention, the first connection target member has a first electrode on the surface, the second connection target member has a second electrode on the surface, The first electrode and the second electrode are electrically connected by the conductive particles, and at least one of the first electrode and the second electrode is a copper electrode.

  The conductive material according to the present invention includes a curable component and a conductive particle containing a curable compound and a cation generator, and further includes both a cation exchanger and an anion exchanger. In spite of being used, when the electrodes of the connection target members are electrically connected, the conduction reliability and the insulation reliability of the obtained connection structure can be improved.

FIG. 1 is a front sectional view schematically showing a connection structure using a conductive material according to an embodiment of the present invention. 2A to 2C are front cross-sectional views for explaining each step of obtaining a connection structure using a conductive material according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

  The conductive material according to the present invention includes a curable component, a cation exchanger, an anion exchanger, and conductive particles. The curable component contains a curable compound and a cation generator.

  When the conductive material according to the present invention has the above-described composition, particularly by using both a cation exchanger and an anion exchanger, the electrode of the connection target member is used although the cation generator is used. When the gaps are electrically connected, the conduction reliability and the insulation reliability of the obtained connection structure can be improved. In particular, even when the connection structure is used in a state of being energized under high humidity, migration hardly occurs in the conductive portions and the electrodes in the conductive particles, and high insulation reliability can be sufficiently ensured.

  In the conductive material according to the present invention, the curable component contains a curable compound and a curing agent. The curing agent contains a cation generator. When the conductive material contains a cation generator, migration in the connection structure tends to occur. On the other hand, the conductive material according to the present invention includes a curable component containing a curable compound and a cation generator and conductive particles, and further includes both a cation exchanger and an anion exchanger. Although the cation generator is used, migration in the connection structure can be effectively suppressed, and insulation reliability can be effectively increased.

  In addition, the present inventors have found that by using a cation generator, the conduction reliability can be effectively increased as compared to the case where a thermosetting agent other than the cation generator (such as an imidazole compound) is used. .

  In addition, the present inventors can use both a cation exchanger and an anion exchanger to use a cation exchanger alone, an anion exchanger alone, or both ion exchangers. It has been found that the occurrence of migration can be suppressed considerably effectively and the insulation reliability can be effectively increased in a conductive material containing a cation generator as compared with the case where is used alone.

  The conductive material according to the present invention does not include a conductive material containing only a cation exchanger as an ion exchanger. The conductive material according to the present invention does not include a conductive material containing only an anion exchanger as an ion exchanger. The conductive material according to the present invention does not include a conductive material that includes both ion exchangers and does not include both a cation exchanger and an anion exchanger as an ion exchanger.

  Moreover, it is preferable to apply a cationic curing system for low temperature rapid curing. The cation generator is used because the ionic component contained in the molecular structure of the cation generator tends to diffuse into the composition and the cation curable compound such as an epoxy compound may contain chlorine ions. When used, electrode corrosion due to a small amount of ionic components is likely to occur. For this reason, when a cation generator is used, there is a problem in connection reliability between electrodes.

  On the other hand, application of an ion exchanger is effective for the above problem, but the effect may not be sufficient. By using both the cation exchanger and the anion exchanger, rather than using only one of the cation exchanger and the anion exchanger, a significant effect on the above problems can be achieved. It was found that it can be obtained. This is because when only one of the cation exchanger and the anion exchanger is used, only one of the ions is trapped, and the balance of the dissociation equilibrium of the cation generator and the like is lost. This is considered to be because the adverse effect of the ionic component in the composition cannot be sufficiently reduced because the salt remains in a free state. In addition, it is more effective to use both the cation exchanger and the anion exchanger than the above-described both ion exchangers having an anion-positive amphoteric ion capturing ability. The reason for this is not clear, but it is conceivable that a compound having an yin and yang amphoteric ion trapping ability cancels the trapping ability because the sites having the respective yin and yang trapping ability are close to each other, thereby reducing the effect.

  As a method of curing the conductive material according to the present invention, a method of irradiating the conductive material with light, a method of heating the conductive material, a method of heating the conductive material after irradiating the conductive material with light, and heating the conductive material Then, a method of irradiating the conductive material with light can be mentioned. In addition, when the photocuring speed and the thermosetting speed are different, light irradiation and heating may be performed simultaneously. Especially, the method of heating a conductive material after irradiating light to a conductive material is preferable. By the combined use of photocuring and heat curing, the conductive material can be cured in a short time.

  The curable compound may be a curable compound (thermosetting compound or light and thermosetting compound) curable by heating, and is curable by irradiation with light (photocurable compound, Or light and thermosetting compounds). The curable compound is preferably a curable compound (thermosetting compound or light and thermosetting compound) that can be cured by heating.

  The conductive material is a conductive material curable by heating, and may include a curable compound (thermosetting compound or light and thermosetting compound) curable by heating as the curable compound. The curable compound curable by heating may be a curable compound (thermosetting compound) that is not cured by light irradiation, and is curable by both light irradiation and heating (light and light). Thermosetting compound).

  The conductive material is a conductive material that can be cured by both light irradiation and heating, and the curable compound is a curable compound that can be cured by light irradiation (a photocurable compound, or light and heat). It is preferable to further contain a curable compound). In this case, the conductive material can be semi-cured (B-staged) by light irradiation to reduce the fluidity of the conductive material, and then the conductive material can be cured by heating. The curable compound that can be cured by light irradiation may be a curable compound (photocurable compound) that is not cured by heating, and is a curable compound that can be cured by both light irradiation and heating (light and light). Thermosetting compound).

  The conductive material according to the present invention includes a curing agent. The conductive material according to the present invention includes a cation generator as the curing agent. The cation generator may be a cation generator that generates cations by heating (thermal cation generator, or light and thermal cation generator), and a cation generator that generates cations by light irradiation (photo cation generation). Agent, or light and thermal cation generator). The curable compound is preferably a cation generator that generates cations by heating (thermal cation generator, or light and thermal cation generator).

  The conductive material according to the present invention may contain a photocuring initiator. The conductive material according to the present invention preferably contains a photoradical generator as the photocuring initiator.

  The conductive material preferably contains a thermosetting compound as the curable compound, and further contains a photocurable compound or light and a thermosetting compound. The conductive material preferably contains a thermosetting compound and a photocurable compound as the curable compound.

  Hereinafter, first, details of each component suitably used for the conductive material according to the present invention will be described.

(Curable compound)
The curable compound contained in the conductive material is not particularly limited. A conventionally known curable compound can be used as the curable compound. As for the said sclerosing | hardenable compound, only 1 type may be used and 2 or more types may be used together.

  The curable compound preferably contains a curable compound having an epoxy group. The curable compound having an epoxy group is an epoxy compound. As for the said curable compound which has an epoxy group, only 1 type may be used and 2 or more types may be used together.

  The curable compound having an epoxy group preferably has an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, chrysene ring, triphenylene ring, tetraphen ring, pyrene ring, pentacene ring, picene ring, and perylene ring. Especially, it is preferable that the said aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring, and it is more preferable that it is a benzene ring or a naphthalene ring. A naphthalene ring is preferred because it has a planar structure and can be cured more rapidly.

  From the viewpoint of enhancing the curability of the conductive material, the content of the curable compound having an epoxy group is preferably 10% by weight or more, more preferably 20% by weight or more, in the total 100% by weight of the curable compound. , 100% by weight or less. The total amount of the curable compound may be the curable compound having the epoxy group. When using together the curable compound which has the said epoxy group, and the other curable compound different from the curable compound which has this epoxy group, hardening which has the said epoxy group in the whole 100 weight% of the said curable compound The content of the functional compound is preferably 99% by weight or less, more preferably 95% by weight or less, still more preferably 90% by weight or less, and particularly preferably 80% by weight or less.

  The curable compound may further contain another curable compound different from the curable compound having an epoxy group. Examples of the other curable compounds include curable compounds having an unsaturated double bond, phenol curable compounds, amino curable compounds, unsaturated polyester curable compounds, polyurethane curable compounds, silicone curable compounds, and polyimide curable compounds. Compounds and the like. As for said other curable compound, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of easily controlling the curing of the conductive material or further improving the conduction reliability in the connection structure, the curable compound may contain a curable compound having an unsaturated double bond. preferable. From the viewpoint of easily controlling the curing of the conductive material or further enhancing the conduction reliability in the connection structure, the curable compound having an unsaturated double bond is a cured product having a (meth) acryloyl group. It is preferable that it is an ionic compound. By using the curable compound having the (meth) acryloyl group, the curing rate is suitable for the entire B-staged conductive material (including the part directly irradiated with light and the part not directly irradiated with light). Therefore, the conduction reliability in the obtained connection structure is further enhanced.

  From the viewpoint of easily controlling the curing rate of the B-staged conductive material layer and further enhancing the conduction reliability of the resulting connection structure, the curable compound having the (meth) acryloyl group is (meth) It preferably has one or two acryloyl groups.

  From the viewpoint of easily controlling the curing rate of the B-staged conductive material layer and further enhancing the conduction reliability of the resulting connection structure, the curable compound having the (meth) acryloyl group is (meth) It preferably has one or two acryloyl groups.

  The curable compound having the (meth) acryloyl group has no epoxy group and has a (meth) acryloyl group, and has a epoxy group and a curable compound having a (meth) acryloyl group. Compounds.

  As the curable compound having the (meth) acryloyl group, an ester compound obtained by reacting a (meth) acrylic acid and a compound having a hydroxyl group, an epoxy obtained by reacting (meth) acrylic acid and an epoxy compound ( A (meth) acrylate, a urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate, or the like is preferably used. The “(meth) acryloyl group” refers to an acryloyl group and a methacryloyl group. The “(meth) acryl” refers to acryl and methacryl. The “(meth) acrylate” refers to acrylate and methacrylate.

  The ester compound obtained by making the said (meth) acrylic acid and the compound which has a hydroxyl group react is not specifically limited. As the ester compound, any of a monofunctional ester compound, a bifunctional ester compound, and a trifunctional or higher functional ester compound can be used.

  The curable compound having an epoxy group and a (meth) acryloyl group is obtained by converting a part of the epoxy group of the compound having two or more epoxy groups into a (meth) acryloyl group. A compound is preferred. This curable compound is a partially (meth) acrylated epoxy compound.

  The curable compound preferably contains a reaction product of a compound having two or more epoxy groups and (meth) acrylic acid. This reaction product is obtained by reacting a compound having two or more epoxy groups with (meth) acrylic acid in the presence of a catalyst such as an acidic catalyst according to a conventional method. It is preferable that 20% or more of the epoxy group is converted (conversion rate) to a (meth) acryloyl group. The conversion is more preferably 30% or more, preferably 80% or less, more preferably 70% or less. Most preferably, 40% or more and 60% or less of the epoxy groups are converted to (meth) acryloyl groups.

  Examples of the partially (meth) acrylated epoxy compound include bisphenol type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, carboxylic acid anhydride-modified epoxy (meth) acrylate, and phenol novolac type epoxy (meth) acrylate. Is mentioned.

  As the curable compound, a modified phenoxy resin in which a part of the epoxy group of the phenoxy resin having two or more epoxy groups is converted to a (meth) acryloyl group may be used. That is, a modified phenoxy resin having an epoxy group and a (meth) acryloyl group may be used.

  The curable compound may be a crosslinkable compound or a non-crosslinkable compound.

  Specific examples of the crosslinkable compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, (poly ) Ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, tri Examples include methylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, polyester (meth) acrylate, and urethane (meth) acrylate.

  Specific examples of the non-crosslinkable compound include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, and the like.

  When a thermosetting compound and a photocurable compound are used in combination, the blending ratio of the photocurable compound and the thermosetting compound is appropriately adjusted according to the type of the photocurable compound and the thermosetting compound. The The conductive material preferably contains a photocurable compound and a thermosetting compound in a weight ratio of 1:99 to 90:10, more preferably 5:95 to 60:40, and more preferably 10:90. More preferably, it is contained at ˜40: 60.

(Curing agent)
The conductive material includes a curing agent. The curing agent may be a thermosetting agent or a photocuring initiator. The curing agent includes a cation generator. Conventionally known cation generators can be used as the cation generator. In the present invention, the cation generator is preferably used as a thermal cation generator for at least thermally curing the conductive material, not as a photo cation generator for only photocuring the conductive material. Furthermore, in the present invention, the cation generator is preferably used as a thermal cation generator for thermosetting the conductive material, not as a photo cation generator for photocuring the conductive material. As for the said cation generator, only 1 type may be used and 2 or more types may be used together.

  As the cation generator, iodonium salts and sulfonium salts are preferably used. For example, as a commercial item of the above cation generator, San-Aid SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150L manufactured by Sanshin Chemical Co., Ltd., K- manufactured by Enomoto Kasei Co., Ltd. PURE, Adeka optomer SP-150, SP-170 manufactured by ADEKA, and the like can be mentioned.

Preferred anion moieties of the cation generator include PF ₆ , BF ₄ , and B (C ₆ F ₅ ) ₄ .

  Other specific examples of the cation generator include 2-butenyldimethylsulfonium tetrakis (pentafluorophenyl) borate, 2-butenyldimethylsulfonium tetrafluoroborate, 2-butenyldimethylsulfonium. Hexafluorophosphate, 2-butenyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, 2-butenyltetramethylenesulfonium tetrafluoroborate, 2-butenyltetramethylenesulfonium hexafluorophosphate, 3-methyl 2-butenyldimethylsulfonium tetrakis (pentafluorophenyl) borate, 3-methyl-2-butenyldimethylsulfonium tetrafluoroborate, 3-methyl-2-butenyldimethylsulfo Um hexafluorophosphate, 3-methyl-2-butenyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, 3-methyl-2-butenyltetramethylenesulfonium tetrafluoroborate, 3-methyl-2-but Tenenyltetramethylenesulfonium hexafluorophosphate, 4-hydroxyphenylcinnamylmethylsulfonium tetrakis (pentafluorophenyl) borate, 4-hydroxyphenylcinnamylmethylsulfonium tetrafluoroborate, 4-hydroxyphenylcinnamylmethylsulfate Phonium hexafluorophosphate, α-naphthylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, α-naphthylmethyltetramethylenes Phonium tetrafluoroborate, α-naphthylmethyltetramethylenesulfonium hexafluorophosphate, cinnamyldimethylsulfonium tetrakis (pentafluorophenyl) borate, cinnamyldimethylsulfonium tetrafluoroborate, cinnamyldimethylsulfonium hexa Fluorophosphate, cinnamyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, cinnamyltetramethylenesulfonium tetrafluoroborate, cinnamyltetramethylenesulfonium hexafluorophosphate, biphenylmethyldimethylsulfonium tetrakis (pentafluoro) Phenyl) borate, biphenylmethyldimethylsulfonium tetrafluoroborate, biphe Nylmethyldimethylsulfonium hexafluorophosphate, biphenylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, biphenylmethyltetramethylenesulfonium tetrafluoroborate, biphenylmethyltetramethylenesulfonium hexafluorophosphate, phenylmethyldimethyl Sulfonium tetrakis (pentafluorophenyl) borate, phenylmethyldimethylsulfonium tetrafluoroborate, phenylmethyldimethylsulfonium hexafluorophosphate, phenylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, phenylmethyltetramethylene Sulfonium tetrafluoroborate, phenyl methyl ester Ramethylene sulfonium hexafluorophosphate, fluorenylmethyldimethylsulfonium tetrakis (pentafluorophenyl) borate, fluorenylmethyldimethylsulfonium tetrafluoroborate, fluorenylmethyldimethylsulfonium hexafluorophosphate, full Examples include oleenylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, fluorenylmethyltetramethylenesulfonium tetrafluoroborate, and fluorenylmethyltetramethylenesulfonium hexafluorophosphate.

  It is preferable that the cation generator release inorganic acid ions by heating or release organic acid ions containing boron atoms by heating. The cation generator is preferably a component that releases inorganic acid ions by heating, and is also preferably a component that releases organic acid ions containing boron atoms by heating.

The cation generator that releases inorganic acid ions by heating is preferably a compound having SbF ⁶⁻ or PF ⁶⁻ as the anion moiety. The cation generator is preferably a compound having SbF ⁶⁻ as the anion moiety, and is preferably a compound having PF ⁶⁻ as the anion moiety.

Anionic portion of the cation generator is _{B (C 6 X 5) 4} - is preferably represented by. The cation generator that releases an organic acid ion containing a boron atom is preferably a compound having an anion moiety represented by the following formula (1).

  In the above formula (1), X represents a halogen atom. X in the formula (1) is preferably a chlorine atom, a bromine atom or a fluorine atom, and more preferably a fluorine atom.

It is preferable that the anion portion of the cation generator is represented by B (C ₆ F ₅ ) ₄ ^— . The cation generator that releases an organic acid ion containing a boron atom is more preferably a compound having an anion moiety represented by the following formula (1A).

  The content of the cation generator is not particularly limited. The content of the cation generator is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, still more preferably 5 parts by weight or more, particularly preferably 100 parts by weight of the curable compound. It is 10 parts by weight or more, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and still more preferably 20 parts by weight or less. When the content of the cation generator relative to the curable compound is not less than the above lower limit and not more than the above upper limit, the conductive material is sufficiently cured.

  The content of the cation generator is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, and still more preferably 5 parts by weight with respect to 100 parts by weight of the curable compound curable by heating. Above, particularly preferably 10 parts by weight or more, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and still more preferably 20 parts by weight or less. When the content of the cation generator relative to the curable compound curable by heating is not less than the above lower limit and not more than the above upper limit, the conductive material is sufficiently thermally cured.

  From the viewpoint of further improving the connection reliability between the electrodes and the connection reliability under high humidity of the connection structure, the conductive material preferably includes both the cation generator and the thermal radical generator. . The thermal radical generator is not particularly limited. As the thermal radical generator, a conventionally known thermal radical generator can be used. As for the said thermal radical generator, only 1 type may be used and 2 or more types may be used together. Here, the “thermal radical generator” means a compound that generates radical species by heating.

  The thermal radical generator is not particularly limited, and examples thereof include azo compounds and peroxides. Examples of the peroxide include diacyl peroxide compounds, peroxyester compounds, hydroperoxide compounds, peroxydicarbonate compounds, peroxyketal compounds, dialkyl peroxide compounds, and ketone peroxide compounds.

  Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), and 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′-azobis (2-methylpropionamide) dihydrate, 2,2′-azobis (2,4,4-trimethylpentane), and the like.

  Examples of the diacyl peroxide compound include benzoyl peroxide, diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, and disuccinic acid peroxide. Examples of the peroxyester compound include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, tert-hexylperoxyneodecanoate, and tert-butylperoxyneo. Decanoate, tert-butylperoxyneoheptanoate, tert-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2 , 5-di (2-ethylhexanoylperoxy) hexane, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert -Butyl peroxyisobutyrate, tert-butyl per Kishiraureto, tert- butylperoxy isophthalate, tert- butylperoxy acetate, tert- butylperoxy octoate and tert- butyl peroxybenzoate, and the like. Examples of the hydroperoxide compound include cumene hydroperoxide and p-menthane hydroperoxide. Examples of the peroxydicarbonate compound 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 generator is preferably 30 ° C or higher, more preferably 40 ° C or higher, preferably 90 ° C or lower, more preferably 80 ° C or lower, still more preferably 70 ° C or lower. It is. If the decomposition temperature for obtaining the 10-hour half-life of the thermal radical generator is less than 30 ° C., the storage stability of the conductive material tends to be reduced, and if it exceeds 90 ° C., The action tends to make it difficult to sufficiently cure the conductive material.

  The content of the thermosetting agent is not particularly limited. The content of the thermosetting agent is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, with respect to 100 parts by weight of the curable compound curable by heating in the curable compound. More preferably 5 parts by weight or more, particularly preferably 10 parts by weight or more, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less. When the content of the thermosetting agent is not less than the above lower limit and not more than the above upper limit, the conductive material can be sufficiently thermoset. When the thermosetting agent is only a cation generator, the content of the thermosetting agent indicates the content of the cation generator, and the thermosetting agent is a cation generator and other thermosetting agents (thermal radicals). In the case of including both of the generator and the like, the total content of the cation generator and the other thermosetting agent is shown.

  When the curing agent contains a thermal radical generator, the content of the thermal radical generator is preferably 0.01 with respect to 100 parts by weight of the curable compound curable by heating in the curable compound. Part by weight or more, more preferably 0.05 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 thermal radical generator is not less than the above lower limit and not more than the above upper limit, the conductive material can be sufficiently thermoset.

  The conductive material may contain a photocuring initiator as the curing agent. The photocuring initiator includes the above-described photocation generator (photocation generator or light and thermal cation generator). The photocuring initiator is not particularly limited. A conventionally known photocuring initiator can be used as the photocuring initiator. From the viewpoint of further enhancing the conduction reliability between the electrodes and the connection reliability of the connection structure, the conductive material preferably contains a photoradical generator. As for the said photocuring initiator, only 1 type may be used and 2 or more types may be used together.

  The photocuring initiator other than the cation generator is not particularly limited, and is not limited to acetophenone photocuring initiator (acetophenone photoradical generator), benzophenone photocuring initiator (benzophenone photoradical generator), thioxanthone, ketal light. Examples thereof include a curing initiator (ketal photo radical generator), halogenated ketone, acyl phosphinoxide, and acyl phosphonate.

  Specific examples of the acetophenone photocuring initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methoxy Examples include acetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-cyclohexylacetophenone. Specific examples of the ketal photocuring initiator include benzyldimethyl ketal.

  The content of the photocuring initiator is not particularly limited. The content of the photocuring initiator is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight with respect to 100 parts by weight of the curable compound that can be cured by light irradiation in the curable compound. Part or more, preferably 2 parts by weight or less, more preferably 1 part by weight or less. When the content of the photocuring initiator is not less than the above lower limit and not more than the above upper limit, the conductive material can be appropriately photocured. By irradiating the conductive material with light and forming a B-stage, the flow of the conductive material can be suppressed. When the photocuring initiator is only a cation generator, the content of the photocuring initiator indicates the content of the cation generating agent, and the photocuring initiator is a cation generator and another photocuring initiator. When both are included, the total content of the cation generator and the other photocuring initiator is shown.

(Ion exchanger)
The cation exchanger and the anion exchanger contained in the conductive material are not particularly limited. As for the said cation exchanger, only 1 type may be used and 2 or more types may be used together. As for the said anion exchanger, only 1 type may be used and 2 or more types may be used together.

  Examples of the cation exchanger include Zr-based cation exchangers and Sb-based cation exchangers. From the viewpoint of further suppressing migration in the connection structure and further improving the insulation reliability, the cation exchanger is preferably a Zr-based cation exchanger, and preferably contains a zirconium atom.

  Examples of commercially available products of the cation exchanger include IXE-100 and IXE-300 (all of which are manufactured by Toagosei Co., Ltd.).

  Examples of the anion exchanger include Bi-based anion exchangers, Mg-Al-based anion exchangers, and Zr-based anion exchangers. From the viewpoint of further suppressing the migration in the connection structure and further improving the insulation reliability, the cation exchanger is preferably an Mg-Al anion exchanger, and includes a magnesium atom and an aluminum atom. It is preferable to include.

  Examples of the commercial product of the anion exchanger include IXE-500, IXE-530, IXE-550, IXE-700F, and IXE-800 (all of which are manufactured by Toagosei Co., Ltd.).

  The neutral exchange capacity of the cation exchanger is preferably 1 meq / g or more, more preferably 2 meq / g or more, preferably 10 meq / g or less, more preferably 4 meq / g or less. When the neutral exchange capacity of the cation exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  The neutral exchange capacity of the anion exchanger is preferably 0.1 meq / g or more, more preferably 1 meq / g or more, preferably 10 meq / g or less, more preferably 5 meq / g or less. When the neutral exchange capacity of the anion exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  The median diameter of the cation exchanger is preferably 0.1 μm or more, more preferably 0.5 μm or more, preferably 10 μm or less, more preferably 3 μm or less. When the median diameter of the cation exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  The median diameter of the anion exchanger is preferably 0.1 μm or more, more preferably 0.5 μm or more, preferably 10 μm or less, more preferably 3 μm or less. When the median diameter of the anion exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  The content of the cation exchanger is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 5 parts by weight or less, more preferably 100 parts by weight of the curable compound. 4 parts by weight or less. When the content of the cation exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  The content of the anion exchanger is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 5 parts by weight or less, more preferably 100 parts by weight of the curable compound. 4 parts by weight or less. When the content of the anion exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  The conductive material preferably contains the cation exchanger and the anion exchanger in a weight ratio of 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, and 6: More preferably, it is included at 4 to 4: 6.

(Conductive particles)
The conductive particles contained in the conductive material electrically connect the electrodes of the first and second connection target members, for example. The conductive particles are not particularly limited as long as they are conductive particles. The said electroconductive particle should just have an electroconductive part on the electroconductive surface. The surface of the conductive part of the conductive particles may be covered with an insulating layer. The surface of the conductive part of the conductive particles may be covered with insulating particles. In these cases, the insulating layer or insulating particles between the conductive portion and the electrode are excluded when the connection target member is connected.

  Examples of the conductive particles include organic particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, or metal particles whose surfaces are covered with a conductive layer (metal layer), and substantially only metal. Examples thereof include metal particles. The conductive particles are preferably conductive particles in which the surfaces of inorganic particles or organic-inorganic hybrid particles excluding organic particles, metal particles, and the like are coated with a conductive layer.

  The conductive part and the metal layer are not particularly limited. Gold, silver, copper, nickel, palladium, tin, etc. are mentioned as a metal which comprises the said electroconductive part. Examples of the metal layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, and a metal layer containing tin.

  From the viewpoint of increasing the contact area between the electrode and the conductive particle and further enhancing the conduction reliability between the electrodes, the conductive particle is composed of a resin particle and a conductive layer (on the surface of the resin particle ( First conductive layer). From the viewpoint of further improving the reliability of conduction between the electrodes, the conductive particles are preferably conductive particles having at least a conductive outer surface made of a low melting point metal. More preferably, the conductive particles include resin particles and a conductive layer disposed on the surface of the resin particles, and at least the outer surface of the conductive layer is a low melting point metal layer.

  The low melting point metal layer is a layer 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 low melting point metal preferably contains tin. In 100% by weight of the low melting point metal or the metal contained in the low melting point metal layer, the content of tin is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 70% by weight or more, particularly preferably 90% by weight. % Or more. When the content of tin is not less than the above lower limit, the connection reliability between the low melting point metal and the electrode is further enhanced. The tin content is determined using a high frequency inductively coupled plasma optical emission spectrometer (“ICP-AES” manufactured by Horiba, Ltd.) or a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu). It can be measured.

  When the outer surface of the conductive portion is a low melting point metal, the low melting point metal is melted and joined to the electrodes, and the low melting point metal conducts between the electrodes. For example, since the low melting point metal and the electrode are not in point contact but in surface contact, the connection resistance is low. In addition, the use of conductive particles having at least a conductive outer surface made of a low-melting-point metal increases the bonding strength between the low-melting-point metal and the electrode. Further, the moisture and heat resistance is further enhanced.

  The low melting point metal which comprises the said low melting metal layer is not specifically limited. The low melting point metal is preferably tin or an alloy containing tin. Examples of 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. Among them, 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 it has excellent wettability with respect to the electrode. More preferably, the alloy is a tin-indium alloy.

  The low melting point metal is preferably solder. The low melting point metal layer is preferably a solder layer. Although the material which comprises this solder is not specifically limited, Based on JISZ3001: welding terminology, it is preferable that it is a filler material whose liquidus is 450 degrees C or less. Examples of the solder composition include metal compositions containing zinc, gold, lead, copper, tin, bismuth, indium and the like. Among them, 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.

  In order to further increase the bonding strength between the low melting point metal and the electrode, the low melting point metal is nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese. Further, it may contain a metal such as chromium, molybdenum and palladium. From the viewpoint of further increasing the bonding strength between the low melting point metal and the electrode, the low melting point metal preferably contains nickel, copper, antimony, aluminum, or zinc. From the viewpoint of further increasing the bonding strength between the low melting point metal and the electrode, the content of these metals for increasing the bonding strength is preferably 100% by weight of the metal contained in the low melting point metal or the low melting point metal layer. It is 0.0001% by weight or more, preferably 1% by weight or less.

  The conductive particles include resin particles and a conductive layer disposed on the surface of the resin particles, and the outer surface of the conductive layer is a low-melting metal layer, and the resin particles and the low-melting metal In addition to the low melting point metal layer, it is preferable to have a second conductive layer between the layers (such as solder layers). In this case, the low melting point metal layer is a part of the entire conductive layer, and the second conductive layer is a part of the entire conductive layer. In the case of using the conductive particles, it is preferable to bring the second conductive layer into contact with the electrode.

  The second conductive layer different from the low melting point metal 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 and cadmium, and alloys thereof. 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.

  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. By using the conductive particles having these preferable conductive layers for the connection between the electrodes, the connection resistance between the electrodes is further reduced. In addition, a low melting point metal layer can be more easily formed on the surface of these preferable conductive layers. The second conductive layer may be a low melting point metal layer such as a solder layer. The conductive particles may have a plurality of low melting point metal layers.

  The thickness of the low melting point metal layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, preferably 50 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, particularly preferably. 3 μm or less. When the thickness of the low melting point metal layer is not less than the above lower limit, the conductivity is sufficiently high. When the thickness of the low melting point metal layer is not more than the above upper limit, the difference in thermal expansion coefficient between the resin particles and the low melting point metal layer becomes small, and the low melting point metal layer is hardly peeled off.

  When the conductive layer is a conductive layer other than the low melting point metal layer, or when the conductive layer has a multilayer structure, the total thickness of the conductive layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, Preferably it is 1 micrometer or more, Preferably it is 50 micrometers or less, More preferably, it is 10 micrometers or less, More preferably, it is 5 micrometers or less, Most preferably, it is 3 micrometers or less.

  Since the size is suitable for the conductive particles in the anisotropic conductive material and the distance between the electrodes can be further reduced, the average particle diameter of the conductive particles is preferably 0.5 μm or more, more It is preferably 1 μm or more, preferably 100 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, particularly preferably 10 μm or less, and most preferably less than 5 μm.

  The average particle diameter of the conductive particles is most preferably 1 μm or more and less than 5 μm. By using the conductive material according to the present invention, even when the average particle diameter of the conductive particles is less than 5 μm and the conductive particles are small, the connection reliability of the connection structure can be sufficiently increased.

  Further, the resin particles can be properly used according to the electrode size or land diameter of the substrate to be mounted.

  From the viewpoint of more reliably connecting the upper and lower electrodes and further suppressing the short circuit between the electrodes adjacent in the lateral direction, the ratio of the average particle diameter C of the conductive particles to the average particle diameter A of the resin particles ( C / A) is more than 1.0, preferably 3.0 or less. In addition, when the second conductive layer is present between the resin particles and the solder layer, the ratio of the resin particles to the average particle size B with respect to the average particle size B of the conductive particle portion excluding the solder layer (B / A) is greater than 1.0, preferably 2.0 or less. Further, when there is the second conductive layer between the resin particles and the solder layer, the average particle diameter B of the conductive particle portion excluding the solder layer having the average particle diameter C of the conductive particles including the solder layer. The ratio (C / B) to is more than 1.0, preferably 2.0 or less. When the ratio (B / A) is within the above range or the ratio (C / B) is within the above range, electrodes that are more reliably connected between the upper and lower electrodes and that are adjacent in the lateral direction The short circuit between them can be further suppressed.

Conductive materials for FOB and FOF applications (anisotropic conductive materials):
The conductive material is preferably used for connection between a flexible printed board and a glass epoxy board (FOB (Film on Board)) or between a flexible printed board and a flexible printed board (FOF (Film on Film)). It is done.

  In FOB and FOF applications, L & S, which is the size of a portion (line) with an electrode and a portion (space) without an electrode, is generally 100 to 500 μm. The average particle diameter of the resin particles used for FOB and FOF applications is preferably 10 to 100 μm. When the average particle diameter of the resin particles is 10 μm or more, the thickness of the conductive material and the connection portion disposed between the electrodes is sufficiently increased, and the adhesive force is further increased. When the average particle diameter of the resin particles is 100 μm or less, a short circuit is more unlikely to occur between adjacent electrodes.

Conductive materials for flip chip applications (anisotropic conductive materials):
The conductive material is suitably used for flip chip applications.

  For flip chip applications, the land diameter is generally 15-80 μm. The average particle size of the resin particles used for flip chip applications is preferably 1 to 15 μm. When the average particle diameter of the resin particles is 1 μm or more, the thickness of the solder layer disposed on the surface of the resin particles can be sufficiently increased, and the electrodes can be more reliably electrically connected. it can. When the average particle diameter of the resin particles is 10 μm or less, a short circuit is more unlikely to occur between adjacent electrodes.

Conductive material for COF (anisotropic conductive material):
The conductive material is preferably used for connection between a semiconductor chip and a flexible printed board (COF (Chip on Film)).

  In a COF application, L & S, which is a dimension between a portion (line) with an electrode and a portion (space) without an electrode (space), is generally 10 to 50 μm. The average particle diameter of the resin particles used for COF applications is preferably 1 to 10 μm. When the average particle diameter of the resin particles is 1 μm or more, the thickness of the solder layer disposed on the surface of the resin particles can be sufficiently increased, and the electrodes can be more reliably electrically connected. it can. When the average particle diameter of the resin particles is 10 μm or less, a short circuit is more unlikely to occur between adjacent electrodes.

  The “average particle diameter” of the conductive particles and the resin particles indicates a number average particle diameter. The average particle diameter of the conductive particles can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.

  The surface of the conductive portion in the conductive particles may be insulated with an insulating material, insulating particles, flux, or the like. It is preferable that the insulating material, the insulating particles, the flux, and the like are removed from the connection portion by being softened and flowed by heat at the time of connection. Thereby, the short circuit between electrodes can be suppressed.

  The content of the conductive particles is not particularly limited. The content of the conductive particles in 100% by weight of the conductive material is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, preferably 40% by weight or less. More preferably, it is 30 weight% or less, More preferably, it is 19 weight% or less. A conductive particle can be easily arrange | positioned between the upper and lower electrodes which should be connected as content of the said electroconductive particle is more than the said minimum and below the said upper limit. Furthermore, it becomes difficult to electrically connect adjacent electrodes that should not be connected via a plurality of conductive particles. That is, a short circuit between adjacent electrodes can be further prevented.

(flux)
The conductive material may contain a flux. By using the flux, the oxide film formed on the electrode surface can be effectively removed. As a result, the conduction reliability in the connection structure is further increased. Note that the conductive material does not necessarily include a flux.

  The flux is not particularly limited. As the flux, a flux generally used for soldering or the like can be used. Examples of 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. Etc. 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, and glutamic acid. Examples of the pine resin include activated pine resin and non-activated pine resin. The flux is preferably rosin. By using rosin, the connection resistance between the electrodes is further reduced.

  The rosin is a rosin composed mainly of abietic acid. The flux is preferably a rosin, and more preferably abietic acid. By using this preferable flux, the connection resistance between the electrodes is further reduced.

  The flux may be dispersed in the binder resin, or may be attached on the surface of the conductive particles.

  The content of the flux in 100% by weight of the conductive material is preferably 0.5% by weight or more, preferably 30% by weight or less, and more preferably 25% by weight or less. When the content of the flux is not less than the above lower limit and not more than the above upper limit, the oxide film formed on the electrode surface can be more effectively removed. Further, when the content of the flux is equal to or more than the lower limit, the effect of adding the flux is more effectively expressed. When the content of the flux is not more than the above upper limit, the hygroscopic property of the cured product is further lowered, and the reliability of the connection structure is further enhanced.

(Other ingredients)
The conductive material preferably contains a filler. By using the filler, the thermal expansion coefficient of the cured material of the conductive material can be suppressed. Specific examples of the filler include silica, aluminum nitride, alumina, glass, boron nitride, silicon nitride, silicone, carbon, graphite, graphene, and talc. As for a filler, only 1 type may be used and 2 or more types may be used together. When a filler having a high thermal conductivity is used, the main curing time is shortened.

  The conductive material may contain a solvent. By using the solvent, the viscosity of the conductive material can be easily adjusted. Examples of the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran, and diethyl ether.

(Details and applications of conductive materials)
The conductive material according to the present invention is preferably an anisotropic conductive material. The conductive material according to the present invention is preferably a conductive material used for electrical connection of electrodes. The conductive material according to the present invention is also preferably a conductive material used for electrical connection of electrodes in an organic electroluminescence display element. The conductive material according to the present invention is a paste-like or film-like conductive material, and is preferably a paste-like conductive material. The paste-like conductive material is a conductive paste. The film-like conductive material is a conductive film. When the conductive material is a conductive film, a film that does not include conductive particles may be laminated on the conductive film that includes the conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

  The conductive material according to the present invention is a conductive paste, and is preferably a conductive paste applied on a connection target member in a paste state.

  The viscosity of the conductive paste at 25 ° C. is preferably 20 Pa · s or more, more preferably 100 Pa · s or more, preferably 1000 Pa · s or less, more preferably 700 Pa · s or less, and further preferably 600 Pa · s or less. . When the viscosity is equal to or higher than the lower limit, sedimentation of conductive particles in the conductive paste can be suppressed. When the viscosity is equal to or lower than the upper limit, the dispersibility of the conductive particles is further increased. If the viscosity of the conductive paste before coating is within the above range, after applying the conductive paste on the first connection target member, the flow of the conductive paste before curing can be further suppressed, and the voids are further reduced. It becomes difficult to occur. The viscosity of the conductive paste at 25 ° C. may be 300 Pa · s or less. The paste form includes liquid.

  The conductive material according to the present invention is preferably a conductive material used for connecting a connection target member having a copper electrode. When a connection target member having a copper electrode is connected using a conductive material, there is a problem that migration is likely to occur due to the copper electrode in the connection structure. On the other hand, by using the conductive material according to the present invention, even if a connection target member having a copper electrode is connected, migration in the connection structure can be effectively suppressed, and insulation reliability can be effectively increased. it can.

  The conductive material according to the present invention can be used for bonding various connection target members. The conductive material is preferably used for obtaining a connection structure in which the first and second connection target members are electrically connected. The conductive material is more preferably used to obtain a connection structure in which the electrodes of the first and second connection target members are electrically connected.

  FIG. 1 is a front sectional view schematically showing an example of a connection structure using a conductive material according to an embodiment of the present invention.

  A connection structure 1 shown in FIG. 1 includes a first connection target member 2, a second connection target member 4, and a connection portion that electrically connects the first and second connection target members 2 and 4. 3. The connecting portion 3 is a cured product layer and is formed by curing a conductive material including the conductive particles 5. The connecting portion 3 is preferably formed by curing an anisotropic conductive material.

  The first connection target member 2 has a plurality of first electrodes 2b on the surface 2a (upper surface). The second connection target member 4 has a plurality of second electrodes 4b on the surface 4a (lower surface). The first electrode 2 b and the second electrode 4 b are electrically connected by one or a plurality of conductive particles 5. Therefore, the first and second connection target members 2 and 4 are electrically connected by the conductive particles 5.

  The connection between the first and second electrodes 2b and 4b is usually made by connecting the first connection target member 2 and the second connection target member 4 with the first and second electrodes 2b and 4b through a conductive material. Is carried out by applying pressure when the conductive material is cured after being overlapped so as to face each other. Generally, the conductive particles 5 are compressed by pressurization.

  The first and second connection target members are not particularly limited. Specific examples of the first and second connection target members include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, and glass boards. . The conductive material is preferably a conductive material used for connecting electronic components.

  The connection structure 1 shown in FIG. 1 can be obtained as follows, for example, through the states shown in FIGS.

  As shown in FIG. 2A, the first connection target member 2 having the first electrode 2b on the surface 2a (upper surface) is prepared. Next, a conductive material including a plurality of conductive particles 5 is disposed on the surface 2 a of the first connection target member 2, and the conductive material layer 3 </ b> A is formed on the surface 2 a of the first connection target member 2. At this time, it is preferable that one or a plurality of conductive particles 5 be arranged on the first electrode 2b.

  Next, the conductive material layer 3A is cured by irradiating the conductive material layer 3A with light. 2A to 2C, the conductive material layer 3A is B-staged by irradiating the conductive material layer 3A with light to advance the curing of the conductive material layer 3A. That is, as shown in FIG. 2B, the B-staged conductive material layer 3B is formed on the surface 2a of the first connection target member 2. By the B-stage, the first connection target member 2 and the B-staged conductive material layer 3B are temporarily bonded. The B-staged conductive material layer 3B is a semi-cured product in a semi-cured state. The B-staged conductive material layer 3B is not completely cured, and thermal curing can be further advanced. However, the conductive material layer 3A may be cured at one time by irradiating the conductive material layer 3A with light or heating the conductive material layer 3A without making the conductive material layer 3A B-staged.

In order to effectively advance the curing of the conductive material layer 3A, the light irradiation intensity when irradiating with light is preferably in the range of 0.1 to 8000 mW / cm ² . The integrated light quantity is preferably 0.1 to 20000 J / cm ² . The light source used when irradiating light is not specifically limited. Examples of the light source include a light source having a sufficient light emission distribution at a wavelength of 420 nm or less. Specific examples of the light source include, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, and an LED lamp.

  Next, as illustrated in FIG. 2C, the second connection target member 4 is laminated on the upper surface 3 a of the conductive material layer 3 </ b> B that has been B-staged. The second connection target member 4 is laminated so that the first electrode 2b on the surface 2a of the first connection target member 2 and the second electrode 4b on the surface 4a of the second connection target member 4 face each other. To do.

  Further, when the second connection target member 4 is laminated, the conductive material layer 3 </ b> B that has been B-staged is heated to further cure the conductive material layer 3 </ b> B that has been B-staged to form the connection portion 3. . However, the B-staged conductive material layer 3B may be heated before the second connection target member 4 is laminated. Furthermore, you may heat the conductive material layer 3B made into B stage after the lamination | stacking of the 2nd connection object member 4. FIG.

  The heating temperature for curing the conductive material layer 3A or the B-staged conductive material layer 3B by heating is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, even more preferably 100 ° C. or higher, and still more preferably 140. More preferably, it is 160 ° C. or more, preferably 250 ° C. or less, more preferably 200 ° C. or less. When the conductive material according to the present invention is used for electrical connection of electrodes in an organic electroluminescence display element, when the conductive material layer 3A or the B-staged conductive material layer 3B is cured, the heating temperature May be 120 ° C. or lower.

  It is preferable to apply pressure when the B-staged conductive material layer 3B is cured. By compressing the conductive particles 5 with the first electrode 2b and the second electrode 4b by pressurization, the contact area between the first and second electrodes 2b, 4b and the conductive particles 5 can be increased. it can. For this reason, conduction reliability can be improved. Further, by compressing the conductive particles 5, even if the distance between the first and second electrodes 2b and 4b increases, the particle diameter of the conductive particles 5 increases so as to follow this expansion.

  By curing the B-staged conductive material layer 3 </ b> B, the first connection target member 2 and the second connection target member 4 are connected via the connection portion 3. Further, the first electrode 2 b and the second electrode 4 b are electrically connected through the conductive particles 5. In this way, the connection structure 1 shown in FIG. 1 using a conductive material can be obtained. Here, since photocuring and thermosetting are used in combination, the conductive material can be cured in a short time.

  The conductive material according to the present invention includes, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a connection between a semiconductor chip and a flexible printed circuit board (COF (Chip on Film)), and a semiconductor chip and glass. It can be used for connection to a substrate (COG (Chip on Glass)) or connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)). Especially, the said electrically-conductive material is suitable for a FOG use or a COG use, and is more suitable for a COG use. The conductive material according to the present invention is preferably a conductive material used for connection between a flexible printed circuit board and a glass substrate or a connection between a semiconductor chip and a glass substrate, and is used for connection between the flexible printed circuit board and the glass substrate. More preferably, it is a conductive material.

  In the connection structure according to the present invention, it is preferable that the second connection target member and the first connection target member are a flexible printed circuit board and a glass substrate, or a semiconductor chip and a glass substrate. More preferably, they are a flexible printed circuit board and a glass substrate.

  The connection structure according to the present invention is preferably an organic electroluminescence display element. The electrodes in the organic electroluminescence display element may be electrically connected by conductive particles contained in the conductive material.

  It is preferable that at least one of the first electrode and the second electrode is a copper electrode. Both the first electrode and the second electrode are preferably copper electrodes. In this case, the effect of suppressing migration by the conductive material according to the present invention is further obtained, and the insulation reliability in the connection structure is further increased.

  The electrode width (first electrode width and second electrode width) is preferably 5 μm or more, more preferably 10 μm or more, preferably 500 μm or less, more preferably 300 μm or less. The inter-electrode width (the first inter-electrode width and the second inter-electrode width) is preferably 3 μm or more, more preferably 10 μm or more, preferably 500 μm or less, more preferably 300 μm or less. Further, L / S (line / space) as electrode width / interelectrode width is preferably 5 μm / 5 μm or more, more preferably 10 μm / 10 μm or more, preferably 500 μm / 500 μm or less, more preferably 300 μm / 300 μm or less. is there.

  In recent years, L / S (line / space) which is the electrode width / interelectrode width in the connection structure has been further reduced. The smaller the L / S of the electrode in the connection structure is, the easier it is to cause insulation failure when migration occurs. On the other hand, by using the conductive material according to the present invention, even if a fine electrode is connected, the occurrence of insulation failure can be effectively suppressed, and insulation reliability can be sufficiently secured.

  Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Reference Examples. The present invention is not limited only to the following examples.

  In the examples and comparative examples, the following materials were used.

(Ion exchanger)
(1) IXE-100 (Zr-based cation exchanger, neutral exchange capacity 3.3 meq / g, manufactured by Toagosei Co., Ltd.)
(2) IXE-700F (Mg-Al anion exchanger, neutral exchange capacity 4.5 meq / g, manufactured by Toagosei Co., Ltd.)
(3) IXE-300 (Sb cation exchanger, neutral exchange capacity 2.3 meq / g, manufactured by Toagosei Co., Ltd.)
(4) IXE-500 (Bi-based anion exchanger, neutral exchange capacity 1.8 meq / g, manufactured by Toagosei Co., Ltd.)
(5) IXE-530 (Bi-based anion exchanger, neutral exchange capacity 1.8 meq / g, manufactured by Toagosei Co., Ltd.)
(6) IXE-633 (Sb, Bi-based ion exchanger, neutral exchange capacity 1.8 meq / g, manufactured by Toagosei Co., Ltd.)

Example 1
(1) Preparation of anisotropic conductive material:
SI-60L which is a cation generator is added to 40 parts by weight of a bisphenol A-modified epoxy resin (“EPICLON EXA-4850-150” manufactured by DIC) and 30 parts by weight of a bisphenol F epoxy resin (“EXA-835LV” manufactured by DIC). 3 parts by weight (Sun Aid manufactured by Sanshin Chemical Co., Ltd.), 20 parts by weight of epoxy acrylate (“EBECRYL 3702” manufactured by Daicel Cytec Co., Ltd.) which is a photocurable compound, and acylphosphine oxide compound (Ciba) which is a photocuring initiator -"DAROCUR TPO" manufactured by Japan Co., Ltd.) 1 part by weight, 10 parts by weight of silica having an average particle diameter of 0.25 μm as filler, 4 parts by weight of conductive particles A having an average particle diameter of 10 μm, and the above (ion exchanger) 1) 1 part by weight of IXE-100 (manufactured by Toagosei Co., Ltd.) and (2) IXE-70 F was added and (Toagosei Co., Ltd.) 1 part by weight, by stirring for 5 minutes at 2000rpm using a planetary stirrer to obtain an anisotropic conductive paste. The conductive particles A used are conductive particles having a metal layer in which a nickel plating layer is formed on the surface of divinylbenzene resin particles and a gold plating layer is formed on the surface of the nickel plating layer. is there.

(2) Fabrication of connection structure (FOG):
A glass substrate (first connection target member) having an L / S of 50 μm / 50 μm and a 1 mm long aluminum electrode pattern formed on the upper surface was prepared. In addition, a flexible printed circuit board (second connection target member) having a gold-plated Cu electrode pattern with a L / S of 50 μm / 50 μm and a length of 2 mm formed on the lower surface was prepared.

On the said glass substrate, the anisotropic conductive paste immediately after preparation was applied using a dispenser so that it might become width 1.5mm and thickness 40 micrometers, and the anisotropic conductive paste layer was formed. Next, the flexible printed circuit board was laminated on the anisotropic conductive paste layer so that the electrodes face each other. A 365 nm ultraviolet ray was irradiated for 3 seconds so that the light irradiation intensity was 3000 mW / cm ^2, and the anisotropic conductive paste layer was semi-cured by photopolymerization to form a B stage. Then, using “BD-02” manufactured by Ohashi Manufacturing Co., Ltd., adjusting the temperature of the thermocompression bonding head so that the temperature of the anisotropic conductive paste layer is 170 ° C. (the main pressure bonding temperature). A pressure-bonding head was placed and the anisotropic conductive paste layer was cured at 170 ° C. for 5 seconds under a pressure of 1 MPa to obtain a connection structure.

(Example 2)
Example 1 except that the amount of (1) IXE-100 was changed to 0.01 parts by weight and the amount of (2) IXE-700F was changed to 0.01 parts by weight. Thus, an anisotropic conductive paste was obtained. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Example 3)
Anisotropic as in Example 1, except that the amount of (1) IXE-100 was changed to 5 parts by weight and that the amount of (2) IXE-700F was changed to 5 parts by weight. Conductive paste was obtained. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

Example 4
An anisotropic conductive paste was obtained in the same manner as in Example 1 except that (2) IXE-700F was changed to (4) IXE-500 (manufactured by Toagosei Co., Ltd.). Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Example 5)
(1) IXE-100 was changed to (3) IXE-300 (manufactured by Toagosei Co., Ltd.) and (2) IXE-700F was changed to (4) IXE-500 (manufactured by Toagosei Co., Ltd.) Except that, an anisotropic conductive paste was obtained in the same manner as in Example 1. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Example 6)
(1) IXE-100 was changed to (3) IXE-300 (made by Toagosei Co., Ltd.) and (2) IXE-700F was changed to (5) IXE-530 (made by Toagosei Co., Ltd.) Except that, an anisotropic conductive paste was obtained in the same manner as in Example 1. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Comparative Example 1)
An anisotropic conductive paste was obtained in the same manner as in Example 1 except that both (1) IXE-100 and (2) IXE-700F were not added. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Comparative Example 2)
An anisotropic conductive paste was obtained in the same manner as in Example 1 except that (1) IXE-100 was not added. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Comparative Example 3)
An anisotropic conductive paste was obtained in the same manner as in Example 1 except that (2) IXE-700F was not added. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Comparative Example 4)
Except for adding 2 parts by weight of IXE-633 (manufactured by Toagosei Co., Ltd.) without adding both (1) IXE-100 and (2) IXE-700F, the same procedure as in Example 1 was performed. An anisotropic conductive paste was obtained. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Reference Example 1)
In the same manner as in Example 1 except that 10 parts by weight of a thermosetting agent (imidazole compound, “2P-4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added without adding SI-60L as a cation generator. An anisotropic conductive paste was obtained. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Reference Example 2)
Without adding SI-60L which is a cation generator, 10 parts by weight of a thermosetting agent (imidazole compound, “2P-4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) and (1) IXE-100, and An anisotropic conductive paste was obtained in the same manner as in Example 1 except that both (2) IXE-700F were not added. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 1.

(Evaluation of Examples 1 to 6, Comparative Examples 1 to 4 and Reference Examples 1 and 2)
(1) Conduction reliability (connection resistance value)
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 connection resistance at 100 locations 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 conduction reliability of the obtained connection structure was determined according to the following criteria.

[Judgment criteria for conduction reliability]
○○: Less than 3Ω ○: 3Ω or more, less than 5Ω ×: 5Ω or more

(2) Moisture-resistant insulation reliability With a voltage of 20 V applied between the measurement terminals insulated from each other of the obtained connection structure, exposure was performed in an atmosphere of 85 ° C. and 85% RH for 500 hours, The change in resistance value between the measuring terminals was measured. The case where the resistance value was 10 ⁵ Ω or less was judged as an insulation failure. Moisture resistance insulation reliability was judged according to the following criteria.

[Criteria for moisture-resistant insulation reliability]
◯: Of the 10 connection structures, there is no connection structure in which insulation failure occurs, and the average resistance value after the moisture-proof insulation reliability test is 10 ⁷ Ω or more. ◯: Of the 10 connection structures There is no connection structure in which insulation failure has occurred, and the average resistance value after the moisture-proof insulation reliability test is 10 ⁶ Ω or more and less than 10 ⁷ Ω Δ: Among 10 connection structures, insulation failure has occurred There is no connection structure, and the average resistance value after the moisture-proof insulation reliability test is 10 ⁵ Ω or more and less than 10 ⁶ Ω x: Of the 10 connection structures, 1 is the connection structure in which insulation failure occurs There are more than

  The results are shown in Table 1 below.

(Example 7)
(1) Production of conductive particles:
Electroless nickel plating was performed on divinylbenzene resin particles having an average particle diameter of 10 μm (manufactured by Sekisui Chemical Co., Ltd., Micropearl SP-210) to form a base nickel plating layer having a thickness of 0.1 μm on the surface of the resin particles. Next, the resin particles on which the base nickel plating layer was formed were subjected to electrolytic copper plating to form a 1 μm thick copper layer. Furthermore, electrolytic plating was performed using an electrolytic plating solution containing tin and bismuth to form a solder layer having a thickness of 1 μm. Thus, a 1 μm thick copper layer is formed on the surface of the resin particles, and a 1 μm thick solder layer (tin: bismuth = 43 wt%: 57 wt%) is formed on the surface of the copper layer. Conductive particles B were prepared.

(2) Preparation of anisotropic conductive material:
SI-60L which is a cation generator is added to 40 parts by weight of a bisphenol A-modified epoxy resin (“EPICLON EXA-4850-150” manufactured by DIC) and 30 parts by weight of a bisphenol F epoxy resin (“EXA-835LV” manufactured by DIC). 3 parts by weight (Sun Aid manufactured by Sanshin Chemical Co., Ltd.), 20 parts by weight of epoxy acrylate (“EBECRYL 3702” manufactured by Daicel Cytec Co., Ltd.) which is a photocurable compound, and acylphosphine oxide compound (Ciba) which is a photocuring initiator -"DAROCUR TPO" manufactured by Japan Co., Ltd.) 1 part by weight, 10 parts by weight of silica having an average particle diameter of 0.25 μm as a filler, 3 parts by weight of rosin as a flux, and 4 parts by weight of the obtained conductive particles B 1 part by weight of (1) IXE-100 (manufactured by Toagosei Co., Ltd.), which is an ion exchanger, An anisotropic conductive paste was obtained by adding 1 part by weight of (2) IXE-700F (manufactured by Toagosei Co., Ltd.) and stirring for 5 minutes at 2000 rpm using a planetary stirrer.

(2) Production of Connection Structure (FOB) A glass epoxy substrate (first connection target member) having a gold-plated Cu electrode pattern with an L / S of 100 μm / 100 μm and a length of 4 mm formed on the upper surface was prepared. In addition, a flexible printed circuit board (second connection target member) having a gold-plated Cu electrode pattern having a L / S of 100 μm / 100 μm and a length of 4 mm formed on the lower surface was prepared.

On the said glass substrate, the anisotropic conductive paste immediately after preparation was applied using a dispenser so that it might become width 1.5mm and thickness 40 micrometers, and the anisotropic conductive paste layer was formed. Next, the flexible printed circuit board was laminated on the anisotropic conductive paste layer so that the electrodes face each other. A 365 nm ultraviolet ray was irradiated for 3 seconds so that the light irradiation intensity was 3000 mW / cm ^2, and the anisotropic conductive paste layer was semi-cured by photopolymerization to form a B stage. Then, using “BD-02” manufactured by Ohashi Manufacturing Co., Ltd., adjusting the temperature of the thermocompression bonding head so that the temperature of the anisotropic conductive paste layer is 170 ° C. (the main pressure bonding temperature). A pressure-bonding head was placed and the anisotropic conductive paste layer was cured at 170 ° C. for 5 seconds under a pressure of 1 MPa to obtain a connection structure.

(Example 8)
Example 1 except that the amount of (1) IXE-100 was changed to 0.01 parts by weight and the amount of (2) IXE-700F was changed to 0.01 parts by weight. Thus, an anisotropic conductive paste was obtained. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

Example 9
Similar to Example 7, except that the blending amount of (1) IXE-100 was changed to 5 parts by weight and that the blending amount of (2) IXE-700F was changed to 5 parts by weight. Conductive paste was obtained. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 10)
An anisotropic conductive paste was obtained in the same manner as in Example 7 except that (2) IXE-700F was changed to (4) IXE-500 (manufactured by Toagosei Co., Ltd.). Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 11)
(1) IXE-100 was changed to (3) IXE-300 (manufactured by Toagosei Co., Ltd.) and (2) IXE-700F was changed to (4) IXE-500 (manufactured by Toagosei Co., Ltd.) Except that, an anisotropic conductive paste was obtained in the same manner as in Example 7. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 12)
(1) IXE-100 was changed to (3) IXE-300 (made by Toagosei Co., Ltd.) and (2) IXE-700F was changed to (5) IXE-530 (made by Toagosei Co., Ltd.) Except that, an anisotropic conductive paste was obtained in the same manner as in Example 7. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 13)
An anisotropic conductive paste was obtained in the same manner as in Example 7 except that rosin as a flux was not blended. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 14)
An anisotropic conductive paste was obtained in the same manner as in Example 7 except that the conductive particle B was changed to the conductive particle A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 15)
An anisotropic conductive paste was obtained in the same manner as in Example 8 except that the conductive particle B was changed to the conductive particle A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 16)
An anisotropic conductive paste was obtained in the same manner as in Example 9 except that the conductive particle B was changed to the conductive particle A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 17)
An anisotropic conductive paste was obtained in the same manner as in Example 10 except that the conductive particles B were changed to the conductive particles A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 18)
An anisotropic conductive paste was obtained in the same manner as in Example 11 except that the conductive particle B was changed to the conductive particle A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 19)
An anisotropic conductive paste was obtained in the same manner as in Example 12 except that the conductive particles B were changed to the conductive particles A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 20)
The type and amount of the thermosetting compound are 40 parts by weight of bisphenol A-modified epoxy resin (DIC Corporation "EPICLON EXA-4850-150") and bisphenol F epoxy resin (DIC Corporation "EXA-835LV") 30 weights. Parts, except that the bisphenol E epoxy resin ("R1710" manufactured by Printec Co., Ltd.) was changed to 70 parts by weight, and the conductive particles B were changed to the conductive particles A in the same manner as in Example 7, An anisotropic conductive paste was obtained. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Example 21)
The type of cation generator was changed from SI-60L (Sun Shin Aid made by Sanshin Chemical Co., Ltd.) to CXC-1612 (K-PURE made by Enomoto Kasei Co., Ltd.), and the conductive particles B were changed to the conductive particles. An anisotropic conductive paste was obtained in the same manner as Example 7 except for changing to A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Comparative Example 5)
An anisotropic conductive paste was obtained in the same manner as in Example 7 except that both (1) IXE-100 and (2) IXE-700F were not added. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Comparative Example 6)
An anisotropic conductive paste was obtained in the same manner as in Example 7 except that (1) IXE-100 was not added. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Comparative Example 7)
An anisotropic conductive paste was obtained in the same manner as in Example 7 except that (2) IXE-700F was not added. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Comparative Example 8)
An anisotropic conductive paste was obtained in the same manner as in Comparative Example 5 except that the conductive particles B were changed to the conductive particles A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Comparative Example 9)
An anisotropic conductive paste was obtained in the same manner as in Comparative Example 6 except that the conductive particles B were changed to the conductive particles A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Comparative Example 10)
An anisotropic conductive paste was obtained in the same manner as in Comparative Example 7 except that the conductive particles B were changed to the conductive particles A. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Comparative Example 11)
Except for adding 2 parts by weight of IXE-633 (manufactured by Toagosei Co., Ltd.) without adding both (1) IXE-100 and (2) IXE-700F, the same procedure as in Example 7 was performed. An anisotropic conductive paste was obtained. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Reference Example 3)
In the same manner as in Example 7 except that 10 parts by weight of a thermosetting agent (imidazole compound, “2P-4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added without adding SI-60L as a cation generator. An anisotropic conductive paste was obtained. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Reference Example 4)
Without adding SI-60L which is a cation generator, 10 parts by weight of a thermosetting agent (imidazole compound, “2P-4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) and (1) IXE-100, and An anisotropic conductive paste was obtained in the same manner as in Example 7 except that both (2) IXE-700F were not added. Using the obtained anisotropic conductive paste, a connection structure was obtained in the same manner as in Example 7.

(Evaluation of Examples 7 to 21, Comparative Examples 5 to 11 and Reference Examples 3 and 4)
(1) Conduction reliability (connection resistance value)
The connection resistance between the upper and lower electrodes of the obtained connection structure was measured by a four-terminal method. The average connection resistance of 10 connection structures 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 conduction reliability of the obtained connection structure was determined according to the following criteria.

[Judgment criteria for conduction reliability]
○○: Less than 8Ω ○: 8Ω or more, less than 10Ω ×: 10Ω or more

(2) Moisture-resistant insulation reliability With a voltage of 15 V applied between the measurement terminals insulated from each other of the obtained connection structure, it was exposed in an atmosphere of 85 ° C. and 85% RH for 500 hours, The change in resistance value between the measuring terminals was measured. The case where the resistance value was 10 ⁵ Ω or less was judged as an insulation failure. Moisture resistance insulation reliability was judged according to the following criteria.

[Criteria for moisture-resistant insulation reliability]
◯: Of the 10 connection structures, there is no connection structure in which insulation failure occurs, and the average resistance value after the moisture-proof insulation reliability test is 10 ⁷ Ω or more. ◯: Of the 10 connection structures There is no connection structure in which insulation failure has occurred, and the average resistance value after the moisture-proof insulation reliability test is 10 ⁶ Ω or more and less than 10 ⁷ Ω Δ: Among 10 connection structures, insulation failure has occurred There is no connection structure, and the average resistance value after the moisture-proof insulation reliability test is 10 ⁵ Ω or more and less than 10 ⁶ Ω x: Of the 10 connection structures, 1 is the connection structure in which insulation failure occurs There are more than

  The results are shown in Table 2 below. In the connection structures of Examples, Comparative Examples, and Reference Examples using the conductive particles B, the solder layer of the conductive particles B is solidified after melting at the time of manufacturing the connection structures, and the electrodes in the connection structures The copper layer of the electroconductive particle B was contacting.

  In addition, the evaluation result of conduction | electrical_connection reliability of Example 3, 16 and Reference Examples 1-4 was both "(circle)". However, the value of the connection resistance in the evaluation of the conduction reliability in Examples 3 and 16 was lower than the value of the connection resistance in Reference Examples 1 to 4.

  It should be noted that the conduction reliability evaluation results of Example 7 and Example 14 are both “◯◯”, and the conduction reliability evaluation results of Example 8 and Example 15 are both “◯◯”. The evaluation results of conduction reliability between Example 10 and Example 17 are both “◯◯”, and the evaluation results of conduction reliability between Example 11 and Example 18 are both “◯◯”. 12 and the evaluation result of the conduction reliability of Example 19 were both “◯◯”.

  However, the connection resistance in the conduction reliability evaluation of Example 7 is 0.7Ω lower than the connection resistance in the conduction reliability evaluation of Example 14, and the connection resistance in the conduction reliability evaluation of Example 8 is Example 15. The connection resistance in the evaluation of conduction reliability of Example 10 is 0.8Ω lower than the connection resistance in the evaluation of conduction reliability of Example 17, 11 is 0.8 Ω lower than the connection resistance in the conduction reliability evaluation in Example 18, and the connection resistance in the conduction reliability evaluation in Example 12 is the conduction reliability in Example 19. It was 0.7Ω lower than the connection resistance in the evaluation.

  In addition, only the evaluation result which used the anisotropic conductive material of the Example, the comparative example, and the reference example for the connection structure (FOG or FOB) was shown. Even when the anisotropic conductive materials of Examples, Comparative Examples and Reference Examples are used for other connection structures not evaluated (FOB, FOG, COF, COG, etc.), Examples and Comparative Examples are further included. Even when the electrodes of the organic electroluminescence display element are electrically connected using the anisotropic conductive material of the reference example as a conductive material, (1) conduction reliability and (2) moisture resistance insulation reliability The evaluation result confirmed that the tendency similar to the evaluation result of the Example mentioned above, a comparative example, and a reference example was shown.

DESCRIPTION OF SYMBOLS 1 ... Connection structure 2 ... 1st connection object member 2a ... Surface 2b ... 1st electrode 3 ... Connection part 3a ... Upper surface 3A ... Conductive material layer 3B ... B-staged conductive material layer 4 ... 2nd connection Target member 4a ... surface 4b ... second electrode 5 ... conductive particles

Claims (10)

Including a curable component, a cation exchanger, an anion exchanger, and conductive particles;
The curable component contains a curable compound and a cation generator ,
The neutral exchange capacity of the cation exchanger is 1 meq / g or more, and the neutral exchange capacity of the anion exchanger is 0.1 meq / g or more,
The content of the cation exchanger is 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the curable compound, and the content of the anion exchanger is 0.01 parts by weight or more. , Ru der than 5 parts by weight, the conductive material.   2. The conductive material according to claim 1, wherein a neutral exchange capacity of the cation exchanger is 2 meq / g or more and a neutral exchange capacity of the anion exchanger is 1 meq / g or more.   The conductive material according to claim 1, wherein the cation exchanger includes a zirconium atom.   The conductive material according to claim 1, wherein the anion exchanger includes a magnesium atom and an aluminum atom. The conductive particles have resin particles and a conductive layer disposed on the surface of the resin particles,
At least the outer surface, having a melting point of low melting point metal layer is 450 ° C. or less, a conductive material according to any one of claims 1 to 4 in the conductive layer. Further comprising a flux, conductive material according to any one of claims 1-5. The conductive material according to any one of claims 1 to 6 , which is a conductive material used for connecting a connection target member having a copper electrode. An anisotropic conductive material, the conductive material according to any one of claims 1-7. A first connection target member, a second connection target member, and a connection portion that electrically connects the first and second connection target members;
The connection structure in which the said connection part is formed with the electrically-conductive material of any one of Claims 1-8 . The first connection object member has a first electrode on a surface;
The second connection object member has a second electrode on the surface,
The first electrode and the second electrode are electrically connected by the conductive particles;
The connection structure according to claim 9 , wherein at least one of the first electrode and the second electrode is a copper electrode.

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