WO2009107699A1 - Curable epoxy composition, anisotropic conductive material and connection structure - Google Patents

Curable epoxy composition, anisotropic conductive material and connection structure Download PDF

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Publication number
WO2009107699A1
WO2009107699A1 PCT/JP2009/053503 JP2009053503W WO2009107699A1 WO 2009107699 A1 WO2009107699 A1 WO 2009107699A1 JP 2009053503 W JP2009053503 W JP 2009053503W WO 2009107699 A1 WO2009107699 A1 WO 2009107699A1
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Prior art keywords
epoxy
curable epoxy
carbon atoms
curable
epoxy composition
Prior art date
Application number
PCT/JP2009/053503
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French (fr)
Japanese (ja)
Inventor
敬士 久保田
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積水化学工業株式会社
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Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to KR1020107019039A priority Critical patent/KR101329887B1/en
Priority to JP2009509200A priority patent/JP4473341B2/en
Priority to CN2009801068189A priority patent/CN101959922B/en
Publication of WO2009107699A1 publication Critical patent/WO2009107699A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3236—Heterocylic compounds
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Definitions

  • the present invention relates to a curable epoxy composition, and more particularly, can be quickly cured at a low temperature, and when used for connection between electrodes such as a circuit board or an electronic component, the gap between the electrodes is efficient.
  • the present invention relates to a curable epoxy composition that can be connected to a conductive layer, an anisotropic conductive material using the curable epoxy composition, and a connection structure.
  • Anisotropic conductive materials such as anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, or anisotropic conductive sheet are widely known.
  • An anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like.
  • an anisotropic conductive material is arranged between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be connected by heating and pressurizing.
  • Patent Document 1 includes an anisotropic containing a thermosetting insulating adhesive, conductive particles, an imidazole latent curing agent, and an amine latent curing agent.
  • a conductive conductive adhesive film is disclosed.
  • Patent Document 1 describes that connection reliability is excellent even when this anisotropic conductive adhesive film is cured at a relatively low temperature. JP-A-9-115335
  • the heating temperature necessary to start curing is relatively low.
  • the curing reaction may not sufficiently proceed at low temperatures. Therefore, in order to connect between the electrodes of the circuit board or the electronic component using this anisotropic conductive adhesive film, it has been necessary to increase the heating temperature or to heat for a long time. Therefore, the electrodes may not be efficiently connected.
  • An object of the present invention is to provide a curable epoxy composition that can be quickly cured at a low temperature and that can efficiently connect a connection target member when used for connection of the connection target member, and the curable epoxy composition.
  • An object of the present invention is to provide an anisotropic conductive material and a connection structure using an object.
  • the epoxy component contains an epoxy component and a curing agent, and the epoxy component has a structure represented by the following formula (1).
  • a curable epoxy composition comprising a single bonded multimer or a mixture of the monomer and the multimer.
  • R1 represents an alkylene group having 1 to 5 carbon atoms
  • R2 represents an alkylene group having 1 to 5 carbon atoms
  • R3 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following formula ( 2)
  • R4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structure represented by the following formula (3).
  • R5 represents an alkylene group having 1 to 5 carbon atoms.
  • R6 represents an alkylene group having 1 to 5 carbon atoms.
  • R3 and R4 are hydrogen atoms.
  • the content of the individually bonded multimer or the mixture of the monomer and the multimer is in the range of 5 to 100% by weight.
  • the epoxy component further includes an epoxy compound having a heterocyclic ring containing a nitrogen atom.
  • the epoxy compound having a heterocyclic ring containing a nitrogen atom is represented by the following formula (7) or the following formula (8).
  • Epoxy compound is represented by the following formula (7) or the following formula (8).
  • R11 to R13 each represents an alkylene group having 1 to 5 carbon atoms
  • X represents an epoxy group or a hydroxymethyl group
  • R14 to R16 each represent an alkylene group having 1 to 5 carbon atoms
  • p, q and r each represents an integer of 1 to 5
  • R17 to R19 each represents an alkylene group having 1 to 5 carbon atoms. Indicates a group.
  • the epoxy compound having a heterocyclic ring containing a nitrogen atom is triglycidyl isocyanurate or trishydroxyethyl isocyanurate triglycidyl ether.
  • the content of the epoxy compound having a heterocyclic ring containing a nitrogen atom is 0.1 to 10% by weight in 100% by weight of the epoxy component. Within range.
  • the epoxy component further includes an epoxy compound having an aromatic ring.
  • the aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring.
  • the anisotropic conductive material according to the present invention contains a curable epoxy composition configured according to the present invention and conductive particles.
  • a connection structure according to the present invention includes a cured product layer and a connection target member connected by the cured product layer, and the cured product layer is formed according to the present invention and conductive particles. It is formed by hardening the anisotropic conductive material containing these.
  • connection structure according to the present invention includes a cured product layer and a connection target member connected by the cured product layer, and the cured product layer cures the curable epoxy composition configured according to the present invention. It is formed by letting.
  • the curable epoxy composition according to the present invention includes an epoxy compound monomer having the above specific structure, a multimer in which at least two epoxy compounds are bonded, or a mixture of the monomer and the multimer. Since it contains a curing agent, it can be quickly cured at a low temperature.
  • connection target members when the curable epoxy composition according to the present invention is used for connecting the connection target members, the connection target members can be efficiently connected.
  • an anisotropic conductive material including the curable epoxy composition according to the present invention and conductive particles is used for connection between electrodes of a circuit board or an electronic component, the electrodes can be efficiently connected.
  • FIG. 1 is a front cross-sectional view schematically showing a connection structure using an anisotropic conductive material including a curable epoxy composition according to an embodiment of the present invention and conductive particles.
  • the curable epoxy composition according to the present invention contains an epoxy component and a curing agent.
  • the epoxy component is a monomer of an epoxy compound having a structure represented by the following formula (1), a multimer in which at least two epoxy compounds are bonded, or a mixture of the monomer and the multimer ( Hereinafter, it may be abbreviated as epoxy component A).
  • the epoxy component A includes a monomer of an epoxy compound having a structure represented by the following formula (1), a multimer in which at least two epoxy compounds are bonded, and a mixture of the monomer and the multimer. Is one of the following.
  • R1 represents an alkylene group having 1 to 5 carbon atoms
  • R2 represents an alkylene group having 1 to 5 carbon atoms
  • R3 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following formula ( 2)
  • R4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structure represented by the following formula (3).
  • R5 represents an alkylene group having 1 to 5 carbon atoms.
  • R6 represents an alkylene group having 1 to 5 carbon atoms.
  • the curing rate of the curable epoxy composition decreases. Moreover, when carbon number of the said alkyl group exceeds 5, the cure rate of a curable epoxy composition will fall. When the carbon number of the alkylene group and the alkyl group is small, the curing rate of the curable epoxy composition is increased.
  • R1 is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group.
  • R2 in the above formula (1) is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group.
  • the alkylene group may be an alkylene group having a linear structure or an alkylene group having a branched structure.
  • the R1 and the R2 may be the same or different.
  • R3 in the above formula (1) is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a structure represented by the above formula (2), a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, Or it is more preferable that it is a structure represented by the said Formula (2), Furthermore, it is more preferable that it is a structure represented by a hydrogen atom, a methyl group, or the said Formula (2).
  • R4 in the above formula (1) is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a structure represented by the above formula (3), and is a hydrogen atom, an alkyl group having 1 or 2 carbon atoms.
  • the alkyl group may be an alkyl group having a linear structure or an alkyl group having a branched structure.
  • R3 and R4 may be the same or different.
  • R5 is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group.
  • R6 in the above formula (3) is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group.
  • the alkylene group may be an alkylene group having a linear structure or an alkylene group having a branched structure.
  • the epoxy compound having a structure represented by the above formula (1) has an unsaturated double bond and at least two epoxy groups. Since the curable epoxy composition of the present invention contains the epoxy component A, it can be quickly cured at a low temperature. Further, when conductive particles are added to the curable epoxy composition of the present invention, and the composition containing the conductive particles is used for connection between electrodes of a circuit board or an electronic component, the electrodes are efficiently connected. it can.
  • Examples of the epoxy compound having the structure represented by the above formula (1) include an epoxy in which R1 is a methylene group, R2 is a methylene group, R3 is a hydrogen atom, and R4 is a hydrogen atom in the above formula (1).
  • R1 is a methylene group
  • R2 is a methylene group
  • R3 is a structure represented by the following formula (4)
  • R4 is a hydrogen atom
  • R1 is a methylene group
  • R2 is a methylene group
  • R3 is a structure represented by the following formula (4)
  • R4 is a hydrogen atom
  • R1 is a methylene group
  • R2 is a methylene group
  • R3 and R4 are epoxy compounds having a structure represented by the following formula (4), respectively.
  • R3 and R4 in the above formula (1) are preferably hydrogen atoms. That is, the epoxy compound having a structure represented by the above formula (1) is preferably an epoxy compound having a structure represented by the following formula (1A).
  • R1 represents an alkylene group having 1 to 5 carbon atoms
  • R2 represents an alkylene group having 1 to 5 carbon atoms
  • R1 is a methylene group
  • R2 is a methylene group
  • R3 is a hydrogen atom
  • R4 is a hydrogen atom.
  • An epoxy compound having a structure represented by the following formula (1B) is more preferable.
  • the epoxy compound having a structure represented by the above formula (1) is a monomer.
  • the epoxy compound having the structure represented by the above formula (1) instead of the monomer of the epoxy compound having the structure represented by the above formula (1) or together with the monomer of the epoxy compound.
  • a multimer in which at least two are bonded may be used.
  • the epoxy component A includes an epoxy compound monomer having a structure represented by the above formula (1), a multimer in which 2 to 10 epoxy compounds are bonded, or the monomer and the large amount.
  • the viscosity of the curable epoxy composition may be too high.
  • the by-product includes a multimer in which two or three of the monomers are bonded. Depending on storage conditions, two or more of the above monomers may be bonded.
  • the epoxy component A is preferably contained in the range of 5 to 80% by weight in 100% by weight of the curable epoxy composition of the present invention, and more preferably in the range of 10 to 70% by weight. preferable.
  • the cure rate in low temperature may not fully be raised.
  • curing agent will become relatively small, and the epoxy component A etc. may not fully be hardened
  • the content of the epoxy component A in 100% by weight of the epoxy component is preferably in the range of 5 to 100% by weight.
  • the epoxy component A and another epoxy component other than the epoxy component A (hereinafter also referred to as epoxy component B) are used in combination, the epoxy component A is contained in 100% by weight of the epoxy component.
  • the amount is preferably in the range of 5 to 90% by weight.
  • a curable epoxy composition can be hardened more rapidly at low temperature.
  • the more preferable lower limit of the content of the epoxy component A in 100% by weight of the epoxy component is 20% by weight, the further preferable lower limit is 40% by weight, the more preferable upper limit is 80% by weight, and the more preferable upper limit is 60% by weight.
  • the curable epoxy composition of the present invention may contain an epoxy component other than the epoxy component A (hereinafter also referred to as epoxy component B).
  • the epoxy component preferably contains, as the epoxy component B, an epoxy compound B3 having a heterocyclic ring containing a nitrogen atom.
  • an epoxy compound B3 having a heterocyclic ring containing a nitrogen atom.
  • the epoxy component may contain an epoxy resin B1 other than the epoxy compound B3 as the epoxy component B.
  • the epoxy component may include an epoxy compound B2 other than the epoxy compound B3 and the epoxy resin B1.
  • the curable epoxy composition of the present invention preferably contains the epoxy compound B2 or the epoxy compound B3, more preferably contains the epoxy compound B2, and further contains the epoxy compound B2 and the epoxy compound B3. Is more preferable.
  • the viscosity of the composition containing the epoxy component A is relatively low.
  • the combined use of the epoxy component A and the epoxy compound B2 can increase the viscosity of the curable epoxy composition.
  • the combined use of the epoxy component A and the epoxy compound B3 can further increase the curing rate of the curable epoxy composition or improve the heat resistance of the cured product of the curable epoxy composition.
  • the combined use of the epoxy component A, the epoxy compound B2, and the epoxy compound B3 increases the curing rate of the curable epoxy composition, improves the heat resistance of the cured product of the curable epoxy composition, and further cures the cured product. It is possible to easily apply the conductive epoxy composition.
  • epoxy resin generally means a low molecular weight polymer or prepolymer having two or more epoxy groups in one molecule and having a molecular weight of 10,000 or less, or an epoxy group of the polymer or prepolymer. It is a curable resin produced by a ring-opening reaction.
  • the curable resin may be a thermosetting resin or a photocurable resin.
  • the epoxy resin B1 include a bisphenol type epoxy resin, an epoxy novolac resin, or an epoxy resin having a naphthalene structure.
  • Examples of the commercially available epoxy compound B2 include Adeka Resin EP-3300S and Adeka Resin EP-3300E (all of which are manufactured by ADEKA).
  • the curable epoxy composition preferably contains at least one of Adeka Resin EP-3300S and Adeka Resin EP-3300E, and more preferably contains Adeka Resin EP-3300S. By using these preferable commercial products, the viscosity of the curable epoxy composition can be effectively increased.
  • the epoxy compound B2 is preferably an epoxy compound having an aromatic ring.
  • the epoxy component preferably includes an epoxy compound having an aromatic ring.
  • the aromatic ring is preferably a benzene ring, a naphthalene ring or an anthracene ring, and more preferably a benzene ring or a naphthalene ring.
  • the curable epoxy composition can be more easily applied.
  • Examples of the epoxy compound having an aromatic ring include resorcinol diglycidyl ether and 1,6-naphthalenediglycidyl ether, and resorcinol diglycidyl ether is particularly preferable.
  • resorcinol diglycidyl ether By using resorcinol diglycidyl ether, the curing rate of the curable epoxy composition can be increased, and the curable epoxy composition can be easily applied.
  • the epoxy compound B3 having a nitrogen-containing heterocycle preferably has at least two epoxy groups, and preferably has three epoxy groups. More preferred.
  • the epoxy compound B3 is preferably an epoxy compound represented by the following formula (7) or the following formula (8).
  • the curing rate of the curable epoxy composition can be increased, and the heat resistance of the cured product of the curable epoxy composition can be further enhanced.
  • R11 to R13 each represents an alkylene group having 1 to 5 carbon atoms, and X represents an epoxy group or a hydroxymethyl group. R11 to R13 may be the same or different.
  • R14 to R16 each represent an alkylene group having 1 to 5 carbon atoms
  • p, q and r each represents an integer of 1 to 5
  • R17 to R19 each represents an alkylene group having 1 to 5 carbon atoms. Indicates a group.
  • R14 to R16 may be the same or different.
  • p, q and r may be the same or different.
  • R17 to R19 may be the same or different.
  • R11 to R13 in the above formula (7) are each preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group. preferable.
  • X in the above formula (7) is preferably an epoxy group.
  • the curing rate of the curable epoxy composition can be increased, and the heat resistance of the cured product of the curable epoxy composition can be further enhanced.
  • R14 to R16 in the above formula (8) are each preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and further more preferably an ethylene group. preferable.
  • p, q and r in the above formula (8) exceed 5, the curing rate of the curable epoxy composition may be lowered.
  • p, q, and r are small, the curing rate of the curable epoxy composition is increased.
  • p, q and r are each preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
  • R17 to R19 in the above formula (8) are each preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group. preferable.
  • the epoxy compound B3 is more preferably an epoxy compound represented by the above formula (7).
  • the curing rate of the curable epoxy composition can be increased, and the heat resistance of the cured product of the curable epoxy composition can be further enhanced.
  • the epoxy compound B3 is preferably trishydroxyethyl isocyanurate triglycidyl ether or triglycidyl isocyanurate, and more preferably triglycidyl isocyanurate. That is, the epoxy compound B3 is preferably an epoxy compound represented by the following formula (7A) or the following formula (8A), and more preferably an epoxy compound represented by the following formula (7A). By using these preferable epoxy compounds, the curing rate of the curable epoxy composition can be further increased.
  • the content of the epoxy compound B2 in 100% by weight of the epoxy component is preferably in the range of 5 to 95% by weight.
  • the epoxy compound B2 is an epoxy compound having an aromatic ring, and the content of the compound having an aromatic ring in 100% by weight of the epoxy component is preferably in the range of 5 to 95% by weight.
  • the viscosity of the curable epoxy composition can be further effectively increased.
  • the more preferable lower limit of the content of the epoxy compound B2 or the epoxy compound having an aromatic ring in 100% by weight of the epoxy component is 15% by weight, the further preferable lower limit is 35% by weight, and the more preferable upper limit is 75% by weight. %, And a more preferable upper limit is 55% by weight.
  • the content of the epoxy compound B3 in 100% by weight of the epoxy component is preferably in the range of 0.1 to 10% by weight.
  • the epoxy compound B3 is an epoxy compound having a heterocyclic ring containing a nitrogen atom, and the content of the epoxy compound having a heterocyclic ring containing a nitrogen atom in 100% by weight of the epoxy component is 0.1 to 10% by weight. It is preferable to be within the range.
  • the content of the epoxy compound B3 or the epoxy compound having a heterocyclic ring containing a nitrogen atom is within this range, the curing rate of the curable epoxy composition is increased, and the heat resistance of the cured product of the curable epoxy composition is increased. Can be further increased.
  • the viscosity (25 ° C.) of the curable epoxy composition is preferably in the range of 20000 to 100,000 mPa ⁇ s.
  • the chlorine ion concentration of the curable epoxy composition is preferably 500 ppm or less. If the chlorine ion concentration is too high, the curing rate of the curable epoxy composition may be slow.
  • the chlorine ion concentration can be measured by, for example, IPC emission analysis.
  • the curing agent is not particularly limited.
  • the curing agent include an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, and an acid anhydride.
  • curing agent is preferable.
  • a storage stability can be improved when the said epoxy component and the said hardening
  • the latent curing agent is preferably a latent imidazole curing agent, a latent polythiol curing agent or a latent amine curing agent. Only 1 type may be used for these hardening
  • the imidazole curing agent is not particularly limited, but 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine or 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.
  • the polythiol curing agent is not particularly limited, and examples include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, and the like. .
  • the amine curing agent is not particularly limited, but is hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraspiro [5.5] undecane. Bis (4-aminocyclohexyl) methane, metaphenylenediamine, diaminodiphenylsulfone and the like.
  • the content of the curing agent is not particularly limited.
  • the curing agent is preferably contained within a range of 1 to 40 parts by weight with respect to a total of 100 parts by weight of the epoxy component.
  • the content of the curing agent is less than 1 part by weight, the curable epoxy composition may not be sufficiently cured.
  • curing agent exceeds 40 weight part, the heat resistance of the hardened
  • the “total 100 parts by weight of epoxy component” means 100 parts by weight of the epoxy component A when the epoxy component B other than the epoxy component A is not included.
  • the epoxy component B is included it means a total of 100 parts by weight of the epoxy component A and the epoxy component B.
  • the curing agent is an imidazole curing agent or a phenol curing agent
  • the imidazole curing agent or the phenol curing agent is contained within a range of 1 to 15 parts by weight with respect to a total of 100 parts by weight of the epoxy component. It is preferred that When the curing agent is an amine curing agent, a polythiol curing agent, or an acid anhydride, the amine curing agent, the polythiol curing agent, or the acid anhydride is 15 to 40 with respect to a total of 100 parts by weight of the epoxy component. It is preferably contained within the range of parts by weight.
  • the curable epoxy composition of the present invention may further contain a polymerizable compound.
  • the polymerizable compound is not particularly limited.
  • a crosslinkable compound or a non-crosslinkable compound is mentioned, for example.
  • the said polymeric compound only 1 type may be used and 2 or more types may be used together.
  • the crosslinkable compound is not particularly limited. 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.
  • non-crosslinkable compound is not particularly limited.
  • 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 Examples include (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acryl
  • the content of the polymerizable compound is not particularly limited.
  • the polymerizable compound is preferably contained within a range of 10 to 60 parts by weight with respect to a total of 100 parts by weight of the epoxy component.
  • content of the said polymeric compound is less than 10 weight part, the heat resistance of the hardened
  • the amount of the polymerizable compound exceeds 60 parts by weight, the viscosity of the curable epoxy composition may be too high.
  • the curable epoxy composition of the present invention preferably contains an adhesive strength adjusting agent.
  • the adhesive strength adjusting agent is preferably a silane coupling agent.
  • the silane coupling agent is not particularly limited.
  • Examples of the silane coupling agent include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino).
  • the content of the silane coupling agent is not particularly limited.
  • the silane coupling agent is preferably contained within a range of 4 to 20 parts by weight with respect to a total of 100 parts by weight of the epoxy component.
  • the adhesive strength of the cured product of the curable epoxy composition to the adherend may be reduced.
  • content of the said silane coupling agent exceeds 20 weight part, a curable epoxy composition may become difficult to harden
  • the curable epoxy composition of the present invention preferably contains inorganic particles.
  • the inorganic particles are not particularly limited. Examples of the inorganic particles include silica, aluminum nitride, and alumina. As for the said inorganic particle, only 1 type may be used and 2 or more types may be used together.
  • the content of the inorganic particles is not particularly limited.
  • the inorganic particles are preferably contained within a range of 3 to 900 parts by weight with respect to a total of 100 parts by weight of the epoxy component.
  • content of the inorganic particles is less than 3 parts by weight, the latent heat expansion of the cured product of the curable epoxy composition may not be suppressed.
  • content of the said inorganic particle exceeds 900 weight part, an inorganic particle may not fully disperse
  • the curable epoxy composition of the present invention may contain a polymerization initiator that generates reactive species by light irradiation or heating. By using the polymerization initiator, the curing rate of the curable epoxy composition can be further increased.
  • the polymerization initiator is not particularly limited.
  • examples of the polymerization initiator include acetophenone polymerization initiators, ketal polymerization initiators, halogenated ketones, acyl phosphinoxides, and acyl phosphonates.
  • the acetophenone polymerization initiator is not particularly limited. Specific examples of the acetophenone polymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methoxyacetophenone 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-cyclohexylacetophenone, and the like.
  • the ketal polymerization initiator is not particularly limited. Specific examples of the ketal polymerization initiator include benzyl dimethyl ketal. As for the said polymerization initiator, only 1 type may be used and 2 or more types may be used together.
  • the content of the polymerization initiator is not particularly limited.
  • the polymerization initiator is preferably contained within a range of 2 to 10 parts by weight with respect to a total of 100 parts by weight of the epoxy component. If the content of the polymerization initiator is less than 2 parts by weight, the effect of adding the polymerization initiator may not be sufficiently obtained. When content of the said polymerization initiator exceeds 10 weight part, the adhesive force of the hardened
  • the method for producing the curable epoxy composition of the present invention is not particularly limited. As a specific example of the method for producing a curable epoxy composition, the epoxy component, the curing agent, and other components added as necessary are blended and mixed thoroughly using a planetary stirrer or the like. A manufacturing method is mentioned.
  • the curable epoxy composition of the present invention is used as a one-component adhesive for bonding liquid crystal panels or semiconductor chips.
  • the curable epoxy composition of the present invention may be a paste-like adhesive or a film-like adhesive.
  • the method for processing the curable epoxy composition of the present invention into a film adhesive is not particularly limited.
  • a method of applying the curable epoxy composition of the present invention to a substrate such as a release paper and processing it into a film-like adhesive, or adding a solvent to the curable epoxy composition of the present invention examples include a method in which a solvent is volatilized at a temperature lower than the activation temperature of the curing agent and then processed into a film adhesive after being applied to the substrate.
  • a method of curing the curable epoxy composition of the present invention a method of heating the curable epoxy composition, a method of irradiating the curable epoxy composition with light, and then heating the curable epoxy composition, curable The method etc. which heat a curable epoxy composition simultaneously with irradiating light to an epoxy composition are mentioned.
  • the heating temperature for curing the curable epoxy composition of the present invention is preferably in the range of 160 to 250 ° C, and more preferably in the range of 160 to 200 ° C. Since the curable epoxy composition of the present invention can be cured at a low temperature, the amount of energy required for heating can be reduced.
  • the curing time becomes long. For example, when the heating temperature is 200 ° C., the curing time exceeds 10 seconds.
  • the curable epoxy composition of the present invention can be cured in a short time even when the heating temperature is 200 ° C. or less. For example, if the heating temperature is 200 ° C., the curing time is 10 at the longest. Less than a second. In this specification, low temperature means a temperature of 200 ° C. or lower.
  • the method of irradiating the curable epoxy composition with light and then heating the curable epoxy composition is more cured than the method of heating alone.
  • the curable epoxy composition can be cured in a short time.
  • the light source used when irradiating light to the curable epoxy composition of the present invention is not particularly limited.
  • 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 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, or a metal halide lamp.
  • a chemical lamp is preferable.
  • the chemical lamp efficiently emits light in the active wavelength region of the polymerization initiator and emits less light in the light absorption wavelength region of components other than the polymerization initiator in the composition. Furthermore, by using a chemical lamp, light can efficiently reach the polymerization initiator present in the composition.
  • the light irradiation intensity in the wavelength region of 365 nm to 420 nm is preferably 0.1 to 100 mW / cm 2 .
  • An anisotropic conductive material can be obtained by including conductive particles in the curable epoxy composition of the present invention.
  • the conductive particles electrically connect the opposing electrical connection portions, for example, between the electrodes of the circuit board and the electrodes of the electronic component.
  • the conductive particles are not particularly limited as long as at least the outer surface has conductivity.
  • Examples of the conductive particles include organic particles, inorganic particles, organic-inorganic hybrid particles, or conductive particles whose surfaces are covered with a metal layer, or metal particles that are substantially composed only of metal. Can be mentioned.
  • the metal layer is not particularly limited. Examples of the metal layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, or a metal layer containing tin.
  • the content of the conductive particles is not particularly limited.
  • the conductive particles are preferably contained within a range of 0.5 to 5 parts by weight with respect to a total of 100 parts by weight of the epoxy component. If the content of the conductive particles is less than 0.5 parts by weight, the electrodes may not be reliably conducted. When content of electroconductive particle exceeds 5 weight part, a short circuit may arise between the adjacent electrodes which should not be conduct
  • the viscosity (25 ° C.) of the anisotropic conductive material is preferably in the range of 20000 to 100,000 mPa ⁇ s. If the viscosity is too low, the conductive particles may settle in the anisotropic conductive material. When the viscosity is too high, the conductive particles may not be sufficiently dispersed in the anisotropic conductive material.
  • the chlorine ion concentration of the anisotropic conductive material is preferably 500 ppm or less. If the chlorine ion concentration is too high, the curing rate of the curable epoxy composition contained in the anisotropic conductive material may be slow.
  • the anisotropic conductive material of the present invention can be used as an anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, anisotropic conductive sheet or the like.
  • anisotropic conductive material containing the conductive particles of the present invention is used as a film-like adhesive such as an anisotropic conductive film or an anisotropic conductive sheet, the film-like shape containing the conductive particles is used.
  • a film-like adhesive that does not contain conductive particles may be laminated on the adhesive.
  • connection structure can be obtained by connecting the connection target members using the anisotropic conductive material of the present invention.
  • the connection target member is preferably at least one of an electronic component and a circuit board.
  • connection structure includes a cured product layer and a connection target member, and the cured product layer is formed by curing the anisotropic conductive material of the present invention or the curable epoxy composition of the present invention. It is preferable.
  • connection structure includes a first connection target member having a first electrical connection portion, a second connection target member having a second electrical connection portion, and first and second electrical connection portions. It is preferable to provide a cured product layer as a connecting portion that electrically connects the two.
  • the cured product layer is formed by curing the anisotropic conductive material of the present invention.
  • FIG. 1 is a front cross-sectional view schematically showing a connection structure using an anisotropic conductive material including a curable epoxy composition according to an embodiment of the present invention and conductive particles.
  • connection structure 1 shown in FIG. 1 is a curing that electrically connects the first connection target member 2, the second connection target member 3, and the first and second connection target members 2 and 3.
  • the cured product layer 4 is a connecting portion and is formed using an anisotropic conductive paste as an anisotropic conductive material including a plurality of conductive particles 5.
  • a plurality of electrodes 2 b are provided on the upper surface 2 a of the first connection target member 2.
  • a plurality of electrodes 3 b are provided on the lower surface 3 a of the second connection target member 3.
  • the second connection target member 3 is laminated on the upper surface 2 a of the first connection target member 2 via a cured product layer 4 formed of an anisotropic conductive paste containing the conductive particles 1.
  • the electrode 2 b and the electrode 3 b are electrically connected by the conductive particles 5.
  • connection structure examples include a connection structure in which electronic parts such as a semiconductor chip, a capacitor, and a diode, and a circuit board such as a printed board, a flexible printed board, and a glass board are conductively connected.
  • the manufacturing method of the connection structure of the present invention is not particularly limited.
  • a manufacturing method of the connection structure a first electrode formed on a first connection target member such as an electronic component or a circuit board, and a second electrode formed on a second connection target member such as an electronic component or a circuit board are used.
  • positioning the said anisotropic conductive material between 2 electrodes, obtaining a laminated body, and heating and pressurizing this laminated body is mentioned.
  • the following materials were prepared as epoxy components for obtaining a curable epoxy composition.
  • Epoxy component A an epoxy compound having a structure represented by the above formula (1B) (an epoxy compound having a structure represented by the above formula (1), In which R1 and R2 are methylene groups and R3 and R4 are hydrogen atoms)
  • Epoxy compound [A-2] an epoxy compound having a structure represented by the above formula (1), wherein R1 and R2 in the above formula (1) are n-propylene groups, and R3 and R4 In which is a hydrogen atom
  • Epoxy compound [A-3] an epoxy compound having a structure represented by the above formula (1), wherein R1 and R2 in the above formula (1) are n-pentylene groups, and R3 and R4 In which is a hydrogen atom
  • Epoxy compound [A-4] an epoxy compound having a structure represented by the above formula (1), wherein R1 and R2 in the above formula (1) are methylene groups, and R3 is the above formula ( 2), R5 in the formula (2) is a methylene group, R4 represents a structure represented by the above formula (3), and R6 in the above formula (3) is methylene.
  • Epoxy compound [A-5] Epoxy compound having a structure represented by the following formula (101)
  • Epoxy compound [A-6] an epoxy compound having a structure represented by the above formula (1), wherein R1 and R2 in the above formula (1) are hexylene groups, and R3 and R4 are hydrogen A compound that is an atom
  • the mixing ratio (monomer: multimer) of the above-mentioned epoxy compounds [A-1] to [A-6] between the monomer and the multimer bonded with at least two is 80% by weight: 20%. %Met.
  • Epoxy component B other than epoxy component A (1) Epoxy compound [B1-1]: Bisphenol A type epoxy resin
  • Epoxy compound [B2-1] Adeka Resin EP-3300S (manufactured by ADEKA)
  • Epoxy compound [B2-2] resorcinol diglycidyl ether
  • Epoxy compound [B3-2] Trishydroxyethyl isocyanurate triglycidyl ether (epoxy compound represented by the above formula (8A))
  • Imidazole curing agent (amine adduct type curing agent (“PN-23J” manufactured by Ajinomoto Fine Techno Co.))
  • TMMP Trimethylolpropane tris-3-mercaptopropionate
  • Example 1 100 parts by weight of the epoxy compound [A-1] (epoxy compound having the structure represented by the formula (1B)) as the epoxy component, 7 parts by weight of silica particles having an average particle size of 0.02 ⁇ m, and a curing agent 40 parts by weight of an imidazole curing agent (amine adduct type curing agent (“PN-23J” manufactured by Ajinomoto Fine Techno Co., Ltd.)) and 4.5 parts by weight of 3-glycidoxypropyltriethoxysilane as a silane coupling agent 2 parts by weight of conductive particles having a particle diameter of 3 ⁇ m were blended to obtain a curable composition.
  • the conductive particles 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.
  • the curable composition obtained at 2000 rpm was stirred for 8 minutes and filtered using a nylon filter paper (pore diameter 10 ⁇ m) to prepare an anisotropic conductive paste as an anisotropic conductive material. .
  • Comparative Example 1 100 parts by weight of the above epoxy compound [B1-1] (bisphenol A type epoxy resin) and 5 parts by weight of 1,2-dimethylimidazole as a curing agent were stirred for 5 minutes at 2000 rpm using a planetary stirrer, Got. 7 parts by weight of silica particles having an average particle diameter of 0.02 ⁇ m and 2 parts by weight of conductive particles having an average particle diameter of 3 ⁇ m were added to the obtained mixture to obtain a curable composition.
  • the conductive particles 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.
  • the curable composition obtained at 2000 rpm was stirred for 8 minutes and filtered with a nylon filter paper (pore size: 10 ⁇ m) to prepare an anisotropic conductive paste as an anisotropic conductive material.
  • Examples 2 to 60 and Comparative Examples 2 and 3 An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the type and blending amount of the epoxy component (the blending unit was parts by weight) were changed as shown in Tables 1 to 6 below.
  • Example 61 An anisotropic conductive paste was obtained in the same manner as in Example 7 except that the type of curing agent was changed as shown in Table 7 below.
  • Example 63 The monomer contained in the epoxy compound [A-1] was isolated using a molecular distillation apparatus (manufactured by Shibata Kagaku Co., Ltd., model “MS-300 type rotating thin film type”). An anisotropic conductive paste was obtained in the same manner as in Example 7, except that a monomer isolated from the epoxy compound [A-1] was used instead of the epoxy compound [A-1].
  • Example 64 The monomer contained in the epoxy compound [A-1] was isolated using a molecular distillation apparatus (manufactured by Shibata Kagaku Co., Ltd., model “MS-300 type rotating thin film type”). Instead of the epoxy compound [A-1], an anisotropic conductive film was obtained in the same manner as in Example 7 except that the polymer after the monomer was isolated from the epoxy compound [A-1] was used. A paste was obtained.
  • the anisotropic conductive pastes obtained in Examples 1 to 64 each had a chlorine ion concentration of 500 ppm or less.
  • a temperature at which the maximum value of tan ⁇ of the obtained measurement sample is measured is measured, and the temperature at which the maximum value is obtained is referred to as a glass transition temperature. did.
  • connection resistance value between the electrodes of the obtained connection structure was measured.
  • the anisotropic conductive pastes of Examples 1 to 64 were used, it was confirmed that the electrodes of the connection structure were conductively connected.
  • the anisotropic conductive pastes of Comparative Examples 1 to 3 were used, the electrodes were not conductively connected.
  • the laminate was subjected to thermocompression bonding for 10 seconds under conditions of a pressure of 98 N and 180 ° C., and the connection resistance value between the electrodes was measured to confirm whether or not the electrodes were conductively connected. If the electrodes are not conductively connected by thermocompression for 10 seconds, prepare a new laminate, thermocompression bond for 20 seconds under the conditions of pressure 98N and 180 ° C, and measure the connection resistance between the electrodes. Thus, it was confirmed whether or not the electrodes were conductively connected. If the electrodes are not conductively connected by thermocompression for 20 seconds, prepare a new laminate, thermocompression for 30 seconds under the conditions of pressure 98N and 180 ° C, and measure the connection resistance between the electrodes. Thus, it was confirmed whether or not the electrodes were conductively connected. The curing time was evaluated according to the following criteria.
  • thermocompression bonding for 10 seconds.
  • the anisotropic conductive pastes of Examples 1 to 64 had a lower peak temperature and a higher calorific value than the anisotropic conductive paste of Comparative Example 1.
  • the anisotropic conductive pastes of Examples 1 to 64 could be cured more quickly than the anisotropic conductive paste of Comparative Example 1.
  • the anisotropic conductive pastes of Comparative Examples 2 and 3 had high peak temperatures and low calorific values, it was difficult to cure them quickly.

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Abstract

Disclosed is a curable epoxy composition which can be quickly cured at low temperatures. When the curable epoxy composition is used for connection of a member to be connected, the member can be efficiently connected by the composition. The curable epoxy composition contains an epoxy component and a curing agent, and the epoxy component includes a monomer of an epoxy compound having a structure represented by formula (1), a polymer wherein at least two of the epoxy compounds are bonded, or a mixture of the monomer and the polymer. (1) In the formula (1), R1 and R2 each represents an alkylene group having 1-5 carbon atoms; R3 represents a hydrogen atom, an alkyl group having 1-5 carbon atoms or a structure represented by formula (2); and R4 represents a hydrogen atom, an alkyl group having 1-5 carbon atoms or a structure represented by formula (3). (2) (3) In the formula (2) and formula (3), R5 and R6 each represents an alkylene group having 1-5 carbon atoms.

Description

硬化性エポキシ組成物、異方性導電材料及び接続構造体Curable epoxy composition, anisotropic conductive material, and connection structure
　本発明は、硬化性エポキシ組成物に関し、より詳細には、低温で速やかに硬化させることができ、回路基板又は電子部品等の電極間の接続に用いられた場合に、該電極間を効率的に接続できる硬化性エポキシ組成物、並びに該硬化性エポキシ組成物を用いた異方性導電材料及び接続構造体に関する。 The present invention relates to a curable epoxy composition, and more particularly, can be quickly cured at a low temperature, and when used for connection between electrodes such as a circuit board or an electronic component, the gap between the electrodes is efficient. The present invention relates to a curable epoxy composition that can be connected to a conductive layer, an anisotropic conductive material using the curable epoxy composition, and a connection structure.
　異方性導電ペースト、異方性導電インク、異方性導電粘接着剤、異方性導電フィルム、又は異方性導電シート等の異方性導電材料が広く知られている。 Anisotropic conductive materials such as anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, or anisotropic conductive sheet are widely known.
　異方性導電材料は、ＩＣチップとフレキシブルプリント回路基板との接続、及びＩＣチップとＩＴＯ電極を有する回路基板との接続等に使用されている。例えば、ＩＣチップの電極と回路基板の電極との間に異方性導電材料を配置した後、加熱及び加圧することにより、これらの電極同士を接続できる。 An anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like. For example, after an anisotropic conductive material is arranged between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be connected by heating and pressurizing.
　上記異方性導電材料の一例として、下記の特許文献１には、熱硬化性絶縁性接着剤と、導電性粒子と、イミダゾール潜在性硬化剤と、アミン潜在性硬化剤とを含有する異方性導電接着フィルムが開示されている。特許文献１には、この異方性導電接着フィルムを比較的低温で硬化させた場合であっても、接続信頼性が優れていると記載されている。
特開平９－１１５３３５号公報 As an example of the anisotropic conductive material, the following Patent Document 1 includes an anisotropic containing a thermosetting insulating adhesive, conductive particles, an imidazole latent curing agent, and an amine latent curing agent. A conductive conductive adhesive film is disclosed. Patent Document 1 describes that connection reliability is excellent even when this anisotropic conductive adhesive film is cured at a relatively low temperature.
JP-A-9-115335
　近年、回路基板又は電子部品の電極間を効率的に接続するために、接続に要する加熱温度を低くし、かつ加圧時間を短くすることが求められている。また、回路基板又は電子部品は加熱により劣化し易いため、加熱温度を低くすることが強く求められている。 In recent years, in order to efficiently connect electrodes of circuit boards or electronic components, it is required to lower the heating temperature required for connection and to shorten the pressurization time. In addition, since circuit boards or electronic components are easily deteriorated by heating, it is strongly required to lower the heating temperature.
　特許文献１に記載の異方性導電接着フィルムでは、硬化を開始させるのに必要な加熱温度が比較的低い。しかしながら、この異方性導電接着フィルムは、低温では硬化反応が充分に進行しないことがあった。そのため、この異方性導電接着フィルムを用いて、回路基板又は電子部品の電極間を接続するために、加熱温度を高くしたり、長時間加熱したりしなければならないことがあった。従って電極間を効率的に接続できないことがあった。 In the anisotropic conductive adhesive film described in Patent Document 1, the heating temperature necessary to start curing is relatively low. However, in this anisotropic conductive adhesive film, the curing reaction may not sufficiently proceed at low temperatures. Therefore, in order to connect between the electrodes of the circuit board or the electronic component using this anisotropic conductive adhesive film, it has been necessary to increase the heating temperature or to heat for a long time. Therefore, the electrodes may not be efficiently connected.
　本発明の目的は、低温で速やかに硬化させることができ、かつ接続対象部材の接続に用いられた場合に、接続対象部材を効率的に接続できる硬化性エポキシ組成物、並びに該硬化性エポキシ組成物を用いた異方性導電材料及び接続構造体を提供することにある。 An object of the present invention is to provide a curable epoxy composition that can be quickly cured at a low temperature and that can efficiently connect a connection target member when used for connection of the connection target member, and the curable epoxy composition. An object of the present invention is to provide an anisotropic conductive material and a connection structure using an object.
　本発明の広い局面によれば、エポキシ成分と、硬化剤とを含有し、前記エポキシ成分が、下記式（１）で表される構造を有するエポキシ化合物の単量体、該エポキシ化合物が少なくとも２個結合された多量体、又は該単量体と該多量体との混合物を含む、硬化性エポキシ組成物が提供される。 According to a wide aspect of the present invention, the epoxy component contains an epoxy component and a curing agent, and the epoxy component has a structure represented by the following formula (1). There is provided a curable epoxy composition comprising a single bonded multimer or a mixture of the monomer and the multimer.
　上記式（１）中、Ｒ１は炭素数１～５のアルキレン基を表し、Ｒ２は炭素数１～５のアルキレン基を表し、Ｒ３は水素原子、炭素数１～５のアルキル基又は下記式（２）で表される構造を表し、Ｒ４は水素原子、炭素数１～５のアルキル基又は下記式（３）で表される構造を表す。 In the above formula (1), R1 represents an alkylene group having 1 to 5 carbon atoms, R2 represents an alkylene group having 1 to 5 carbon atoms, R3 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following formula ( 2), R4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structure represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000007
 　上記式（２）中、Ｒ５は炭素数１～５のアルキレン基を表す。
Figure JPOXMLDOC01-appb-C000007
 In the above formula (2), R5 represents an alkylene group having 1 to 5 carbon atoms.
Figure JPOXMLDOC01-appb-C000008
 　上記式（３）中、Ｒ６は炭素数１～５のアルキレン基を表す。
Figure JPOXMLDOC01-appb-C000008
 In the above formula (3), R6 represents an alkylene group having 1 to 5 carbon atoms.
　本発明に係る硬化性エポキシ組成物のある特定の局面では、前記式（１）中、Ｒ３及びＲ４は水素原子である。 In a specific aspect of the curable epoxy composition according to the present invention, in the formula (1), R3 and R4 are hydrogen atoms.
　本発明に係る硬化性エポキシ組成物の他の特定の局面では、前記エポキシ成分１００重量％中、前記式（１）で表される構造を有するエポキシ化合物の単量体、該エポキシ化合物が少なくとも２個結合された多量体、又は該単量体と該多量体との混合物の含有量は、５～１００重量％の範囲内である。 In another specific aspect of the curable epoxy composition according to the present invention, in 100% by weight of the epoxy component, a monomer of an epoxy compound having a structure represented by the formula (1), the epoxy compound being at least 2 The content of the individually bonded multimer or the mixture of the monomer and the multimer is in the range of 5 to 100% by weight.
　本発明に係る硬化性エポキシ組成物の別の特定の局面では、前記エポキシ成分は、窒素原子を含む複素環を有するエポキシ化合物をさらに含む。 In another specific aspect of the curable epoxy composition according to the present invention, the epoxy component further includes an epoxy compound having a heterocyclic ring containing a nitrogen atom.
　本発明に係る硬化性エポキシ組成物のさらに別の特定の局面では、前記窒素原子を含む複素環を有するエポキシ化合物は、下記式（７）で表される化合物、又は下記式（８）で表されるエポキシ化合物である。 In still another specific aspect of the curable epoxy composition according to the present invention, the epoxy compound having a heterocyclic ring containing a nitrogen atom is represented by the following formula (7) or the following formula (8). Epoxy compound.
Figure JPOXMLDOC01-appb-C000009
 　上記式（７）中、Ｒ１１～Ｒ１３はそれぞれ炭素数１～５のアルキレン基を表し、Ｘはエポキシ基又はヒドロキシメチル基を表す。
Figure JPOXMLDOC01-appb-C000009
 In the above formula (7), R11 to R13 each represents an alkylene group having 1 to 5 carbon atoms, and X represents an epoxy group or a hydroxymethyl group.
Figure JPOXMLDOC01-appb-C000010
 　上記式（８）中、Ｒ１４～Ｒ１６はそれぞれ炭素数１～５のアルキレン基を示し、ｐ、ｑ及びｒはそれぞれ１～５の整数を示し、Ｒ１７～Ｒ１９はそれぞれ炭素数１～５のアルキレン基を示す。
Figure JPOXMLDOC01-appb-C000010
 In the above formula (8), R14 to R16 each represent an alkylene group having 1 to 5 carbon atoms, p, q and r each represents an integer of 1 to 5, and R17 to R19 each represents an alkylene group having 1 to 5 carbon atoms. Indicates a group.
　本発明に係る硬化性エポキシ組成物の別の特定の局面では、前記窒素原子を含む複素環を有するエポキシ化合物は、トリグリシジルイソシアヌレート、又はトリスヒドロキシエチルイソシアヌレートトリグリシジルエーテルである。 In another specific aspect of the curable epoxy composition according to the present invention, the epoxy compound having a heterocyclic ring containing a nitrogen atom is triglycidyl isocyanurate or trishydroxyethyl isocyanurate triglycidyl ether.
　本発明に係る硬化性エポキシ組成物のさらに別の特定の局面では、前記エポキシ成分１００重量％中、前記窒素原子を含む複素環を有するエポキシ化合物の含有量は、０．１～１０重量％の範囲内である。 In still another specific aspect of the curable epoxy composition according to the present invention, the content of the epoxy compound having a heterocyclic ring containing a nitrogen atom is 0.1 to 10% by weight in 100% by weight of the epoxy component. Within range.
　本発明に係る硬化性エポキシ組成物の他の特定の局面では、前記エポキシ成分は、芳香族環を有するエポキシ化合物をさらに含む。 In another specific aspect of the curable epoxy composition according to the present invention, the epoxy component further includes an epoxy compound having an aromatic ring.
　本発明に係る硬化性エポキシ組成物のさらに他の特定の局面では、前記芳香族環は、ベンゼン環、ナフタレン環、又はアントラセン環である。 In yet another specific aspect of the curable epoxy composition according to the present invention, the aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring.
　本発明に係る異方性導電材料は、本発明に従って構成された硬化性エポキシ組成物と、導電性粒子とを含有する。 The anisotropic conductive material according to the present invention contains a curable epoxy composition configured according to the present invention and conductive particles.
　本発明に係る接続構造体は、硬化物層と、該硬化物層により接続された接続対象部材とを備え、前記硬化物層が、本発明に従って構成された硬化性エポキシ組成物と導電性粒子とを含有する異方性導電材料を硬化させることにより形成されている。 A connection structure according to the present invention includes a cured product layer and a connection target member connected by the cured product layer, and the cured product layer is formed according to the present invention and conductive particles. It is formed by hardening the anisotropic conductive material containing these.
　また、本発明に係る接続構造体は、硬化物層と、該硬化物層により接続された接続対象部材とを備え、前記硬化物層が、本発明に従って構成された硬化性エポキシ組成物を硬化させることにより形成されている。 The connection structure according to the present invention includes a cured product layer and a connection target member connected by the cured product layer, and the cured product layer cures the curable epoxy composition configured according to the present invention. It is formed by letting.
（発明の効果）
　本発明に係る硬化性エポキシ組成物は、上記特定の構造を有するエポキシ化合物の単量体、該エポキシ化合物が少なくとも２個結合された多量体、又は該単量体と該多量体との混合物と、硬化剤とを含むため、低温で速やかに硬化させることができる。 (The invention's effect)
The curable epoxy composition according to the present invention includes an epoxy compound monomer having the above specific structure, a multimer in which at least two epoxy compounds are bonded, or a mixture of the monomer and the multimer. Since it contains a curing agent, it can be quickly cured at a low temperature.
　また、本発明に係る硬化性エポキシ組成物を接続対象部材の接続に用いると、該接続対象部材を効率的に接続できる。本発明に係る硬化性エポキシ組成物と導電性粒子とを含む異方性導電材料を回路基板又は電子部品等の電極間の接続に用いると、該電極間を効率的に接続できる。 Further, when the curable epoxy composition according to the present invention is used for connecting the connection target members, the connection target members can be efficiently connected. When an anisotropic conductive material including the curable epoxy composition according to the present invention and conductive particles is used for connection between electrodes of a circuit board or an electronic component, the electrodes can be efficiently connected.
図１は、本発明の一実施形態に係る硬化性エポキシ組成物と、導電性粒子とを含む異方性導電材料を用いた接続構造体を模式的に示す正面断面図である。FIG. 1 is a front cross-sectional view schematically showing a connection structure using an anisotropic conductive material including a curable epoxy composition according to an embodiment of the present invention and conductive particles.
符号の説明Explanation of symbols
　１…接続構造体
　２…第１の接続対象部材
　２ａ…上面
　２ｂ…電極
　３…第２の接続対象部材
　３ａ…下面
　３ｂ…電極
　４…硬化物層
　５…導電性粒子 DESCRIPTION OF SYMBOLS 1 ... Connection structure 2 ... 1st connection object member 2a ... Upper surface 2b ... Electrode 3 ... 2nd connection object member 3a ... Lower surface 3b ... Electrode 4 ... Cured material layer 5 ... Conductive particle
　以下、本発明を詳述する。 Hereinafter, the present invention will be described in detail.
　（硬化性エポキシ組成物）
　本発明に係る硬化性エポキシ組成物は、エポキシ成分と、硬化剤とを含有する。このエポキシ成分は、下記式（１）で表される構造を有するエポキシ化合物の単量体、該エポキシ化合物が少なくとも２個結合された多量体、又は該単量体と該多量体との混合物（以下、エポキシ成分Ａと略記することがある。）を含む。 (Curable epoxy composition)
The curable epoxy composition according to the present invention contains an epoxy component and a curing agent. The epoxy component is a monomer of an epoxy compound having a structure represented by the following formula (1), a multimer in which at least two epoxy compounds are bonded, or a mixture of the monomer and the multimer ( Hereinafter, it may be abbreviated as epoxy component A).
　上記エポキシ成分Ａは、下記式（１）で表される構造を有するエポキシ化合物の単量体、該エポキシ化合物が少なくとも２個結合された多量体、及び該単量体と該多量体との混合物の内のいずれかである。 The epoxy component A includes a monomer of an epoxy compound having a structure represented by the following formula (1), a multimer in which at least two epoxy compounds are bonded, and a mixture of the monomer and the multimer. Is one of the following.
Figure JPOXMLDOC01-appb-C000011
 　上記式（１）中、Ｒ１は炭素数１～５のアルキレン基を表し、Ｒ２は炭素数１～５のアルキレン基を表し、Ｒ３は水素原子、炭素数１～５のアルキル基又は下記式（２）で表される構造を表し、Ｒ４は水素原子、炭素数１～５のアルキル基又は下記式（３）で表される構造を表す。
Figure JPOXMLDOC01-appb-C000011
 In the above formula (1), R1 represents an alkylene group having 1 to 5 carbon atoms, R2 represents an alkylene group having 1 to 5 carbon atoms, R3 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following formula ( 2), R4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structure represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000012
 　上記式（２）中、Ｒ５は炭素数１～５のアルキレン基を表す。
Figure JPOXMLDOC01-appb-C000012
 In the above formula (2), R5 represents an alkylene group having 1 to 5 carbon atoms.
Figure JPOXMLDOC01-appb-C000013
 　上記式（３）中、Ｒ６は炭素数１～５のアルキレン基を表す。
Figure JPOXMLDOC01-appb-C000013
 In the above formula (3), R6 represents an alkylene group having 1 to 5 carbon atoms.
　上記アルキレン基の炭素数が５を超えると、硬化性エポキシ組成物の硬化速度が低下する。また、上記アルキル基の炭素数が５を超えると、硬化性エポキシ組成物の硬化速度が低下する。上記アルキレン基及び上記アルキル基の炭素数が小さいと、硬化性エポキシ組成物の硬化速度が高くなる。 When the number of carbon atoms of the alkylene group exceeds 5, the curing rate of the curable epoxy composition decreases. Moreover, when carbon number of the said alkyl group exceeds 5, the cure rate of a curable epoxy composition will fall. When the carbon number of the alkylene group and the alkyl group is small, the curing rate of the curable epoxy composition is increased.
　上記式（１）中のＲ１は、炭素数１～３のアルキレン基であることが好ましく、炭素数１又は２のアルキレン基であることがより好ましく、さらにメチレン基であることがより好ましい。上記式（１）中のＲ２は、炭素数１～３のアルキレン基であることが好ましく、炭素数１又は２のアルキレン基であることがより好ましく、さらにメチレン基であることがより好ましい。なお、上記アルキレン基は直鎖構造を有するアルキレン基であってもよく、分岐構造を有するアルキレン基であってもよい。また、上記Ｒ１と上記Ｒ２とは、同一であってもよく、異なっていてもよい。 In the above formula (1), R1 is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group. R2 in the above formula (1) is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group. The alkylene group may be an alkylene group having a linear structure or an alkylene group having a branched structure. The R1 and the R2 may be the same or different.
　上記式（１）中のＲ３は、水素原子、炭素数１～３のアルキル基又は上記式（２）で表される構造であることが好ましく、水素原子、炭素数１もしくは２のアルキル基、又は上記式（２）で表される構造であることがより好ましく、さらに水素原子、メチル基又は上記式（２）で表される構造であることがより好ましい。上記式（１）中のＲ４は、水素原子、炭素数１～３のアルキル基又は上記式（３）で表される構造であることが好ましく、水素原子、炭素数１もしく２のアルキル基、又は上記式（３）で表される構造であることがより好ましく、さらに水素原子、メチル基又は上記式（３）で表される構造であることがより好ましい。なお、上記アルキル基は、直鎖構造を有するアルキル基であってもよく、分岐構造を有するアルキル基であってもよい。また、上記Ｒ３と上記Ｒ４とは、同一であってもよく、異なっていてもよい。 R3 in the above formula (1) is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a structure represented by the above formula (2), a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, Or it is more preferable that it is a structure represented by the said Formula (2), Furthermore, it is more preferable that it is a structure represented by a hydrogen atom, a methyl group, or the said Formula (2). R4 in the above formula (1) is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a structure represented by the above formula (3), and is a hydrogen atom, an alkyl group having 1 or 2 carbon atoms. Or a structure represented by the above formula (3), more preferably a hydrogen atom, a methyl group, or a structure represented by the above formula (3). In addition, the alkyl group may be an alkyl group having a linear structure or an alkyl group having a branched structure. Further, R3 and R4 may be the same or different.
　上記式（２）中のＲ５は、炭素数１～３のアルキレン基であることが好ましく、炭素数１又は２のアルキレン基であることがより好ましく、さらにメチレン基であることがより好ましい。上記式（３）中のＲ６は、炭素数１～３のアルキレン基であることが好ましく、炭素数１又は２のアルキレン基であることがより好ましく、さらにメチレン基であることがより好ましい。なお、上記アルキレン基は直鎖構造を有するアルキレン基であってもよく、分岐構造を有するアルキレン基であってもよい。 In the above formula (2), R5 is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group. R6 in the above formula (3) is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group. The alkylene group may be an alkylene group having a linear structure or an alkylene group having a branched structure.
　上記式（１）で表される構造を有するエポキシ化合物は、不飽和二重結合と、少なくとも２個のエポキシ基とを有することを特徴とする。本発明の硬化性エポキシ組成物は、上記エポキシ成分Ａを含むため、低温で速やかに硬化させることができる。さらに、本発明の硬化性エポキシ組成物に導電性粒子を添加し、該導電性粒子を含む組成物を回路基板又は電子部品等の電極間の接続に用いると、該電極間を効率的に接続できる。 The epoxy compound having a structure represented by the above formula (1) has an unsaturated double bond and at least two epoxy groups. Since the curable epoxy composition of the present invention contains the epoxy component A, it can be quickly cured at a low temperature. Further, when conductive particles are added to the curable epoxy composition of the present invention, and the composition containing the conductive particles is used for connection between electrodes of a circuit board or an electronic component, the electrodes are efficiently connected. it can.
　上記式（１）で表される構造を有するエポキシ化合物としては、例えば、上記式（１）中、Ｒ１がメチレン基、Ｒ２がメチレン基、Ｒ３が水素原子、及び、Ｒ４が水素原子であるエポキシ化合物、上記式（１）中、Ｒ１がメチレン基、Ｒ２がメチレン基、Ｒ３が下記式（４）で表される構造、及び、Ｒ４が水素原子であるエポキシ化合物、並びに上記式（１）中、Ｒ１がメチレン基、Ｒ２がメチレン基、及び、Ｒ３及びＲ４がそれぞれ下記式（４）で表される構造であるエポキシ化合物等が挙げられる。 Examples of the epoxy compound having the structure represented by the above formula (1) include an epoxy in which R1 is a methylene group, R2 is a methylene group, R3 is a hydrogen atom, and R4 is a hydrogen atom in the above formula (1). In the above formula (1), R1 is a methylene group, R2 is a methylene group, R3 is a structure represented by the following formula (4), and R4 is a hydrogen atom, and in the above formula (1) R1 is a methylene group, R2 is a methylene group, and R3 and R4 are epoxy compounds having a structure represented by the following formula (4), respectively.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　硬化性エポキシ組成物を低温でより一層速やかに硬化させることができるので、上記式（１）中のＲ３及びＲ４は水素原子であることが好ましい。すなわち、上記式（１）で表される構造を有するエポキシ化合物は、下記式（１Ａ）で表される構造を有するエポキシ化合物であることが好ましい。 Since the curable epoxy composition can be cured more rapidly at a low temperature, R3 and R4 in the above formula (1) are preferably hydrogen atoms. That is, the epoxy compound having a structure represented by the above formula (1) is preferably an epoxy compound having a structure represented by the following formula (1A).
Figure JPOXMLDOC01-appb-C000015
 　上記式（１）中、Ｒ１は炭素数１～５のアルキレン基を表し、Ｒ２は炭素数１～５のアルキレン基を表す。
Figure JPOXMLDOC01-appb-C000015
 In the above formula (1), R1 represents an alkylene group having 1 to 5 carbon atoms, and R2 represents an alkylene group having 1 to 5 carbon atoms.
　また、硬化性エポキシ組成物を低温でさらに一層速やかに硬化させることができるので、上記式（１）中、Ｒ１がメチレン基、Ｒ２がメチレン基、Ｒ３が水素原子、及び、Ｒ４が水素原子である、下記式（１Ｂ）で表される構造を有するエポキシ化合物がより好ましい。 Further, since the curable epoxy composition can be cured more rapidly at a low temperature, in the above formula (1), R1 is a methylene group, R2 is a methylene group, R3 is a hydrogen atom, and R4 is a hydrogen atom. An epoxy compound having a structure represented by the following formula (1B) is more preferable.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記式（１）で表される構造を有するエポキシ化合物は、単量体である。本発明では、上記式（１）で表される構造を有するエポキシ化合物の単量体にかえて、又は該エポキシ化合物の単量体とともに、上記式（１）で表される構造を有するエポキシ化合物が少なくとも２個結合された多量体を用いてもよい。なかでも、上記エポキシ成分Ａは、上記式（１）で表される構造を有するエポキシ化合物の単量体、該エポキシ化合物が２～１０個結合された多量体、又は該単量体と該多量体との混合物であることが好ましく、上記エポキシ化合物の単量体、該エポキシ化合物が２個又は３個結合された多量体、又は該単量体と該多量体との混合物であることがより好ましく、さらに該単量体と該多量体との混合物であることがより好ましい。上記式（１）で表される構造を有するエポキシ化合物が１０個を超えて結合された多量体を用いると、硬化性エポキシ組成物の粘度が高くなりすぎることがある。なお、上記式（１）で表される構造を有するエポキシ化合物の単量体を用いた場合には、副生成物として、上記単量体が２個又は３個結合された多量体が含まれたり、保管条件によって、上記単量体が２個以上結合したりすることがある。 The epoxy compound having a structure represented by the above formula (1) is a monomer. In the present invention, the epoxy compound having the structure represented by the above formula (1) instead of the monomer of the epoxy compound having the structure represented by the above formula (1) or together with the monomer of the epoxy compound. A multimer in which at least two are bonded may be used. Among them, the epoxy component A includes an epoxy compound monomer having a structure represented by the above formula (1), a multimer in which 2 to 10 epoxy compounds are bonded, or the monomer and the large amount. A mixture of the monomer and the multimer, or a mixture of two or three of the epoxy compounds, or a mixture of the monomer and the multimer. More preferably, it is a mixture of the monomer and the multimer. When a multimer in which more than 10 epoxy compounds having a structure represented by the above formula (1) are combined is used, the viscosity of the curable epoxy composition may be too high. In addition, when the monomer of the epoxy compound having the structure represented by the above formula (1) is used, the by-product includes a multimer in which two or three of the monomers are bonded. Depending on storage conditions, two or more of the above monomers may be bonded.
　本発明の硬化性エポキシ組成物１００重量％中に、上記エポキシ成分Ａは５～８０重量％の範囲内で含有されることが好ましく、１０～７０重量％の範囲内で含有されることがより好ましい。上記エポキシ成分Ａの含有量が少なすぎると、低温での硬化速度を充分に高めることができないことがある。上記エポキシ成分Ａの含有量が多すぎると、硬化剤の含有量が相対的に少なくなり、エポキシ成分Ａ等を充分に硬化させることができないことがある。 The epoxy component A is preferably contained in the range of 5 to 80% by weight in 100% by weight of the curable epoxy composition of the present invention, and more preferably in the range of 10 to 70% by weight. preferable. When there is too little content of the said epoxy component A, the cure rate in low temperature may not fully be raised. When there is too much content of the said epoxy component A, content of a hardening | curing agent will become relatively small, and the epoxy component A etc. may not fully be hardened | cured.
　上記エポキシ成分１００重量％中の上記エポキシ成分Ａの含有量は、５～１００重量％の範囲内であることが好ましい。また、上記エポキシ成分Ａと該エポキシ成分Ａ以外の他のエポキシ成分（以下、エポキシ成分Ｂともいう。）とが併用される場合には、上記エポキシ成分１００重量％中の上記エポキシ成分Ａの含有量は、５～９０重量％の範囲内にあることが好ましい。上記エポキシ成分Ａの含有量が上記好ましい範囲内にある場合には、硬化性エポキシ組成物を低温でより一層速やかに硬化させることができる。上記エポキシ成分１００重量％中の上記エポキシ成分Ａの含有量のより好ましい下限は２０重量％であり、さらに好ましい下限は４０重量％であり、より好ましい上限は８０重量％であり、さらに好ましい上限は６０重量％である。 The content of the epoxy component A in 100% by weight of the epoxy component is preferably in the range of 5 to 100% by weight. When the epoxy component A and another epoxy component other than the epoxy component A (hereinafter also referred to as epoxy component B) are used in combination, the epoxy component A is contained in 100% by weight of the epoxy component. The amount is preferably in the range of 5 to 90% by weight. When content of the said epoxy component A exists in the said preferable range, a curable epoxy composition can be hardened more rapidly at low temperature. The more preferable lower limit of the content of the epoxy component A in 100% by weight of the epoxy component is 20% by weight, the further preferable lower limit is 40% by weight, the more preferable upper limit is 80% by weight, and the more preferable upper limit is 60% by weight.
　本発明の硬化性エポキシ組成物は、上記エポキシ成分Ａ以外の他のエポキシ成分（以下、エポキシ成分Ｂともいう。）を含んでいてもよい。 The curable epoxy composition of the present invention may contain an epoxy component other than the epoxy component A (hereinafter also referred to as epoxy component B).
　上記エポキシ成分は、上記エポキシ成分Ｂとして、窒素原子を含む複素環を有するエポキシ化合物Ｂ３を含むことが好ましい。エポキシ化合物Ｂ３の使用により、硬化性エポキシ組成物の硬化物の耐熱性をより一層高くすることができる。また、硬化物の耐熱性をより一層高くすることができるので、窒素原子を含む複素環はトリアジン骨格であることが好ましい。 The epoxy component preferably contains, as the epoxy component B, an epoxy compound B3 having a heterocyclic ring containing a nitrogen atom. By using the epoxy compound B3, the heat resistance of the cured product of the curable epoxy composition can be further increased. Moreover, since the heat resistance of hardened | cured material can be made still higher, it is preferable that the heterocyclic ring containing a nitrogen atom is a triazine skeleton.
　また、上記エポキシ成分は、上記エポキシ成分Ｂとして上記エポキシ化合物Ｂ３以外のエポキシ樹脂Ｂ１を含んでいてもよい。また、上記エポキシ成分は、上記エポキシ化合物Ｂ３及びエポキシ樹脂Ｂ１以外のエポキシ化合物Ｂ２を含んでいてもよい。 The epoxy component may contain an epoxy resin B1 other than the epoxy compound B3 as the epoxy component B. The epoxy component may include an epoxy compound B2 other than the epoxy compound B3 and the epoxy resin B1.
　本発明の硬化性エポキシ組成物は、上記エポキシ化合物Ｂ２又は上記エポキシ化合物Ｂ３を含むことが好ましく、上記エポキシ化合物Ｂ２を含むことがより好ましく、さらに上記エポキシ化合物Ｂ２と上記エポキシ化合物Ｂ３とを含むことがより好ましい。 The curable epoxy composition of the present invention preferably contains the epoxy compound B2 or the epoxy compound B3, more preferably contains the epoxy compound B2, and further contains the epoxy compound B2 and the epoxy compound B3. Is more preferable.
　上記エポキシ成分Ａを含む組成物の粘度は比較的低い。上記エポキシ成分Ａと、上記エポキシ化合物Ｂ２との併用により、硬化性エポキシ組成物の粘度を高めることができる。また、上記エポキシ成分Ａと上記エポキシ化合物Ｂ３との併用により、硬化性エポキシ組成物の硬化速度をより一層速くしたり、硬化性エポキシ組成物の硬化物の耐熱性を向上させたりすることができる。特に上記エポキシ成分Ａと上記エポキシ化合物Ｂ２と上記エポキシ化合物Ｂ３との併用により、硬化性エポキシ組成物の硬化速度を速くし、硬化性エポキシ組成物の硬化物の耐熱性を向上させ、さらに、硬化性エポキシ組成物を塗工しやすくことができる。 The viscosity of the composition containing the epoxy component A is relatively low. The combined use of the epoxy component A and the epoxy compound B2 can increase the viscosity of the curable epoxy composition. Moreover, the combined use of the epoxy component A and the epoxy compound B3 can further increase the curing rate of the curable epoxy composition or improve the heat resistance of the cured product of the curable epoxy composition. . In particular, the combined use of the epoxy component A, the epoxy compound B2, and the epoxy compound B3 increases the curing rate of the curable epoxy composition, improves the heat resistance of the cured product of the curable epoxy composition, and further cures the cured product. It is possible to easily apply the conductive epoxy composition.
　なお、「エポキシ樹脂」とは、一般的には、１分子中にエポキシ基を２個以上有し、かつ分子量１００００以下の低分子量のポリマーもしくはプレポリマー、又は該ポリマーもしくはプレポリマーのエポキシ基の開環反応によって生じた硬化性樹脂である。硬化性樹脂は、熱硬化性樹脂であってもよく、光硬化性樹脂であってもよい。 The “epoxy resin” generally means a low molecular weight polymer or prepolymer having two or more epoxy groups in one molecule and having a molecular weight of 10,000 or less, or an epoxy group of the polymer or prepolymer. It is a curable resin produced by a ring-opening reaction. The curable resin may be a thermosetting resin or a photocurable resin.
　上記エポキシ樹脂Ｂ１の具体例としては、ビスフェノール型エポキシ樹脂、エポキシノボラック樹脂、又はナフタレン構造を有するエポキシ樹脂等が挙げられる。 Specific examples of the epoxy resin B1 include a bisphenol type epoxy resin, an epoxy novolac resin, or an epoxy resin having a naphthalene structure.
　上記エポキシ化合物Ｂ２の市販品としては、例えば、アデカレジンＥＰ－３３００Ｓ及びアデカレジンＥＰ－３３００Ｅ（以上、いずれもＡＤＥＫＡ社製）が挙げられる。硬化性エポキシ組成物は、アデカレジンＥＰ－３３００Ｓ及びアデカレジンＥＰ－３３００Ｅの内の少なくとも一方を含むことが好ましく、アデカレジンＥＰ－３３００Ｓを含むことがより好ましい。これらの好ましい市販品の使用により、硬化性エポキシ組成物の粘度を効果的に高めることができる。 Examples of the commercially available epoxy compound B2 include Adeka Resin EP-3300S and Adeka Resin EP-3300E (all of which are manufactured by ADEKA). The curable epoxy composition preferably contains at least one of Adeka Resin EP-3300S and Adeka Resin EP-3300E, and more preferably contains Adeka Resin EP-3300S. By using these preferable commercial products, the viscosity of the curable epoxy composition can be effectively increased.
　また、上記エポキシ化合物Ｂ２は、芳香族環を有するエポキシ化合物であることが好ましい。上記エポキシ成分は、芳香族環を有するエポキシ化合物を含むことが好ましい。芳香族環を有するエポキシ化合物の使用により、硬化性エポキシ組成物の硬化速度を速くし、硬化性エポキシ組成物を塗工しやすくすることができる。 The epoxy compound B2 is preferably an epoxy compound having an aromatic ring. The epoxy component preferably includes an epoxy compound having an aromatic ring. By using an epoxy compound having an aromatic ring, the curing rate of the curable epoxy composition can be increased, and the curable epoxy composition can be easily applied.
　上記芳香族環は、ベンゼン環、ナフタレン環、又はアントラセン環であることが好ましく、ベンゼン環、又はナフタレン環であることがより好ましい。この場合には、硬化性エポキシ組成物をさらに一層塗工しやすくすることができる。 The aromatic ring is preferably a benzene ring, a naphthalene ring or an anthracene ring, and more preferably a benzene ring or a naphthalene ring. In this case, the curable epoxy composition can be more easily applied.
　上記芳香族環を有するエポキシ化合物としては、レゾルシノールジグリシジルエーテル又は１,６－ナフタレンジグリシジルエーテルが挙げられ、レゾルシノールジグリシジルエーテルが特に好ましい。レゾルシノールジグリシジルエーテルの使用により、硬化性エポキシ組成物の硬化速度を速くし、硬化性エポキシ組成物を塗工しやすくすることができる。 Examples of the epoxy compound having an aromatic ring include resorcinol diglycidyl ether and 1,6-naphthalenediglycidyl ether, and resorcinol diglycidyl ether is particularly preferable. By using resorcinol diglycidyl ether, the curing rate of the curable epoxy composition can be increased, and the curable epoxy composition can be easily applied.
　硬化性エポキシ組成物の硬化速度をより一層速くすることができるので、上記窒素を含む複素環を有するエポキシ化合物Ｂ３は、少なくとも２つのエポキシ基を有することが好ましく、３つのエポキシ基を有することがより好ましい。 Since the curing rate of the curable epoxy composition can be further increased, the epoxy compound B3 having a nitrogen-containing heterocycle preferably has at least two epoxy groups, and preferably has three epoxy groups. More preferred.
　上記エポキシ化合物Ｂ３は、下記式（７）又は下記式（８）で表されるエポキシ化合物であることが好ましい。これらの好ましいエポキシ化合物の使用により、硬化性エポキシ組成物の硬化速度を速くし、硬化性エポキシ組成物の硬化物の耐熱性をより一層高めることができる。 The epoxy compound B3 is preferably an epoxy compound represented by the following formula (7) or the following formula (8). By using these preferable epoxy compounds, the curing rate of the curable epoxy composition can be increased, and the heat resistance of the cured product of the curable epoxy composition can be further enhanced.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記式（７）中、Ｒ１１～Ｒ１３はそれぞれ炭素数１～５のアルキレン基を表し、Ｘはエポキシ基又はヒドロキシメチル基を表す。Ｒ１１～Ｒ１３は同一であってもよく、異なっていてもよい。 In the above formula (7), R11 to R13 each represents an alkylene group having 1 to 5 carbon atoms, and X represents an epoxy group or a hydroxymethyl group. R11 to R13 may be the same or different.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記式（８）中、Ｒ１４～Ｒ１６はそれぞれ炭素数１～５のアルキレン基を示し、ｐ、ｑ及びｒはそれぞれ１～５の整数を示し、Ｒ１７～Ｒ１９はそれぞれ炭素数１～５のアルキレン基を示す。Ｒ１４～Ｒ１６は同一であってもよく、異なっていてもよい。ｐ、ｑ及びｒは同一であってもよく、異なっていてもよい。Ｒ１７～Ｒ１９は同一であってもよく、異なっていてもよい。 In the above formula (8), R14 to R16 each represent an alkylene group having 1 to 5 carbon atoms, p, q and r each represents an integer of 1 to 5, and R17 to R19 each represents an alkylene group having 1 to 5 carbon atoms. Indicates a group. R14 to R16 may be the same or different. p, q and r may be the same or different. R17 to R19 may be the same or different.
　上記式（７）中のＲ１１～Ｒ１３の炭素数が５を超えると、硬化性エポキシ組成物の硬化速度が低くなることがある。Ｒ１１～Ｒ１３の炭素数が小さいと、硬化性エポキシ組成物の硬化速度が高くなる。上記式（７）中のＲ１１～Ｒ１３はそれぞれ、炭素数１～３のアルキレン基であることが好ましく、炭素数１又は２のアルキレン基であることがより好ましく、さらにメチレン基であることがより好ましい。 When the carbon number of R11 to R13 in the above formula (7) exceeds 5, the curing rate of the curable epoxy composition may be lowered. When the carbon number of R11 to R13 is small, the curing rate of the curable epoxy composition is increased. R11 to R13 in the above formula (7) are each preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group. preferable.
　上記式（７）中のＸはエポキシ基であることが好ましい。この場合には、硬化性エポキシ組成物の硬化速度を速くし、硬化性エポキシ組成物の硬化物の耐熱性をより一層高めることができる。 X in the above formula (7) is preferably an epoxy group. In this case, the curing rate of the curable epoxy composition can be increased, and the heat resistance of the cured product of the curable epoxy composition can be further enhanced.
　上記式（８）中のＲ１４～Ｒ１６の炭素数が５を超えると、硬化性エポキシ組成物の硬化速度が低くなることがある。Ｒ１４～Ｒ１６の炭素数が小さいと、硬化性エポキシ組成物の硬化速度が高くなる。上記式（８）中のＲ１４～Ｒ１６はそれぞれ、炭素数２～４のアルキレン基であることが好ましく、炭素数２又は３のアルキレン基であることがより好ましく、さらにエチレン基であることがより好ましい。 When the carbon number of R14 to R16 in the above formula (8) exceeds 5, the curing rate of the curable epoxy composition may be lowered. When the carbon number of R14 to R16 is small, the curing rate of the curable epoxy composition is increased. R14 to R16 in the above formula (8) are each preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and further more preferably an ethylene group. preferable.
　また、上記式（８）中のｐ、ｑ及びｒが５を超えると、硬化性エポキシ組成物の硬化速度が低くなることがある。ｐ、ｑ及びｒが小さいと、硬化性エポキシ組成物の硬化速度が高くなる。上記式（８）中のｐ、ｑ及びｒはそれぞれ、１～３の整数であることが好ましく、１又は２であることがより好ましく、さらに１であることがより好ましい。 Further, when p, q and r in the above formula (8) exceed 5, the curing rate of the curable epoxy composition may be lowered. When p, q, and r are small, the curing rate of the curable epoxy composition is increased. In the formula (8), p, q and r are each preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
　上記式（８）中のＲ１７～Ｒ１９の炭素数が５を超えると、硬化性エポキシ組成物の硬化速度が低くなることがある。Ｒ１７～Ｒ１９の炭素数が小さいと、硬化性エポキシ組成物の硬化速度が高くなる。上記式（８）中のＲ１７～Ｒ１９はそれぞれ、炭素数１～３のアルキレン基であることが好ましく、炭素数１又は２のアルキレン基であることがより好ましく、さらにメチレン基であることがより好ましい。 When the carbon number of R17 to R19 in the above formula (8) exceeds 5, the curing rate of the curable epoxy composition may be lowered. When the carbon number of R17 to R19 is small, the curing rate of the curable epoxy composition is increased. R17 to R19 in the above formula (8) are each preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group. preferable.
　上記エポキシ化合物Ｂ３は、上記式（７）で表されるエポキシ化合物であることがより好ましい。上記式（７）で表されるエポキシ化合物の使用により、硬化性エポキシ組成物の硬化速度を速くし、硬化性エポキシ組成物の硬化物の耐熱性をさらに一層高めることができる。 The epoxy compound B3 is more preferably an epoxy compound represented by the above formula (7). By using the epoxy compound represented by the formula (7), the curing rate of the curable epoxy composition can be increased, and the heat resistance of the cured product of the curable epoxy composition can be further enhanced.
　上記エポキシ化合物Ｂ３は、トリスヒドロキシエチルイソシアヌレートトリグリシジルエーテル又はトリグリシジルイソシアヌレートであることが好ましく、トリグリシジルイソシアヌレートであることがより好ましい。すなわち、上記エポキシ化合物Ｂ３は、下記式（７Ａ）又は下記式（８Ａ）で表されるエポキシ化合物であることが好ましく、下記式（７Ａ）で表されるエポキシ化合物であることがより好ましい。これらの好ましいエポキシ化合物の使用により、硬化性エポキシ組成物の硬化速度をさらに一層高めることができる。 The epoxy compound B3 is preferably trishydroxyethyl isocyanurate triglycidyl ether or triglycidyl isocyanurate, and more preferably triglycidyl isocyanurate. That is, the epoxy compound B3 is preferably an epoxy compound represented by the following formula (7A) or the following formula (8A), and more preferably an epoxy compound represented by the following formula (7A). By using these preferable epoxy compounds, the curing rate of the curable epoxy composition can be further increased.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　エポキシ成分１００重量％中の上記エポキシ化合物Ｂ２の含有量は、５～９５重量％の範囲内であることが好ましい。また、上記エポキシ化合物Ｂ２が芳香族環を有するエポキシ化合物であって、エポキシ成分１００重量％中の芳香族環を有する化合物の含有量が、５～９５重量％の範囲内であることが好ましい。上記エポキシ化合物Ｂ２又は芳香族環を有するエポキシ化合物の含有量がこの範囲内にあることにより、硬化性エポキシ組成物の粘度をより一層効果的に高めことができる。上記エポキシ成分１００重量％中の上記エポキシ化合物Ｂ２又は芳香族環を有するエポキシ化合物の含有量のより好ましい下限は１５重量％であり、さらに好ましい下限は３５重量％であり、より好ましい上限は７５重量％であり、さらに好ましい上限は５５重量％である。 The content of the epoxy compound B2 in 100% by weight of the epoxy component is preferably in the range of 5 to 95% by weight. The epoxy compound B2 is an epoxy compound having an aromatic ring, and the content of the compound having an aromatic ring in 100% by weight of the epoxy component is preferably in the range of 5 to 95% by weight. When the content of the epoxy compound B2 or the epoxy compound having an aromatic ring is within this range, the viscosity of the curable epoxy composition can be further effectively increased. The more preferable lower limit of the content of the epoxy compound B2 or the epoxy compound having an aromatic ring in 100% by weight of the epoxy component is 15% by weight, the further preferable lower limit is 35% by weight, and the more preferable upper limit is 75% by weight. %, And a more preferable upper limit is 55% by weight.
　エポキシ成分１００重量％中の上記エポキシ化合物Ｂ３の含有量は０．１～１０重量％の範囲内であることが好ましい。また、上記エポキシ化合物Ｂ３が窒素原子を含む複素環を有するエポキシ化合物であって、エポキシ成分１００重量％中の窒素原子を含む複素環を有するエポキシ化合物の含有量が、０．１～１０重量％の範囲内であることが好ましい。上記エポキシ化合物Ｂ３又は窒素原子を含む複素環を有するエポキシ化合物の含有量がこの範囲内にあることにより、硬化性エポキシ組成物の硬化速度を速くし、硬化性エポキシ組成物の硬化物の耐熱性をより一層高めることができる。 The content of the epoxy compound B3 in 100% by weight of the epoxy component is preferably in the range of 0.1 to 10% by weight. The epoxy compound B3 is an epoxy compound having a heterocyclic ring containing a nitrogen atom, and the content of the epoxy compound having a heterocyclic ring containing a nitrogen atom in 100% by weight of the epoxy component is 0.1 to 10% by weight. It is preferable to be within the range. When the content of the epoxy compound B3 or the epoxy compound having a heterocyclic ring containing a nitrogen atom is within this range, the curing rate of the curable epoxy composition is increased, and the heat resistance of the cured product of the curable epoxy composition is increased. Can be further increased.
　硬化性エポキシ組成物の粘度（２５℃）は、２００００～１０００００ｍＰａ・ｓの範囲内にあることが好ましい。 The viscosity (25 ° C.) of the curable epoxy composition is preferably in the range of 20000 to 100,000 mPa · s.
　また、硬化性エポキシ組成物の塩素イオン濃度は、５００ｐｐｍ以下であることが好ましい。上記塩素イオン濃度が高すぎると、硬化性エポキシ組成物の硬化速度が遅くなることがある。なお、上記塩素イオン濃度は、例えば、ＩＰＣ発光分析により測定できる。 The chlorine ion concentration of the curable epoxy composition is preferably 500 ppm or less. If the chlorine ion concentration is too high, the curing rate of the curable epoxy composition may be slow. The chlorine ion concentration can be measured by, for example, IPC emission analysis.
　上記硬化剤は特に限定されない。上記硬化剤としては、イミダゾール硬化剤、アミン硬化剤、フェノール硬化剤、ポリチオール硬化剤又は酸無水物等が挙げられる。なかでも、硬化性エポキシ組成物を低温でより一層速やかに硬化させることができるので、イミダゾール硬化剤、ポリチオール硬化剤又はアミン硬化剤が好ましい。また、上記エポキシ成分と上記硬化剤とを混合したときに保存安定性を高めることができるので、潜在性の硬化剤が好ましい。潜在性の硬化剤は、潜在性イミダゾール硬化剤、潜在性ポリチオール硬化剤又は潜在性アミン硬化剤であることが好ましい。これらの硬化剤は１種のみが用いられてもよく、２種以上が併用されてもよい。なお、上記硬化剤は、ポリウレタン樹脂又はポリエステル樹脂等の高分子物質で被覆されていてもよい。 The curing agent is not particularly limited. Examples of the curing agent include an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, and an acid anhydride. Especially, since a curable epoxy composition can be hardened more rapidly at low temperature, an imidazole hardening | curing agent, a polythiol hardening | curing agent, or an amine hardening | curing agent is preferable. Moreover, since a storage stability can be improved when the said epoxy component and the said hardening | curing agent are mixed, a latent hardening | curing agent is preferable. The latent curing agent is preferably a latent imidazole curing agent, a latent polythiol curing agent or a latent amine curing agent. Only 1 type may be used for these hardening | curing agents, and 2 or more types may be used together. In addition, the said hardening | curing agent may be coat | covered with polymeric substances, such as a polyurethane resin or a polyester resin.
　上記イミダゾール硬化剤としては、特に限定されないが、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾリウムトリメリテート、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン又は２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンイソシアヌル酸付加物等が挙げられる。
　上記ポリチオール硬化剤としては、特に限定されないが、トリメチロールプロパン　トリス－３－メルカプトプロピオネート、ペンタエリスリトール　テトラキス－３－メルカプトプロピオネート又はジペンタエリスリトール　ヘキサ－３－メルカプトプロピオネート等が挙げられる。 The imidazole curing agent is not particularly limited, but 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine or 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.
The polythiol curing agent is not particularly limited, and examples include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, and the like. .
　上記アミン硬化剤としては、特に限定されないが、ヘキサメチレンジアミン、オクタメチレンジアミン、デカメチレンジアミン、３，９－ビス（３－アミノプロピル）２，４，８，１０－テトラスピロ[５．５]ウンデカン、ビス（４－アミノシクロヘキシル）メタン、メタフェニレンジアミン又はジアミノジフェニルスルホン等が挙げられる。 The amine curing agent is not particularly limited, but is hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraspiro [5.5] undecane. Bis (4-aminocyclohexyl) methane, metaphenylenediamine, diaminodiphenylsulfone and the like.
　上記硬化剤の含有量は特に限定されない。上記エポキシ成分の合計１００重量部に対して、上記硬化剤は１～４０重量部の範囲内で含有されることが好ましい。上記硬化剤の含有量が１重量部未満であると、硬化性エポキシ組成物が充分に硬化しないことがある。上記硬化剤の含有量が４０重量部を超えると、硬化性エポキシ組成物の硬化物の耐熱性が低下することがある。なお、「エポキシ成分の合計１００重量部」とは、上記エポキシ成分Ａ以外の他のエポキシ成分Ｂが含まれない場合には、上記エポキシ成分Ａ１００重量部を意味し、上記エポキシ成分Ａ以外の他のエポキシ成分Ｂが含まれる場合には、上記エポキシ成分Ａと上記エポキシ成分Ｂとの合計１００重量部を意味する。 The content of the curing agent is not particularly limited. The curing agent is preferably contained within a range of 1 to 40 parts by weight with respect to a total of 100 parts by weight of the epoxy component. When the content of the curing agent is less than 1 part by weight, the curable epoxy composition may not be sufficiently cured. When content of the said hardening | curing agent exceeds 40 weight part, the heat resistance of the hardened | cured material of a curable epoxy composition may fall. The “total 100 parts by weight of epoxy component” means 100 parts by weight of the epoxy component A when the epoxy component B other than the epoxy component A is not included. When the epoxy component B is included, it means a total of 100 parts by weight of the epoxy component A and the epoxy component B.
　なお、上記硬化剤がイミダゾール硬化剤、又はフェノール硬化剤である場合、上記エポキシ成分の合計１００重量部に対して、イミダゾール硬化剤、又はフェノール硬化剤は、１～１５重量部の範囲内で含有されることが好ましい。また、上記硬化剤がアミン硬化剤、ポリチオール硬化剤、又は酸無水物である場合、上記エポキシ成分の合計１００重量部に対して、アミン硬化剤、ポリチオール硬化剤、又は酸無水物は１５～４０重量部の範囲内で含有されることが好ましい。 When the curing agent is an imidazole curing agent or a phenol curing agent, the imidazole curing agent or the phenol curing agent is contained within a range of 1 to 15 parts by weight with respect to a total of 100 parts by weight of the epoxy component. It is preferred that When the curing agent is an amine curing agent, a polythiol curing agent, or an acid anhydride, the amine curing agent, the polythiol curing agent, or the acid anhydride is 15 to 40 with respect to a total of 100 parts by weight of the epoxy component. It is preferably contained within the range of parts by weight.
　組成物の粘度を調整するために、あるいは塗布した組成物が濡れ広がらないようにするために、本発明の硬化性エポキシ組成物は、重合性化合物をさらに含有してもよい。上記重合性化合物は特に限定されない。上記重合性化合物としては、例えば、架橋性化合物又は非架橋性化合物が挙げられる。上記重合性化合物は、１種のみが用いられてもよく、２種以上が併用されてもよい。 In order to adjust the viscosity of the composition or to prevent the applied composition from getting wet and spreading, the curable epoxy composition of the present invention may further contain a polymerizable compound. The polymerizable compound is not particularly limited. As said polymeric compound, a crosslinkable compound or a non-crosslinkable compound is mentioned, for example. As for the said polymeric compound, only 1 type may be used and 2 or more types may be used together.
　上記架橋性化合物は特に限定されない。上記架橋性化合物の具体例としては、例えば、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、グリセリンメタクリレートアクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリメタクリレート、（メタ）アクリル酸アリル、（メタ）アクリル酸ビニル、ジビニルベンゼン、ポリエステル（メタ）アクリレート、又はウレタン（メタ）アクリレート等が挙げられる。 The crosslinkable compound is not particularly limited. 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.
　上記非架橋性化合物は特に限定されない。上記非架橋性化合物の具体例としては、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、又はテトラデシル（メタ）アクリレート等が挙げられる。 The above non-crosslinkable compound is not particularly limited. 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 Examples include (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and tetradecyl (meth) acrylate.
　上記重合性化合物の含有量は特に限定されない。上記エポキシ成分の合計１００重量部に対して、上記重合性化合物は１０～６０重量部の範囲内で含有されることが好ましい。上記重合性化合物の含有量が１０重量部未満であると、硬化性エポキシ組成物の硬化物の耐熱性が低下することがある。上記重合性化合物の量が６０重量部を超えると、硬化性エポキシ組成物の粘度が高くなりすぎることがある。 The content of the polymerizable compound is not particularly limited. The polymerizable compound is preferably contained within a range of 10 to 60 parts by weight with respect to a total of 100 parts by weight of the epoxy component. When content of the said polymeric compound is less than 10 weight part, the heat resistance of the hardened | cured material of a curable epoxy composition may fall. When the amount of the polymerizable compound exceeds 60 parts by weight, the viscosity of the curable epoxy composition may be too high.
　被着体に対する、硬化性エポキシ組成物の硬化物の接着力を高めることができるので、本発明の硬化性エポキシ組成物は、接着力調整剤を含有することが好ましい。上記接着力調整剤は、シランカップリング剤であることが好ましい。 Since the adhesive force of the cured product of the curable epoxy composition to the adherend can be increased, the curable epoxy composition of the present invention preferably contains an adhesive strength adjusting agent. The adhesive strength adjusting agent is preferably a silane coupling agent.
　上記シランカップリング剤は特に限定されない。上記シランカップリング剤としては、例えば、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルジメチルエトキシシラン、３－アミノプロピルメチルジエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリアセトキシシラン、ビニルトリクロロシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－クロロプロピルトリメトキシシラン、３－クロロプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、ドデシルトリエトキシシラン、ヘキシルトリメトキシシラン、ｔ－ブチルイソブチルジエトキシシラン、メチルフェニルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン又はメチルフェニルジメトキシシラン等が挙げられる。上記シランカップリング剤は、１種のみが用いられてもよいし、２種以上が併用されてもよい。 The silane coupling agent is not particularly limited. Examples of the silane coupling agent include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-chloropropyl Pyrtrimethoxysilane, 3-chloropropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dodecyltriethoxysilane Hexyltrimethoxysilane, t-butylisobutyldiethoxysilane, methylphenyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, methylphenyldimethoxysilane, and the like. As for the said silane coupling agent, only 1 type may be used and 2 or more types may be used together.
　上記シランカップリング剤の含有量は特に限定されない。上記エポキシ成分の合計１００重量部に対して、上記シランカップリング剤は４～２０重量部の範囲内で含有されることが好ましい。上記シランカップリング剤の含有量が４重量部未満であると、被着体に対する、硬化性エポキシ組成物の硬化物の接着力が低下することがある。上記シランカップリング剤の含有量が２０重量部を超えると、硬化性エポキシ組成物が硬化しにくくなることがある。 The content of the silane coupling agent is not particularly limited. The silane coupling agent is preferably contained within a range of 4 to 20 parts by weight with respect to a total of 100 parts by weight of the epoxy component. When the content of the silane coupling agent is less than 4 parts by weight, the adhesive strength of the cured product of the curable epoxy composition to the adherend may be reduced. When content of the said silane coupling agent exceeds 20 weight part, a curable epoxy composition may become difficult to harden | cure.
　本発明の硬化性エポキシ組成物は、無機粒子を含有することが好ましい。上記無機粒子の使用により、硬化性エポキシ組成物の硬化物の潜熱膨張を抑制できる。上記無機粒子は特に限定されない。上記無機粒子としては、シリカ、窒化アルミニウム、又はアルミナ等が挙げられる。上記無機粒子は１種のみが用いられてもよく、２種以上が併用されてもよい。 The curable epoxy composition of the present invention preferably contains inorganic particles. By using the inorganic particles, latent heat expansion of the cured product of the curable epoxy composition can be suppressed. The inorganic particles are not particularly limited. Examples of the inorganic particles include silica, aluminum nitride, and alumina. As for the said inorganic particle, only 1 type may be used and 2 or more types may be used together.
　上記無機粒子の含有量は特に限定されない。上記エポキシ成分の合計１００重量部に対して、上記無機粒子は３～９００重量部の範囲内で含有されることが好ましい。上記無機粒子の含有量が３重量部未満であると、硬化性エポキシ組成物の硬化物の潜熱膨張を抑制できないことがある。上記無機粒子の含有量が９００重量部を超えると、硬化性エポキシ組成物中に無機粒子が充分に分散しないことがある。 The content of the inorganic particles is not particularly limited. The inorganic particles are preferably contained within a range of 3 to 900 parts by weight with respect to a total of 100 parts by weight of the epoxy component. When the content of the inorganic particles is less than 3 parts by weight, the latent heat expansion of the cured product of the curable epoxy composition may not be suppressed. When content of the said inorganic particle exceeds 900 weight part, an inorganic particle may not fully disperse | distribute in a curable epoxy composition.
　本発明の硬化性エポキシ組成物は、光照射または加熱により反応活性種を生じさせる重合開始剤を含有してもよい。上記重合開始剤の使用により、硬化性エポキシ組成物の硬化速度をより一層高めることができる。 The curable epoxy composition of the present invention may contain a polymerization initiator that generates reactive species by light irradiation or heating. By using the polymerization initiator, the curing rate of the curable epoxy composition can be further increased.
　上記重合開始剤は特に限定されない。上記重合開始剤としては、例えば、アセトフェノン重合開始剤、ケタール重合開始剤、ハロゲン化ケトン、アシルホスフィノキシド、又はアシルホスフォナート等が挙げられる。上記アセトフェノン重合開始剤は特に限定されない。上記アセトフェノン重合開始剤の具体例としては、４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、メトキシアセトフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２－ヒドロキシ－２－シクロヘキシルアセトフェノン等が挙げられる。また、上記ケタール重合開始剤は特に限定されない。上記ケタール重合開始剤の具体例としては、ベンジルジメチルケタール等が挙げられる。上記重合開始剤は１種のみが用いられてもよく、２種以上が併用されてもよい。 The polymerization initiator is not particularly limited. Examples of the polymerization initiator include acetophenone polymerization initiators, ketal polymerization initiators, halogenated ketones, acyl phosphinoxides, and acyl phosphonates. The acetophenone polymerization initiator is not particularly limited. Specific examples of the acetophenone polymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methoxyacetophenone 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-cyclohexylacetophenone, and the like. The ketal polymerization initiator is not particularly limited. Specific examples of the ketal polymerization initiator include benzyl dimethyl ketal. As for the said polymerization initiator, only 1 type may be used and 2 or more types may be used together.
　上記重合開始剤の含有量は特に限定されない。上記エポキシ成分の合計１００重量部に対して、上記重合開始剤は２～１０重量部の範囲内で含有されることが好ましい。上記重合開始剤の含有量が２重量部未満であると、重合開始剤を添加した効果が充分に得られないことがある。上記重合開始剤の含有量が１０重量部を超えると、被着体に対する、硬化性エポキシ組成物の硬化物の接着力が低下することがある。 The content of the polymerization initiator is not particularly limited. The polymerization initiator is preferably contained within a range of 2 to 10 parts by weight with respect to a total of 100 parts by weight of the epoxy component. If the content of the polymerization initiator is less than 2 parts by weight, the effect of adding the polymerization initiator may not be sufficiently obtained. When content of the said polymerization initiator exceeds 10 weight part, the adhesive force of the hardened | cured material of a curable epoxy composition with respect to a to-be-adhered body may fall.
　本発明の硬化性エポキシ組成物の製造方法は特に限定されない。硬化性エポキシ組成物の製造方法の具体例としては、上記エポキシ成分と、上記硬化剤と、必要に応じて添加される他の成分とを配合し、遊星式攪拌機等を用いて充分に混合する製造方法が挙げられる。 The method for producing the curable epoxy composition of the present invention is not particularly limited. As a specific example of the method for producing a curable epoxy composition, the epoxy component, the curing agent, and other components added as necessary are blended and mixed thoroughly using a planetary stirrer or the like. A manufacturing method is mentioned.
　本発明の硬化性エポキシ組成物は、一液型接着剤として、液晶パネル又は半導体チップ等の接着に用いられる。本発明の硬化性エポキシ組成物は、ペースト状の接着剤であってもよく、フィルム状の接着剤であってもよい。 The curable epoxy composition of the present invention is used as a one-component adhesive for bonding liquid crystal panels or semiconductor chips. The curable epoxy composition of the present invention may be a paste-like adhesive or a film-like adhesive.
　本発明の硬化性エポキシ組成物をフィルム状の接着剤に加工する方法は特に限定されない。例えば、本発明の硬化性エポキシ組成物を離型紙等の基材に塗布し、フィルム状の接着剤に加工する方法、又は本発明の硬化性エポキシ組成物に溶剤を加えて、離型紙等の基材に塗布した後、上記硬化剤の活性温度よりも低い温度で溶剤を揮発させ、フィルム状の接着剤に加工する方法等が挙げられる。 The method for processing the curable epoxy composition of the present invention into a film adhesive is not particularly limited. For example, a method of applying the curable epoxy composition of the present invention to a substrate such as a release paper and processing it into a film-like adhesive, or adding a solvent to the curable epoxy composition of the present invention, Examples of the method include a method in which a solvent is volatilized at a temperature lower than the activation temperature of the curing agent and then processed into a film adhesive after being applied to the substrate.
　本発明の硬化性エポキシ組成物を硬化させる方法としては、硬化性エポキシ組成物を加熱する方法、硬化性エポキシ組成物に光を照射し、次いで、硬化性エポキシ組成物を加熱する方法、硬化性エポキシ組成物に光を照射すると同時に、硬化性エポキシ組成物を加熱する方法等が挙げられる。 As a method of curing the curable epoxy composition of the present invention, a method of heating the curable epoxy composition, a method of irradiating the curable epoxy composition with light, and then heating the curable epoxy composition, curable The method etc. which heat a curable epoxy composition simultaneously with irradiating light to an epoxy composition are mentioned.
　本発明の硬化性エポキシ組成物を硬化させる際の加熱温度は、１６０～２５０℃の範囲内にあることが好ましく、１６０～２００℃の範囲内にあることがより好ましい。本発明の硬化性エポキシ組成物は低温で硬化させることができるので、加熱に要するエネルギー量を低減できる。 The heating temperature for curing the curable epoxy composition of the present invention is preferably in the range of 160 to 250 ° C, and more preferably in the range of 160 to 200 ° C. Since the curable epoxy composition of the present invention can be cured at a low temperature, the amount of energy required for heating can be reduced.
　従来の硬化性エポキシ組成物では、上記加熱温度が２００℃以下であると、硬化時間が長くなり、例えば加熱温度が２００℃であれば硬化時間が１０秒を超えてしまう。これに対し、本発明の硬化性エポキシ組成物では、上記加熱温度が２００℃以下であっても、短時間で硬化させることができ、例えば加熱温度が２００℃であれば硬化時間は長くとも１０秒未満である。なお、本明細書において、低温とは２００℃以下の温度を意味する。 In the conventional curable epoxy composition, when the heating temperature is 200 ° C. or less, the curing time becomes long. For example, when the heating temperature is 200 ° C., the curing time exceeds 10 seconds. In contrast, the curable epoxy composition of the present invention can be cured in a short time even when the heating temperature is 200 ° C. or less. For example, if the heating temperature is 200 ° C., the curing time is 10 at the longest. Less than a second. In this specification, low temperature means a temperature of 200 ° C. or lower.
　なお、本発明の硬化性エポキシ組成物を硬化させる方法として、硬化性エポキシ組成物に光を照射し、次いで、硬化性エポキシ組成物を加熱する方法によれば、加熱のみする方法よりも、硬化性エポキシ組成物を短時間で硬化させることができる。 In addition, as a method of curing the curable epoxy composition of the present invention, the method of irradiating the curable epoxy composition with light and then heating the curable epoxy composition is more cured than the method of heating alone. The curable epoxy composition can be cured in a short time.
　本発明の硬化性エポキシ組成物に光を照射する際に用いる光源は特に限定されない。該光源としては、例えば、波長４２０ｎｍ以下に充分な発光分布を有する光源等が挙げられる。また、光源の具体例としては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、又はメタルハライドランプ等が挙げられる。なかでも、ケミカルランプが好ましい。ケミカルランプは、重合開始剤の活性波長領域の光を効率よく発光するとともに、組成物中の重合開始剤以外の他の成分の光吸収波長領域における発光量が少ない。さらに、ケミカルランプの使用により、組成物の内部に存在する重合開始剤まで効率よく光を到達させることができる。 The light source used when irradiating light to the curable epoxy composition of the present invention is not particularly 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 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, or a metal halide lamp. Of these, a chemical lamp is preferable. The chemical lamp efficiently emits light in the active wavelength region of the polymerization initiator and emits less light in the light absorption wavelength region of components other than the polymerization initiator in the composition. Furthermore, by using a chemical lamp, light can efficiently reach the polymerization initiator present in the composition.
　例えば、アセトフェノン基を有する開裂型の重合開始剤が含有されている場合には、３６５ｎｍ～４２０ｎｍの波長領域での光照射強度は、０．１～１００ｍＷ／ｃｍ２であることが好ましい。 For example, when a cleavage type polymerization initiator having an acetophenone group is contained, the light irradiation intensity in the wavelength region of 365 nm to 420 nm is preferably 0.1 to 100 mW / cm 2 .
　（異方性導電材料）
　本発明の硬化性エポキシ組成物に導電性粒子を含有させることにより、異方性導電材料を得ることができる。 (Anisotropic conductive material)
An anisotropic conductive material can be obtained by including conductive particles in the curable epoxy composition of the present invention.
　上記導電性粒子は、対向する電気的接続部分間、例えば回路基板の電極と電子部品の電極との間等を電気的に接続する。上記導電性粒子は、少なくとも外表面が導電性を有する粒子であれば特に限定されない。上記導電性粒子としては、例えば、有機粒子、無機粒子、有機無機ハイブリッド粒子、もしくは金属粒子等の表面を金属層で被覆した導電性粒子、又は実質的に金属のみで構成される金属粒子等が挙げられる。上記金属層は特に限定されない。上記金属層としては、金層、銀層、銅層、ニッケル層、パラジウム層、又は錫を含有する金属層等が挙げられる。 The conductive particles electrically connect the opposing electrical connection portions, for example, between the electrodes of the circuit board and the electrodes of the electronic component. The conductive particles are not particularly limited as long as at least the outer surface has conductivity. Examples of the conductive particles include organic particles, inorganic particles, organic-inorganic hybrid particles, or conductive particles whose surfaces are covered with a metal layer, or metal particles that are substantially composed only of metal. Can be mentioned. The metal layer is not particularly limited. Examples of the metal layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, or a metal layer containing tin.
　上記導電性粒子の含有量は特に限定されない。上記エポキシ成分の合計１００重量部に対して、上記導電性粒子は０．５～５重量部の範囲内で含有されることが好ましい。上記導電性粒子の含有量が０．５重量部未満であると、電極同士を確実に導通させることができないことがある。導電性粒子の含有量が５重量部を超えると、導通されてはならない隣接する電極間で短絡が生じることがある。 The content of the conductive particles is not particularly limited. The conductive particles are preferably contained within a range of 0.5 to 5 parts by weight with respect to a total of 100 parts by weight of the epoxy component. If the content of the conductive particles is less than 0.5 parts by weight, the electrodes may not be reliably conducted. When content of electroconductive particle exceeds 5 weight part, a short circuit may arise between the adjacent electrodes which should not be conduct | electrically_connected.
　異方性導電材料が液状又はペースト状である場合に、異方性導電材料の粘度（２５℃）は、２００００～１０００００ｍＰａ・ｓの範囲内にあることが好ましい。上記粘度が低すぎると、導電性粒子が、異方性導電材料中において沈降してしまうことがある。上記粘度が高すぎると、導電性粒子が、異方性導電材料中に充分に分散しないことがある。 When the anisotropic conductive material is liquid or pasty, the viscosity (25 ° C.) of the anisotropic conductive material is preferably in the range of 20000 to 100,000 mPa · s. If the viscosity is too low, the conductive particles may settle in the anisotropic conductive material. When the viscosity is too high, the conductive particles may not be sufficiently dispersed in the anisotropic conductive material.
　また、異方性導電材料の塩素イオン濃度は、５００ｐｐｍ以下であることが好ましい。上記塩素イオン濃度が高すぎると、異方性導電材料に含まれている硬化性エポキシ組成物の硬化速度が遅くなることがある。 Further, the chlorine ion concentration of the anisotropic conductive material is preferably 500 ppm or less. If the chlorine ion concentration is too high, the curing rate of the curable epoxy composition contained in the anisotropic conductive material may be slow.
　本発明の異方性導電材料は、異方性導電ペースト、異方性導電インク、異方性導電粘接着剤、異方性導電フィルム、又は異方性導電シート等として使用され得る。本発明の導電性粒子を含む異方性導電材料が、異方性導電フィルム又は異方性導電シート等のフィルム状の接着剤として使用される場合には、該導電性粒子を含むフィルム状の接着剤に、導電性粒子を含まないフィルム状の接着剤が積層されていてもよい。 The anisotropic conductive material of the present invention can be used as an anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, anisotropic conductive sheet or the like. When the anisotropic conductive material containing the conductive particles of the present invention is used as a film-like adhesive such as an anisotropic conductive film or an anisotropic conductive sheet, the film-like shape containing the conductive particles is used. A film-like adhesive that does not contain conductive particles may be laminated on the adhesive.
　（接続構造体）
　本発明の異方性導電材料を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。接続対象部材は、電子部品及び回路基板の内の少なくとも一方であることが好ましい。 (Connection structure)
A connection structure can be obtained by connecting the connection target members using the anisotropic conductive material of the present invention. The connection target member is preferably at least one of an electronic component and a circuit board.
　上記接続構造体は、硬化物層と、接続対象部材とを備え、該硬化物層が、本発明の異方性導電材料又は本発明の硬化性エポキシ組成物を硬化させることにより形成されていることが好ましい。 The connection structure includes a cured product layer and a connection target member, and the cured product layer is formed by curing the anisotropic conductive material of the present invention or the curable epoxy composition of the present invention. It is preferable.
　上記接続構造体は、第１の電気的接続部を有する第１の接続対象部材と、第２の電気的接続部を有する第２の接続対象部材と、第１，第２の電気的接続部を電気的に接続している接続部分としての硬化物層とを備えることが好ましい。この硬化物層が、本発明の異方性導電材料を硬化させることにより形成されている。 The connection structure includes a first connection target member having a first electrical connection portion, a second connection target member having a second electrical connection portion, and first and second electrical connection portions. It is preferable to provide a cured product layer as a connecting portion that electrically connects the two. The cured product layer is formed by curing the anisotropic conductive material of the present invention.
　図１は、本発明の一実施形態に係る硬化性エポキシ組成物と、導電性粒子とを含む異方性導電材料を用いた接続構造体を模式的に示す正面断面図である。 FIG. 1 is a front cross-sectional view schematically showing a connection structure using an anisotropic conductive material including a curable epoxy composition according to an embodiment of the present invention and conductive particles.
　図１に示す接続構造体１は、第１の接続対象部材２と、第２の接続対象部材３と、第１，第２の接続対象部材２，３とを電気的に接続している硬化物層４とを備える。硬化物層４は、接続部分であり、複数の導電性粒子５を含む異方性導電材料としての異方性導電ペーストを用いて形成されている。 The connection structure 1 shown in FIG. 1 is a curing that electrically connects the first connection target member 2, the second connection target member 3, and the first and second connection target members 2 and 3. A physical layer 4. The cured product layer 4 is a connecting portion and is formed using an anisotropic conductive paste as an anisotropic conductive material including a plurality of conductive particles 5.
　第１の接続対象部材２の上面２ａに、複数の電極２ｂが設けられている。第２の接続対象部材３の下面３ａに、複数の電極３ｂが設けられている。第１の接続対象部材２の上面２ａに、導電性粒子１を含有する異方性導電ペーストにより形成された硬化物層４を介して、第２の接続対象部材３が積層されている。電極２ｂと電極３ｂとが、導電性粒子５により電気的に接続されている。 A plurality of electrodes 2 b are provided on the upper surface 2 a of the first connection target member 2. A plurality of electrodes 3 b are provided on the lower surface 3 a of the second connection target member 3. The second connection target member 3 is laminated on the upper surface 2 a of the first connection target member 2 via a cured product layer 4 formed of an anisotropic conductive paste containing the conductive particles 1. The electrode 2 b and the electrode 3 b are electrically connected by the conductive particles 5.
　上記接続構造体としては、具体的には、半導体チップ、コンデンサ及びダイオード等の電子部品、並びにプリント基板、フレキシブルプリント基板及びガラス基板等の回路基板が導電接続された接続構造体が挙げられる。 Specific examples of the connection structure include a connection structure in which electronic parts such as a semiconductor chip, a capacitor, and a diode, and a circuit board such as a printed board, a flexible printed board, and a glass board are conductively connected.
　本発明の接続構造体の製造方法は特に限定されない。接続構造体の製造方法としては、電子部品又は回路基板等の第１の接続対象部材に形成された第１の電極と、電子部品又は回路基板等の第２の接続対象部材に形成された第２の電極との間に、上記異方性導電材料を配置して、積層体を得た後、該積層体を加熱、加圧する製造方法が挙げられる。 The manufacturing method of the connection structure of the present invention is not particularly limited. As a manufacturing method of the connection structure, a first electrode formed on a first connection target member such as an electronic component or a circuit board, and a second electrode formed on a second connection target member such as an electronic component or a circuit board are used. The manufacturing method of arrange | positioning the said anisotropic conductive material between 2 electrodes, obtaining a laminated body, and heating and pressurizing this laminated body is mentioned.
　以下、本発明について、実施例および比較例を挙げて具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited only to the following examples.
　硬化性エポキシ組成物を得るためのエポキシ成分として、下記の材料を用意した。 The following materials were prepared as epoxy components for obtaining a curable epoxy composition.
　［エポキシ成分Ａ］
　（１）エポキシ化合物［Ａ－１］：上記式（１Ｂ）で表される構造を有するエポキシ化合物（上記式（１）で表される構造を有するエポキシ化合物であって、上記式（１）中のＲ１及びＲ２がメチレン基であり、Ｒ３及びＲ４が水素原子である化合物） [Epoxy component A]
(1) Epoxy compound [A-1]: an epoxy compound having a structure represented by the above formula (1B) (an epoxy compound having a structure represented by the above formula (1), In which R1 and R2 are methylene groups and R3 and R4 are hydrogen atoms)
　（２）エポキシ化合物［Ａ－２］：上記式（１）で表される構造を有するエポキシ化合物であって、上記式（１）中のＲ１及びＲ２がｎ－プロピレン基であり、Ｒ３及びＲ４が水素原子である化合物 (2) Epoxy compound [A-2]: an epoxy compound having a structure represented by the above formula (1), wherein R1 and R2 in the above formula (1) are n-propylene groups, and R3 and R4 In which is a hydrogen atom
　（３）エポキシ化合物［Ａ－３］：上記式（１）で表される構造を有するエポキシ化合物であって、上記式（１）中のＲ１及びＲ２がｎ－ペンチレン基であり、Ｒ３及びＲ４が水素原子である化合物 (3) Epoxy compound [A-3]: an epoxy compound having a structure represented by the above formula (1), wherein R1 and R2 in the above formula (1) are n-pentylene groups, and R3 and R4 In which is a hydrogen atom
　（４）エポキシ化合物［Ａ－４］：上記式（１）で表される構造を有するエポキシ化合物であって、上記式（１）中のＲ１及びＲ２がメチレン基であり、Ｒ３が上記式（２）で表される構造を表し、かつ式（２）中のＲ５がメチレン基であり、Ｒ４が上記式（３）で表される構造を表し、かつ上記式（３）中のＲ６がメチレン基である化合物 (4) Epoxy compound [A-4]: an epoxy compound having a structure represented by the above formula (1), wherein R1 and R2 in the above formula (1) are methylene groups, and R3 is the above formula ( 2), R5 in the formula (2) is a methylene group, R4 represents a structure represented by the above formula (3), and R6 in the above formula (3) is methylene. The compound that is the group
　（５）エポキシ化合物［Ａ－５］：下記式（１０１）で表される構造を有するエポキシ化合物 (5) Epoxy compound [A-5]: Epoxy compound having a structure represented by the following formula (101)
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　（６）エポキシ化合物［Ａ－６］：上記式（１）で表される構造を有するエポキシ化合物であって、上記式（１）中のＲ１及びＲ２がヘキシレン基であり、Ｒ３及びＲ４が水素原子である化合物 (6) Epoxy compound [A-6]: an epoxy compound having a structure represented by the above formula (1), wherein R1 and R2 in the above formula (1) are hexylene groups, and R3 and R4 are hydrogen A compound that is an atom
　なお、上記エポキシ化合物［Ａ－１］～［Ａ－６］の、単量体と少なくとも２個結合された多量体との混合比率（単量体：多量体）は、８０重量％：２０重量％であった。 The mixing ratio (monomer: multimer) of the above-mentioned epoxy compounds [A-1] to [A-6] between the monomer and the multimer bonded with at least two is 80% by weight: 20%. %Met.
　［エポキシ成分Ａ以外のエポキシ成分Ｂ］
　（１）エポキシ化合物［Ｂ１－１］：ビスフェノールＡ型エポキシ樹脂 [Epoxy component B other than epoxy component A]
(1) Epoxy compound [B1-1]: Bisphenol A type epoxy resin
　（２）エポキシ化合物［Ｂ２－１］：アデカレジンＥＰ－３３００Ｓ（ＡＤＥＫＡ社製） (2) Epoxy compound [B2-1]: Adeka Resin EP-3300S (manufactured by ADEKA)
　（３）エポキシ化合物［Ｂ２－２］：レゾルシノールジグリシジルエーテル (3) Epoxy compound [B2-2]: resorcinol diglycidyl ether
　（４）エポキシ化合物［Ｂ３－１］：トリグリシジルイソシアヌレート（上記式（７Ａ）で表されるエポキシ化合物） (4) Epoxy compound [B3-1]: Triglycidyl isocyanurate (epoxy compound represented by the above formula (7A))
　（５）エポキシ化合物［Ｂ３－２］：トリスヒドロキシエチルイソシアヌレートトリグリシジルエーテル（上記式（８Ａ）で表されるエポキシ化合物） (5) Epoxy compound [B3-2]: Trishydroxyethyl isocyanurate triglycidyl ether (epoxy compound represented by the above formula (8A))
　また、硬化性エポキシ組成物を得るための硬化剤として、下記の材料を用意した。 Also, the following materials were prepared as curing agents for obtaining a curable epoxy composition.
　［硬化剤］
　（１）イミダゾール硬化剤（アミンアダクト型硬化剤（味の素ファインテクノ社製「ＰＮ－２３Ｊ」）） [Curing agent]
(1) Imidazole curing agent (amine adduct type curing agent (“PN-23J” manufactured by Ajinomoto Fine Techno Co.))
　（２）１，２－ジメチルイミダゾール (2) 1,2-dimethylimidazole
　（３）アミン硬化剤（エチレンジアミン） (3) Amine curing agent (ethylenediamine)
　（４）ポリチオール硬化剤（ＳＣ有機化学社製「ＴＭＭＰ：トリメチロールプロパントリス－３－メルカプトプロピオネート」） (4) Polythiol curing agent (“TMMP: Trimethylolpropane tris-3-mercaptopropionate” manufactured by SC Organic Chemical Co., Ltd.)
　（実施例１）
　上記エポキシ成分としての上記エポキシ化合物［Ａ－１］（上記式（１Ｂ）で表される構造を有するエポキシ化合物）１００重量部と、平均粒子径０．０２μｍのシリカ粒子７重量部と、硬化剤としてイミダゾール硬化剤（アミンアダクト型硬化剤（味の素ファインテクノ社製「ＰＮ－２３Ｊ」））４０重量部と、シランカップリング剤として３－グリシドキシプロピルトリエトキシシラン４．５重量部と、平均粒子径３μｍの導電性粒子２重量部とを配合し、硬化性組成物を得た。なお、用いた上記導電性粒子は、ジビニルベンゼン樹脂粒子の表面にニッケルめっき層が形成されており、かつ該ニッケルめっき層の表面に金めっき層が形成されている金属層を有する導電性粒子である。 Example 1
100 parts by weight of the epoxy compound [A-1] (epoxy compound having the structure represented by the formula (1B)) as the epoxy component, 7 parts by weight of silica particles having an average particle size of 0.02 μm, and a curing agent 40 parts by weight of an imidazole curing agent (amine adduct type curing agent (“PN-23J” manufactured by Ajinomoto Fine Techno Co., Ltd.)) and 4.5 parts by weight of 3-glycidoxypropyltriethoxysilane as a silane coupling agent 2 parts by weight of conductive particles having a particle diameter of 3 μm were blended to obtain a curable composition. The conductive particles 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.
　遊星式攪拌機を用いて、２０００ｒｐｍで得られた硬化性組成物を８分間攪拌し、ナイロン製ろ紙（孔径１０μｍ）を用いてろ過し、異方性導電材料としての異方性導電ペーストを作製した。 Using a planetary stirrer, the curable composition obtained at 2000 rpm was stirred for 8 minutes and filtered using a nylon filter paper (pore diameter 10 μm) to prepare an anisotropic conductive paste as an anisotropic conductive material. .
　（比較例１）
　上記エポキシ化合物［Ｂ１－１］（ビスフェノールＡ型エポキシ樹脂）１００重量部と、硬化剤として１，２－ジメチルイミダゾール５重量部とを、遊星式攪拌機を用いて、２０００ｒｐｍで５分間攪拌し、混合物を得た。得られた混合物に、平均粒子径０．０２μｍのシリカ粒子７重量部と、平均粒子径３μｍの導電性粒子２重量部とを添加し、硬化性組成物を得た。なお、用いた上記導電性粒子は、ジビニルベンゼン樹脂粒子の表面にニッケルめっき層が形成されており、かつ該ニッケルめっき層の表面に金めっき層が形成されている金属層を有する導電性粒子である。 (Comparative Example 1)
100 parts by weight of the above epoxy compound [B1-1] (bisphenol A type epoxy resin) and 5 parts by weight of 1,2-dimethylimidazole as a curing agent were stirred for 5 minutes at 2000 rpm using a planetary stirrer, Got. 7 parts by weight of silica particles having an average particle diameter of 0.02 μm and 2 parts by weight of conductive particles having an average particle diameter of 3 μm were added to the obtained mixture to obtain a curable composition. The conductive particles 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.
　遊星式攪拌機を用いて、２０００ｒｐｍで得られた硬化性組成物を８分間攪拌し、ナイロン製ろ紙（孔径１０μｍ）でろ過し、異方性導電材料としての異方性導電ペーストを作製した。 Using a planetary stirrer, the curable composition obtained at 2000 rpm was stirred for 8 minutes and filtered with a nylon filter paper (pore size: 10 μm) to prepare an anisotropic conductive paste as an anisotropic conductive material.
　（実施例２～６０及び比較例２、３）
　エポキシ成分の種類及び配合量（配合単位は重量部）を下記の表１～６に示すように変更したこと以外は実施例１と同様にして、異方性導電ペーストを得た。 (Examples 2 to 60 and Comparative Examples 2 and 3)
An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the type and blending amount of the epoxy component (the blending unit was parts by weight) were changed as shown in Tables 1 to 6 below.
　（実施例６１、６２）
　硬化剤の種類を下記の表７に示すように変更したこと以外は実施例７と同様にして、異方性導電ペーストを得た。 (Examples 61 and 62)
An anisotropic conductive paste was obtained in the same manner as in Example 7 except that the type of curing agent was changed as shown in Table 7 below.
　（実施例６３）
　分子蒸留装置（柴田科学社製、型式「ＭＳ－３００型回転薄膜式」）を用いて、上記エポキシ化合物［Ａ－１］に含まれている単量体を単離した。上記エポキシ化合物［Ａ－１］のかわりに、エポキシ化合物［Ａ－１］から単離された単量体を用いたこと以外は実施例７と同様にして、異方性導電ペーストを得た。 (Example 63)
The monomer contained in the epoxy compound [A-1] was isolated using a molecular distillation apparatus (manufactured by Shibata Kagaku Co., Ltd., model “MS-300 type rotating thin film type”). An anisotropic conductive paste was obtained in the same manner as in Example 7, except that a monomer isolated from the epoxy compound [A-1] was used instead of the epoxy compound [A-1].
　（実施例６４）
　分子蒸留装置（柴田科学社製、型式「ＭＳ－３００型回転薄膜式」）を用いて、上記エポキシ化合物［Ａ－１］に含まれている単量体を単離した。上記エポキシ化合物［Ａ－１］のかわりに、エポキシ化合物［Ａ－１］から単量体が単離された後の多量体を用いたこと以外は実施例７と同様にして、異方性導電ペーストを得た。 (Example 64)
The monomer contained in the epoxy compound [A-1] was isolated using a molecular distillation apparatus (manufactured by Shibata Kagaku Co., Ltd., model “MS-300 type rotating thin film type”). Instead of the epoxy compound [A-1], an anisotropic conductive film was obtained in the same manner as in Example 7 except that the polymer after the monomer was isolated from the epoxy compound [A-1] was used. A paste was obtained.
　なお、実施例１～６４にて得られた異方性導電ペーストの塩素イオン濃度はそれぞれ、５００ｐｐｍ以下であった。 The anisotropic conductive pastes obtained in Examples 1 to 64 each had a chlorine ion concentration of 500 ppm or less.
　（評価）
　（１）ピーク温度及び発熱量
　示差走査熱量計（ティーエーインスツルメンツ社製、型式「ＤＳＣ２９２０」）を用いて、昇温速度１０℃／分の条件で、実施例及び比較例で得られた異方性導電ペーストのピーク温度と発熱量とを測定した。なお、上記条件にて測定した場合、ピーク温度が１４０℃以下である異方性導電ペーストを合格とした。 (Evaluation)
(1) Peak temperature and calorific value Anisotropy obtained in Examples and Comparative Examples using a differential scanning calorimeter (manufactured by TI Instruments, model “DSC2920”) at a temperature rising rate of 10 ° C./min. The peak temperature and calorific value of the conductive paste were measured. In addition, when measured on the said conditions, the anisotropic conductive paste whose peak temperature is 140 degrees C or less was set as the pass.
　（２）ガラス転移温度
　異方性導電ペーストをフッ素樹脂製の型内に充填し、１５０℃で３０分間加熱することにより、縦１ｍｍ×横２０ｍｍ×厚み０．３ｍｍの測定サンプルを得た。 (2) Glass transition temperature An anisotropic conductive paste was filled in a fluororesin mold and heated at 150 ° C. for 30 minutes to obtain a measurement sample measuring 1 mm long × 20 mm wide × 0.3 mm thick.
　動的粘弾性装置ＤＭＡ（ティーエーインスツルメンツ社製、型式「Ｑ８００」）を用いて、得られた測定サンプルのｔａｎδの最大値となる温度を測定し、該最大値となる温度をガラス転移温度とした。 Using a dynamic viscoelastic device DMA (manufactured by TA Instruments, model “Q800”), a temperature at which the maximum value of tan δ of the obtained measurement sample is measured is measured, and the temperature at which the maximum value is obtained is referred to as a glass transition temperature. did.
　（３）吸水率
　異方性導電ペーストをフッ素樹脂製の型内に充填し、１５０℃で３０分間加熱することにより、縦２ｍｍ×横２０ｍｍ×厚み０．４ｍｍの測定サンプルを得た。 (3) Water Absorption Rate An anisotropic conductive paste was filled in a fluororesin mold and heated at 150 ° C. for 30 minutes to obtain a measurement sample of 2 mm long × 20 mm wide × 0.4 mm thick.
　得られた測定サンプルを８５℃及び相対湿度８５％の高温高湿下に２４時間放置した。放置前の測定サンプルの重量と、放置後の測定サンプルの重量とから、下記式により、吸水率を求めた。
　吸水率（重量％）＝（放置後の重量－放置前の重量）／（放置前の重量）×１００ The obtained measurement sample was left under high temperature and high humidity at 85 ° C. and a relative humidity of 85% for 24 hours. From the weight of the measurement sample before being left and the weight of the measurement sample after being left, the water absorption was determined by the following formula.
Water absorption rate (% by weight) = (weight after being left−weight before being left) / (weight before being left) × 100
　（４）硬化時間
　ＩＴＯ電極（Ｌ／Ｓ＝１０μｍ）が上面に設けられたガラス基板（縦５０ｍｍ×横５０ｍｍ×厚み１ｍｍ）を用意した。さらに、金バンプ（縦１０μｍ×横１５μｍ×高さ３０μｍ）が下面に設けられた半導体チップ（縦２ｍｍ×横４０ｍｍ×厚み０．３ｍｍ）を用意した。上記ガラス基板上に、実施例及び比較例の各異方性導電ペーストを塗工した。次に、異方性導電ペーストが塗工されたガラス基板上に、上記半導体チップを積層し、積層体を得た。得られた積層体を、圧力９８Ｎ及び１９０℃の条件で１０秒間熱圧着し、接続構造体を得た。得られた接続構造体の電極間の接続抵抗値を測定した。この結果、実施例１～６４の各異方性導電ペーストを用いた場合では、接続構造体の電極間が導電接続されていることを確認した。比較例１～３の各異方性導電ペーストを用いた場合では、電極間が導電接続されていなかった。 (4) Curing time A glass substrate (length 50 mm × width 50 mm × thickness 1 mm) provided with an ITO electrode (L / S = 10 μm) on the upper surface was prepared. Further, a semiconductor chip (vertical 2 mm × horizontal 40 mm × thickness 0.3 mm) provided with gold bumps (vertical 10 μm × horizontal 15 μm × height 30 μm) was prepared. The anisotropic conductive pastes of Examples and Comparative Examples were applied on the glass substrate. Next, the semiconductor chip was laminated on the glass substrate coated with the anisotropic conductive paste to obtain a laminate. The obtained laminate was thermocompression bonded for 10 seconds under conditions of a pressure of 98 N and 190 ° C. to obtain a connection structure. The connection resistance value between the electrodes of the obtained connection structure was measured. As a result, when the anisotropic conductive pastes of Examples 1 to 64 were used, it was confirmed that the electrodes of the connection structure were conductively connected. When the anisotropic conductive pastes of Comparative Examples 1 to 3 were used, the electrodes were not conductively connected.
　また、上記積層体を、圧力９８Ｎ及び１８０℃の条件で１０秒間熱圧着し、電極間の接続抵抗値を測定することにより、電極間が導電接続されているか否かを確認した。１０秒間の熱圧着で電極間が導電接続されていなかった場合は、新たな積層体を準備し、圧力９８Ｎ及び１８０℃の条件で２０秒間熱圧着し、電極間の接続抵抗値を測定することにより、電極間が導電接続されているか否かを確認した。２０秒間の熱圧着で電極間が導電接続されていなかった場合は、新たな積層体を準備し、圧力９８Ｎ及び１８０℃の条件で３０秒間熱圧着し、電極間の接続抵抗値を測定することにより、電極間が導電接続されているか否かを確認した。以下の基準により、硬化時間を評価した。 Further, the laminate was subjected to thermocompression bonding for 10 seconds under conditions of a pressure of 98 N and 180 ° C., and the connection resistance value between the electrodes was measured to confirm whether or not the electrodes were conductively connected. If the electrodes are not conductively connected by thermocompression for 10 seconds, prepare a new laminate, thermocompression bond for 20 seconds under the conditions of pressure 98N and 180 ° C, and measure the connection resistance between the electrodes. Thus, it was confirmed whether or not the electrodes were conductively connected. If the electrodes are not conductively connected by thermocompression for 20 seconds, prepare a new laminate, thermocompression for 30 seconds under the conditions of pressure 98N and 180 ° C, and measure the connection resistance between the electrodes. Thus, it was confirmed whether or not the electrodes were conductively connected. The curing time was evaluated according to the following criteria.
　［硬化時間の評価基準］
　◎：１０秒間の熱圧着で、電極間が導電接続されていた。
　○：２０秒間の熱圧着で、電極間が導電接続されていた。
　△：３０秒間の熱圧着で、電極間が導電接続されていた。
　×：３０秒間熱圧着しても、電極間が導電接続されていなかった。 [Evaluation criteria for curing time]
A: The electrodes were conductively connected by thermocompression bonding for 10 seconds.
A: The electrodes were conductively connected by thermocompression bonding for 20 seconds.
Δ: The electrodes were conductively connected by thermocompression bonding for 30 seconds.
X: The electrodes were not conductively connected even after thermocompression bonding for 30 seconds.
　結果を下記の表１～７に示す。 The results are shown in Tables 1 to 7 below.
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　実施例１～６４の異方性導電ペーストでは、比較例１の異方性導電ペーストと比較して、ピーク温度が低く、かつ発熱量が高かった。また、比較例１の異方性導電ペーストよりも、実施例１～６４の異方性導電ペーストの方が、速やかに硬化させることができた。また、比較例２、３の異方性導電ペーストは、ピーク温度が高く、発熱量が低いため、速やかに硬化させることが困難であった。 The anisotropic conductive pastes of Examples 1 to 64 had a lower peak temperature and a higher calorific value than the anisotropic conductive paste of Comparative Example 1. In addition, the anisotropic conductive pastes of Examples 1 to 64 could be cured more quickly than the anisotropic conductive paste of Comparative Example 1. Moreover, since the anisotropic conductive pastes of Comparative Examples 2 and 3 had high peak temperatures and low calorific values, it was difficult to cure them quickly.

Claims (12)

  1. 　エポキシ成分と、硬化剤とを含有し、
    　前記エポキシ成分が、下記式（１）で表される構造を有するエポキシ化合物の単量体、該エポキシ化合物が少なくとも２個結合された多量体、又は該単量体と該多量体との混合物を含む、硬化性エポキシ組成物。
    Figure JPOXMLDOC01-appb-C000001
     　上記式（１）中、Ｒ１は炭素数１～５のアルキレン基を表し、Ｒ２は炭素数１～５のアルキレン基を表し、Ｒ３は水素原子、炭素数１～５のアルキル基又は下記式（２）で表される構造を表し、Ｒ４は水素原子、炭素数１～５のアルキル基又は下記式（３）で表される構造を表す。
    Figure JPOXMLDOC01-appb-C000002
     　上記式（２）中、Ｒ５は炭素数１～５のアルキレン基を表す。
    Figure JPOXMLDOC01-appb-C000003
     　上記式（３）中、Ｒ６は炭素数１～５のアルキレン基を表す。     Containing an epoxy component and a curing agent,
    The epoxy component is a monomer of an epoxy compound having a structure represented by the following formula (1), a multimer in which at least two epoxy compounds are bonded, or a mixture of the monomer and the multimer. A curable epoxy composition comprising.
    Figure JPOXMLDOC01-appb-C000001
     In the above formula (1), R1 represents an alkylene group having 1 to 5 carbon atoms, R2 represents an alkylene group having 1 to 5 carbon atoms, R3 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following formula ( 2), R4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structure represented by the following formula (3).
    Figure JPOXMLDOC01-appb-C000002
     In the above formula (2), R5 represents an alkylene group having 1 to 5 carbon atoms.
    Figure JPOXMLDOC01-appb-C000003
     In the above formula (3), R6 represents an alkylene group having 1 to 5 carbon atoms.
  2. 　前記式（１）中、Ｒ３及びＲ４は水素原子である、請求項１に記載の硬化性エポキシ組成物。 The curable epoxy composition according to claim 1, wherein R3 and R4 in the formula (1) are hydrogen atoms.
  3. 　前記エポキシ成分１００重量％中、前記式（１）で表される構造を有するエポキシ化合物の単量体、該エポキシ化合物が少なくとも２個結合された多量体、又は該単量体と該多量体との混合物の含有量が、５～１００重量％の範囲内である、請求項１または２に記載の硬化性エポキシ組成物。 In 100% by weight of the epoxy component, a monomer of an epoxy compound having a structure represented by the formula (1), a multimer in which at least two epoxy compounds are bonded, or the monomer and the multimer The curable epoxy composition according to claim 1 or 2, wherein the content of the mixture is in the range of 5 to 100% by weight.
  4. 　前記エポキシ成分が、窒素原子を含む複素環を有するエポキシ化合物をさらに含む、請求項１に記載の硬化性エポキシ組成物。 The curable epoxy composition according to claim 1, wherein the epoxy component further comprises an epoxy compound having a heterocyclic ring containing a nitrogen atom.
  5. 　前記窒素原子を含む複素環を有するエポキシ化合物は、下記式（７）で表されるエポキシ化合物、又は下記式（８）で表されるエポキシ化合物である、請求項４に記載の硬化性エポキシ組成物。
    Figure JPOXMLDOC01-appb-C000004
     　上記式（７）中、Ｒ１１～Ｒ１３はそれぞれ炭素数１～５のアルキレン基を表し、Ｘはエポキシ基又はヒドロキシメチル基を表す。
    Figure JPOXMLDOC01-appb-C000005
     　上記式（８）中、Ｒ１４～Ｒ１６はそれぞれ炭素数１～５のアルキレン基を示し、ｐ、ｑ及びｒはそれぞれ１～５の整数を示し、Ｒ１７～Ｒ１９はそれぞれ炭素数１～５のアルキレン基を示す。     The curable epoxy composition according to claim 4, wherein the epoxy compound having a heterocyclic ring containing a nitrogen atom is an epoxy compound represented by the following formula (7) or an epoxy compound represented by the following formula (8). object.
    Figure JPOXMLDOC01-appb-C000004
     In the above formula (7), R11 to R13 each represents an alkylene group having 1 to 5 carbon atoms, and X represents an epoxy group or a hydroxymethyl group.
    Figure JPOXMLDOC01-appb-C000005
     In the above formula (8), R14 to R16 each represent an alkylene group having 1 to 5 carbon atoms, p, q and r each represents an integer of 1 to 5, and R17 to R19 each represents an alkylene group having 1 to 5 carbon atoms. Indicates a group.
  6. 　前記窒素原子を含む複素環を有するエポキシ化合物は、トリグリシジルイソシアヌレート、又はトリスヒドロキシエチルイソシアヌレートトリグリシジルエーテルである、請求項５に記載の硬化性エポキシ組成物。 The curable epoxy composition according to claim 5, wherein the epoxy compound having a heterocyclic ring containing a nitrogen atom is triglycidyl isocyanurate or trishydroxyethyl isocyanurate triglycidyl ether.
  7. 　前記エポキシ成分１００重量％中、前記窒素原子を含む複素環を有するエポキシ化合物の含有量が、０．１～１０重量％の範囲内である、請求項４～６のいずれか１項に記載の硬化性エポキシ組成物。 The content of the epoxy compound having a heterocyclic ring containing a nitrogen atom in 100% by weight of the epoxy component is in the range of 0.1 to 10% by weight. Curable epoxy composition.
  8. 　前記エポキシ成分が、芳香族環を有するエポキシ化合物をさらに含む、請求項１または４に記載の硬化性エポキシ組成物。 The curable epoxy composition according to claim 1 or 4, wherein the epoxy component further comprises an epoxy compound having an aromatic ring.
  9. 　前記芳香族環が、ベンゼン環、ナフタレン環、又はアントラセン環である、請求項８に記載の硬化性エポキシ組成物。 The curable epoxy composition according to claim 8, wherein the aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring.
  10. 　請求項１に記載の硬化性エポキシ組成物と、導電性粒子とを含有する異方性導電材料。 An anisotropic conductive material containing the curable epoxy composition according to claim 1 and conductive particles.
  11. 　硬化物層と、該硬化物層により接続された接続対象部材とを備え、
    　前記硬化物層が、請求項１に記載の硬化性エポキシ組成物と導電性粒子とを含有する異方性導電材料を硬化させることにより形成されている、接続構造体。     A cured product layer, and a connection target member connected by the cured product layer,
    The connection structure in which the said hardened | cured material layer is formed by hardening the anisotropic electrically-conductive material containing the curable epoxy composition and electroconductive particle of Claim 1.
  12. 　硬化物層と、該硬化物層により接続された接続対象部材とを備え、
    　前記硬化物層が、請求項１に記載の硬化性エポキシ組成物を硬化させることにより形成されている、接続構造体。     A cured product layer, and a connection target member connected by the cured product layer,
    The connection structure in which the said hardened | cured material layer is formed by hardening the curable epoxy composition of Claim 1.
PCT/JP2009/053503 2008-02-28 2009-02-26 Curable epoxy composition, anisotropic conductive material and connection structure WO2009107699A1 (en)

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