WO2023068109A1 - 硬化性樹脂組成物、硬化物及び接着剤 - Google Patents

硬化性樹脂組成物、硬化物及び接着剤 Download PDF

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WO2023068109A1
WO2023068109A1 PCT/JP2022/037880 JP2022037880W WO2023068109A1 WO 2023068109 A1 WO2023068109 A1 WO 2023068109A1 JP 2022037880 W JP2022037880 W JP 2022037880W WO 2023068109 A1 WO2023068109 A1 WO 2023068109A1
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Prior art keywords
resin composition
curable resin
composition according
curing agent
latent curing
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English (en)
French (fr)
Japanese (ja)
Inventor
啓介 太田
亮 小川
慎介 山田
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Adeka Corp
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Adeka Corp
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Priority to EP22883413.1A priority Critical patent/EP4421122A4/en
Priority to US18/697,963 priority patent/US20250002707A1/en
Priority to JP2023554529A priority patent/JPWO2023068109A1/ja
Priority to CN202280066927.8A priority patent/CN118055978A/zh
Publication of WO2023068109A1 publication Critical patent/WO2023068109A1/ja
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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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
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    • 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
    • C08G59/40—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 curing agents used
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    • C08G59/5006—Amines aliphatic
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    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
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    • 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
    • C08G59/40—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 curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
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    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
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    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
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Definitions

  • the present invention relates to a curable resin composition containing a cyanate ester resin, an epoxy resin, a latent curing agent and a conductive filler.
  • solder has been used as a conductive bonding agent for electronic components, but in many cases Sn--Pb alloy is used. However, since it contains lead, it is feared that it may adversely affect the human body and the environment. Therefore, a conductive adhesive obtained by blending a conductive filler with a polymer material has been applied as an alternative to solder.
  • the conductive adhesive has advantages such as low environmental load, low-temperature mounting, and ability to maintain adhesive strength even at high temperatures.
  • Patent Document 1 proposes blending conductive particles such as metal particles into an adhesive composition obtained by containing a cyanate ester resin, an epoxy resin and a latent curing agent.
  • a core-shell type curing agent having a modified imidazole as a nucleus is described as a suitable one, but it was not satisfactory in conductivity and curability.
  • the problem to be solved by the present invention is to provide a curable resin composition from which a cured product with excellent conductivity and curability can be obtained.
  • the present inventors have found that in a curable resin composition containing a cyanate ester resin, an epoxy resin, a latent curing agent and a conductive filler, by using an amine-based latent curing agent having an active hydrogen as the latent curing agent, The present inventors have found that a curable resin composition can provide a cured product having excellent electrical conductivity, and have completed the present invention.
  • the present invention provides (A) a cyanate ester resin, (B) an epoxy resin, (C) a latent curing agent containing an amine-based latent curing agent having an active hydrogen reacted with an amine compound and an epoxy compound, and ( D) A curable resin composition containing a conductive filler.
  • FIG. 1 is an SEM image of the cured product of Example 1.
  • FIG. 2 is an SEM image of the cured product of Comparative Example 3.
  • FIG. 3 is an SEM image of the cured product of Example 2.
  • FIG. 4 is an SEM image of the cured product of Comparative Example 1.
  • FIG. 5 is an SEM image of the cured product of Example 3.
  • the curable resin composition of the present invention is described below.
  • the cyanate ester resin which is the component (A) used in the present invention may be any compound having two or more cyanate groups, and can be used without particular limitation in terms of molecular structure, molecular weight and the like.
  • Examples of the cyanate ester resin include compounds represented by the following formula (1), compounds represented by the following formula (2), and polymers thereof.
  • Y 1 represents a divalent hydrocarbon group that is unsubstituted or substituted with a fluorine atom or a cyanato group, or represents —O—, —S—, or a single bond
  • a 1 and A 2 each independently represents a phenylene group that is unsubstituted or substituted with 1 to 4 alkyl groups.
  • m is an integer of 1 or more, and Y 2 and Y 3 each independently represent -S-, or are unsubstituted or substituted with a fluorine atom or a cyanato group. represents a hydrocarbon group, R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 4 carbon atoms, and n is each independently an integer of 0 to 2.
  • Examples of Y 1 in formula (1) and Y 2 and Y 3 in formula (2) include groups represented by the following formulas (Y-1) to (Y-9).
  • n is an integer of 4 to 12
  • R 7 and R 8 each independently represent a hydrogen atom or an unsubstituted or fluorine atom-substituted methyl group. * is a bond. represents.
  • cyanate ester resin Commercially available products of the cyanate ester resin include cyanate LECy, PT-15, PT30, PT-60, etc. manufactured by Lonza, L-10, XU366, XU371, XU378, etc. manufactured by Huntsman, CA200 manufactured by Mitsubishi Gas Chemical Co., Ltd. etc., but not limited to these. These cyanate ester resins may be used alone or in combination of two or more.
  • cyanate ester resins bisphenol type, biphenyl type, and novolak phenol type cyanate ester resins are preferable, and bisphenol type cyanate ester resins such as bisphenol A type, bisphenol E type, and bisphenol F type are particularly preferable. be.
  • the epoxy resin which is the component (B) used in the present invention, may have two or more epoxy groups in the molecule, and can be used without any particular restrictions on its molecular structure, molecular weight, and the like.
  • epoxy resin examples include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol and phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(orthocresol), ethylidene.
  • Bisphenol isopropylidenebisphenol (bisphenol A), isopropylidenebis(orthocresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene) , 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, ortho-cresol novolak, ethyl Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as phenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, and terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polypropylene glycol,
  • epoxy resins polyglycidyl ether compounds of polynuclear polyhydric phenol compounds are preferred.
  • the content of the epoxy resin as component (B) is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass, per 100 parts by mass of the cyanate ester resin as component (A). It is more preferable because a cured product having excellent physical properties can be obtained.
  • the latent curing agent which is the component (C) used in the present invention, contains an amine-based latent curing agent having active hydrogen obtained by reacting an amine compound and an epoxy compound.
  • the amine compound is an amine compound having one or more active hydrogens, and examples include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, hexa Alkylenediamines such as methylenediamine; Polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; Polyoxyalkylenepolyamines such as polyoxypropylenediamine and polyoxypropylenetriamine; 1,4-diaminocyclohexane, 1, 3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 4,4′-diaminodicyclohexylmethane, 1,3-
  • the active hydrogen equivalent of the amine compound is preferably 10 or more and 300 or less, more preferably 15 or more and 150 or less, from the viewpoint of the balance between curability and storage stability.
  • alkylenediamines such as ethylenediamine and 1,2-propylenediamine
  • polyalkylenepolyamines such as diethylenetriamine and triethylenetetramine
  • polyoxyalkylenepolyamines such as dioxypropylenediamine, polyoxypropylenepolyamine and polyoxyethylenepolyamine
  • Alicyclic amines such as isophoronediamine, 1,3-diaminomethylcyclohexane, N-(2-aminoethyl)piperazine and the like are particularly preferred.
  • 1,2-propylenediamine, dioxypropylenediamine and N-(2-aminoethyl)piperazine are preferred.
  • epoxy compounds examples include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol and phloroglucinol; ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(ortho-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene) ), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolak, ortho-cresol novolak, Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as ethylphenol novolak, butylphenol novolak, oc
  • the epoxy compound may be either a glycidyl type epoxy compound or a cycloalkene oxide type epoxy compound represented by an epoxidized product of a cyclic olefin compound. Moreover, when it is a glycidyl type, it may be either an aromatic epoxy compound having an aromatic ring or an aliphatic epoxy compound having no aromatic ring. From the viewpoint of reactivity, it is preferable to use a glycidyl-type epoxy compound, and from the viewpoint of heat resistance, it is more preferable to use a glycidyl-type aromatic epoxy compound.
  • the amine-based latent curing agent is obtained by reacting an amine compound and an epoxy compound. , in particular, it is preferable to react an amount of 0.2 to 0.8 equivalents.
  • amount of the epoxy compound By setting the amount of the epoxy compound to the amine compound at the lower limit or more, it is preferable because the storage stability of the curable resin composition can be improved. preferred because it is
  • the method for producing the amine-based latent curing agent is not particularly limited, but if necessary, a method of using a solvent and reacting under heating at normal temperature to 140° C. for 1 to 10 hours can be mentioned. When a solvent is used, the solvent can be removed under heating under normal pressure or under reduced pressure after the reaction is completed.
  • Solvents used in the production of the amine-based latent curing agent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexane; tetrahydrofuran, 1,2-dimethoxy Ethers such as ethane, 1,2-diethoxyethane and propylene glycol monomethyl ether; Esters such as ethyl acetate and n-butyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Carbon tetrachloride, chloroform and trichlorethylene , halogenated aliphatic hydrocarbons such as methylene chloride; and halogenated aromatic hydrocarbons such as chlorobenzene.
  • ketones such as methyl ethyl ketone, methyl am
  • the latent curing agent which is the component (C) used in the present invention, further contains a phenolic resin so that stability can be improved.
  • phenol resin examples include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, trisphenylolmethane.
  • Resin tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol cocondensation novolac resin, naphthol-cresol cocondensation novolac resin, biphenyl-modified phenolic resin (polyhydric phenol compound with phenolic nucleus linked by bismethylene group), biphenyl-modified Naphthol resin (polyvalent naphthol compound in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenolic resin (compound having a phenol skeleton, triazine ring and primary amino group in the molecular structure), and alkoxy group-containing aromatic ring Examples include polyhydric phenol compounds such as modified novolac resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
  • a phenolic resin with a softening point of 50 to 200°C.
  • the amount of the phenol resin used is preferably 10 to 100 parts by mass, particularly preferably 20 to 60 parts by mass, per 100 parts by mass of the amine-based latent curing agent. When the amount is 10 parts by mass or more, sufficient curability can be obtained.
  • the latent curing agent which is the component (C) used in the present invention
  • the latent curing agent which is the component (C) used in the present invention
  • it may be pulverized using a pulverizer such as a jet mill.
  • the latent curing agent may contain a latent curing agent other than the amine-based latent curing agent and the phenolic resin.
  • latent curing agents include, for example, dibasic oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, and the like.
  • the content of the latent curing agent, which is the component (C), is not particularly limited. It is preferably 1 to 70 parts by mass, more preferably 3 to 60 parts by mass, per 100 parts by mass of the total amount of a certain epoxy resin.
  • the conductive filler which is the component (D) used in the present invention, may be any material as long as it has conductivity.
  • Examples include metal particles such as gold, silver, nickel, copper, solder; tin oxide, indium oxide, zinc oxide. metal oxides such as; carbon black, graphite, carbon nanotubes, carbon fibers and the like; and nonmetallic glass, ceramics, plastics, etc. coated with the conductive layer.
  • the average particle size of these particles is preferably 0.1 to 50 ⁇ m, particularly 0.5 to 30 ⁇ m, from the viewpoint of excellent ease of entering into gaps and excellent meltability, and sufficient effect of imparting conductivity. is preferred.
  • the average particle size is measured using a particle size distribution analyzer using laser diffraction.
  • the shape of the particles includes spherical, flat, plate-like, flake-like, flaky, rod-like, dendritic, fibrous, needle-like, scale-like, horn-like, and polyhedral shapes, but is particularly limited. not a thing
  • the content of the conductive filler as the component (D) is preferably 30 to 90% by mass, particularly 50 to 80% by mass, in the curable resin composition from the viewpoint of sufficient conductivity-imparting effect. Preferably.
  • the cured product contains the conductive filler. It is believed that localization (see SEM images in FIGS. 1 to 4) occurs and conductivity is improved by forming and increasing conductive paths. No localization is observed when no cyanate ester resin is used or when an amine-based latent curing agent having no active hydrogen is used.
  • a known curing accelerator can be used together as needed.
  • these curing accelerators include phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-un Imidazoles such as decylimidazole and 1-cyanoethyl-2-methylimidazole; imidazole salts which are salts of said imidazoles with trimellitic acid, isocyanuric acid, boron, etc.; benzyldimethylamine, 2,4,6-tris ( Amines such as dimethylaminomethyl)phenol; Quaternary ammonium salts such as trimethylammonium chloride; 3-(p-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethyl Urea such
  • the curable resin composition of the present invention may contain various additives as necessary.
  • Additives include phenol compounds such as biphenol; reactive diluents such as p-tert-butyl glycidyl ether, n-butyl glycidyl ether, and C12-13 mixed alcohol glycidyl ether; dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar.
  • non-reactive diluents such as; silica such as fused silica and crystalline silica; aluminum oxide (alumina), magnesium oxide, zinc oxide, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, boron nitride , powders of zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, potassium titanate, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, etc., or beads obtained by spheroidizing these, and fillers such as glass fiber, pulp fiber, synthetic fiber and ceramic fiber; reinforcing materials such as glass cloth, aramid cloth and carbon fiber; pigments; ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)
  • the curable resin composition of the present invention When curing the curable resin composition of the present invention, it is preferable to heat at, for example, 80 to 200° C., in order to exhibit physical properties as a cured product.
  • the curable resin composition of the present invention can be used in a wide range of applications as an adhesive.
  • the cured product since the cured product has excellent conductivity, it can be suitably used for electronic applications such as semiconductor encapsulation and adhesives for electronic parts.
  • Example 1 to 4 and Comparative Examples 1 to 3 Each component was mixed according to the formulation shown in Table 1 below to produce a resin composition, which was subjected to the following tests. The evaluation results are shown in Table 1 below. In addition, the numerical value of the composition of Table 1 represents a mass part.
  • EP-1 EP-4901E manufactured by ADEKA Corporation (bisphenol F type epoxy resin)
  • EP-2 ED-509S (4-tert-butylphenyl glycidyl ether) manufactured by ADEKA Corporation
  • CY-1 LECy (bisphenol-type cyanate ester resin) manufactured by Lonza
  • EH-1 latent curing agent (EH-1) produced in Production Example 1
  • EH-2 latent curing agent (EH-2) produced in Production Example 2
  • EH-3 latent curing agent (EH-3) produced in Production Example 3
  • EH-4 Dicyandiamide KBM-403: Shin-Etsu Chemical Co., Ltd.
  • Ag-1 flat silver particles with an average particle size of 4.8 ⁇ m
  • Ag-2 spherical silver particles with an average particle size of 0.9 ⁇ m
  • Ag-3 dendritic electrolytic silver powder with an average particle size of 1.0 ⁇ m
  • Ag/Cu- 1 Flat silver-plated copper powder with an average particle size of 6.0 ⁇ m
  • ⁇ Conductivity> The curable resin compositions of Examples and Comparative Examples were coated on a glass plate using a bar code so as to have a thickness of 100 to 300 ⁇ m. It was cured by heating for 30 minutes in a circulating constant temperature bath kept at 150°C. The film thickness of the obtained cured film was measured, and the volume resistivity was measured as an evaluation of conductivity. The volume resistivity ( ⁇ cm) was calculated using a 4-terminal 4-probe resistivity meter (Loresta GPMPC-T610, manufactured by Mitsubishi Chemical Analytic Tech). A was assigned when the resistance value was 1.0 ⁇ 10 ⁇ 2 ⁇ cm or less, and B was assigned when the resistance value was over 1.0 ⁇ 10 ⁇ 2 ⁇ cm.
  • ⁇ Gel Time> Set the temperature of the hot plate to 150 ⁇ 2 ° C., place about 1 g of the curable compositions of Examples and Comparative Examples on this hot plate, and measure the time until stirring becomes impossible (gel time) while stirring. bottom. A sample with a gel time of less than 10 seconds was rated as A, and a sample with a gel time of 10 seconds or longer was rated as B.
  • FIG. 1 is an image of the cured product of Example 1 magnified 4000 times
  • FIG. 2 is an image of the cured product of Comparative Example 3 magnified 4000 times
  • FIG. 3 is an image of the cured product of Example 2 magnified 2000 times
  • 4 is an image obtained by enlarging the cured product of Comparative Example 1 by 2000 times.
  • the curable resin composition of the present invention is a curable resin composition from which a cured product having excellent conductivity and curability can be obtained.
  • the present invention since it is possible to provide a curable resin composition that gives a cured product having excellent conductivity, it can be suitably used as a conductive material such as a solder substitute material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2022/037880 2021-10-18 2022-10-11 硬化性樹脂組成物、硬化物及び接着剤 Ceased WO2023068109A1 (ja)

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EP22883413.1A EP4421122A4 (en) 2021-10-18 2022-10-11 CURABLE RESIN COMPOSITION, CURED OBJECT, AND ADHESIVE
US18/697,963 US20250002707A1 (en) 2021-10-18 2022-10-11 Curable resin composition, cured product, and adhesive
JP2023554529A JPWO2023068109A1 (https=) 2021-10-18 2022-10-11
CN202280066927.8A CN118055978A (zh) 2021-10-18 2022-10-11 固化性树脂组合物、固化物及粘接剂

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Publication number Priority date Publication date Assignee Title
JPH09279121A (ja) 1996-04-15 1997-10-28 Hitachi Chem Co Ltd 接着剤組成物および該組成物からなる接続部材
JPH11134940A (ja) * 1997-10-24 1999-05-21 Sumitomo Metal Mining Co Ltd 導電性樹脂ペースト
JP2004352785A (ja) * 2003-05-27 2004-12-16 Sumitomo Bakelite Co Ltd 異方導電性接着剤
WO2009001658A1 (ja) * 2007-06-22 2008-12-31 Adeka Corporation 一液型シアネート－エポキシ複合樹脂組成物
WO2011099292A1 (ja) * 2010-02-12 2011-08-18 株式会社Adeka 無溶剤一液型シアン酸エステル－エポキシ複合樹脂組成物
JP2012532942A (ja) * 2009-07-08 2012-12-20 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 導電性接着剤
WO2021049390A1 (ja) * 2019-09-09 2021-03-18 株式会社Adeka 硬化性樹脂組成物
WO2022190745A1 (ja) * 2021-03-08 2022-09-15 株式会社Adeka 硬化性樹脂組成物、硬化物及び接着剤

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09279121A (ja) 1996-04-15 1997-10-28 Hitachi Chem Co Ltd 接着剤組成物および該組成物からなる接続部材
JPH11134940A (ja) * 1997-10-24 1999-05-21 Sumitomo Metal Mining Co Ltd 導電性樹脂ペースト
JP2004352785A (ja) * 2003-05-27 2004-12-16 Sumitomo Bakelite Co Ltd 異方導電性接着剤
WO2009001658A1 (ja) * 2007-06-22 2008-12-31 Adeka Corporation 一液型シアネート－エポキシ複合樹脂組成物
JP2012532942A (ja) * 2009-07-08 2012-12-20 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 導電性接着剤
WO2011099292A1 (ja) * 2010-02-12 2011-08-18 株式会社Adeka 無溶剤一液型シアン酸エステル－エポキシ複合樹脂組成物
WO2021049390A1 (ja) * 2019-09-09 2021-03-18 株式会社Adeka 硬化性樹脂組成物
WO2022190745A1 (ja) * 2021-03-08 2022-09-15 株式会社Adeka 硬化性樹脂組成物、硬化物及び接着剤

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Title
See also references of EP4421122A4

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EP4421122A4 (en) 2025-10-15
CN118055978A (zh) 2024-05-17
US20250002707A1 (en) 2025-01-02
EP4421122A1 (en) 2024-08-28

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