WO2022202610A1 - Epoxy resin composition, epoxy resin cured product - Google Patents
Epoxy resin composition, epoxy resin cured product Download PDFInfo
- Publication number
- WO2022202610A1 WO2022202610A1 PCT/JP2022/012297 JP2022012297W WO2022202610A1 WO 2022202610 A1 WO2022202610 A1 WO 2022202610A1 JP 2022012297 W JP2022012297 W JP 2022012297W WO 2022202610 A1 WO2022202610 A1 WO 2022202610A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- resin composition
- compound
- formula
- mass
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 126
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- -1 carboxylic acid compounds Chemical class 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008646 thermal stress Effects 0.000 abstract description 6
- 230000006866 deterioration Effects 0.000 abstract description 5
- 238000001723 curing Methods 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000010494 dissociation reaction Methods 0.000 description 7
- 230000005593 dissociations Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 230000035882 stress Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229930003836 cresol Natural products 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- RUGWIVARLJMKDM-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)furan Chemical compound C1OC1COCC1=CC=CO1 RUGWIVARLJMKDM-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 101001139126 Homo sapiens Krueppel-like factor 6 Proteins 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 238000009833 condensation Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 239000000976 ink Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
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- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- PGGYWYZJYRRNPJ-UHFFFAOYSA-N cyclohexanone;n,n-dimethylformamide Chemical compound CN(C)C=O.O=C1CCCCC1 PGGYWYZJYRRNPJ-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08G59/26—Di-epoxy compounds heterocyclic
-
- 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
- C08G59/40—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
Definitions
- the present invention relates to epoxy resin compositions and epoxy resin cured products.
- Epoxy resin has excellent moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, etc., and has been used in fields such as molding materials, adhesive materials, electronic parts, and ink materials. Epoxy resins are also used as sealing materials for electronic components such as semiconductor devices.
- cured epoxy resins used as sealing materials are required not to crack or peel off due to stress such as thermal expansion or thermal contraction.
- stress such as thermal expansion or thermal contraction.
- Patent Document 1 it has been studied to add various additives to the epoxy resin.
- the present invention has been made in view of such circumstances, and provides an epoxy resin composition capable of suppressing cracks and peeling due to thermal stress while suppressing the deterioration of the inherent mechanical and thermal properties of epoxy resins. It provides
- an epoxy resin (A) 100 parts by mass of an epoxy resin (A), 5 to 90 parts by mass of a compound (B) represented by the following formula (1), and 10 to 90 parts by mass of a curing agent (C) are included.
- An epoxy resin composition is provided.
- the epoxy resin composition of one embodiment of the present invention contains an epoxy resin (A), a compound (B), and a curing agent (C).
- Epoxy resin (A) means a compound other than compound (B) having multiple epoxy groups (preferably multiple glycidyl groups).
- the number of epoxy groups in one molecule of the epoxy resin (A) is, for example, 2, 3 or 4, preferably 2 or 3, more preferably 2.
- the epoxy equivalent of the epoxy resin (A) is, for example, 120 to 400 (g/eq). eq) and may be in a range between any two of the values exemplified herein. Epoxy equivalent can be measured according to JIS K 7236:2009.
- the epoxy resin (A) is preferably liquid at 25°C from the viewpoint of handling.
- the weight average molecular weight (Mw) of the epoxy resin (A) is, for example, 240 to 600, specifically, for example, 240, 280, 320, 360, 400, 440, 480, 520, 560, 600, It may be in a range between any two of the numerical values exemplified here. Mw can be measured by a gel permeation chromatography (GPC) method.
- the epoxy resin (A) preferably does not have a reactive functional group selected from an amino group, a carboxyl group, a phenolic hydroxyl group, and a thiol group, and is not a carboxylic acid anhydride. Since such a reactive functional group has high reactivity with the epoxy group, it reacts with the epoxy group contained in the compound (B) to form a bond between the epoxy resin (A) and the compound (B). This is because the mechanical properties and thermophysical properties inherent in the epoxy resin tend to deteriorate.
- the epoxy resin (A) and the compound (B) are bonded via the curing agent (C), and the epoxy resin (A) and the compound (B) are It is preferred not to react directly.
- the epoxy resin (A) and the compound (B) may not cure. preferable.
- the epoxy resin (A) preferably does not have an addition reaction site (hereinafter referred to as "DA reaction addition site") formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure. This is because such an addition reaction portion tends to deteriorate the mechanical properties and thermophysical properties inherent in the epoxy resin.
- DA reaction addition site an addition reaction site formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure.
- Examples of the epoxy resin (A) include bifunctional or crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin; Novolac epoxy resins such as epoxy resins, phenol novolak epoxy resins, and naphthol novolak epoxy resins; Aralkyl-type epoxy resins; trifunctional epoxy resins such as triphenolmethane-type epoxy resins and alkyl-modified triphenolmethane-type epoxy resins are preferred. Particularly preferred are cresol novolac type epoxy resins and biphenylene skeleton-containing phenol aralkyl type epoxy resins.
- Examples of commercially available epoxy resins (A) are as follows. ⁇ Biphenyl type epoxy resin: YX4000 (Mitsubishi Chemical) ⁇ Bisphenol A type epoxy resin: jER-828 (Mitsubishi Chemical) ⁇ Bisphenol F type epoxy resin: EPICLON 830 (DIC) ⁇ Cresol novolac type epoxy resin: EPICLON N-680 (DIC) ⁇ Biphenylene skeleton-containing phenol aralkyl type epoxy resin: NC3000 (Nippon Kayaku)
- Compound (B) is a compound represented by the following formula (1).
- Compound (B) comprises a DA reaction adduct.
- the DA addition reaction part dissociates when the cured epoxy resin is exposed to high temperatures, thereby relieving the stress of the cured epoxy resin and suppressing the occurrence of cracks and peeling in the cured epoxy resin. .
- the content of the compound (B) with respect to 100 parts by mass of the epoxy resin (A) is 5 to 90 parts by mass, preferably 5 to 80 parts by mass, more preferably 5 to 60 parts by mass. If the content of the compound (B) is too small, the stress relaxation effect will not be sufficiently exhibited. If the content of the compound (B) is too large, the mechanical properties and thermophysical properties tend to deteriorate significantly. Specifically, this content is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 parts by mass. , within a range between any two of the numerical values exemplified herein.
- R 1 is * 2 —(CH 2 ) a —X—(CH 2 ) b —* 1 or * 2 —Ar 1 —(CH 2 ) a —X—(CH 2 ) b ⁇ * 1
- * 1 is the bond with the epoxy group
- * 2 is the bond with the other group
- X is a group represented by -O-, -S-, -NR 2 - or -COO-
- R 2 is -CH 3 , -C 2 H 5 or -(CH 2 ) a - a group represented by CH(O) CH2
- Ar 1 is an unsubstituted phenyl group or a phenyl group substituted with 1 to 4 (eg, 1,2,3,4) methyl or ethyl groups
- a is an integer of 0 to 5 (eg, 0, 1, 2, 3, 4, 5)
- b is an integer of 1 to 5 (eg, 1, 2, 3, 4, 5)
- Y is a
- R 3 is —(CH 2 ) d —, —[(CH 2 ) d —O] e —(CH 2 ) d —, —Ar 2 —, or —Ar 3 —R 4 -Ar 3 -
- d is an integer of 1 to 8 (eg, 1,2,3,4,5,6,7,8)
- e is an integer of 1 to 3 (eg, 1,2,3)
- Ar 2 and Ar 3 are each an unsubstituted phenyl group, a phenyl group substituted with 1 to 4 (eg, 1,2,3,4) methyl or ethyl groups, an unsubstituted biphenyl group, or a biphenyl group substituted with 1 to 8 (e.g., 1,2,3,4,5,6,7,8) methyl or ethyl groups
- R 4 is -(CH 2 ) f -, -O-, -S-, -SO-, -SO 2 -
- Y in formula (1) is preferably a group represented by formula (2).
- the compound (B) has two DA reaction addition sites, so that the stress relaxation effect is remarkable.
- R 3 in formula (2) is preferably -Ar 3 -R 4 -Ar 3 -.
- the compound (B) can be obtained, for example, by subjecting a conjugated diene compound represented by formula (3) and a dienophile compound represented by formula (4) or (5) to Diels-Alder reaction.
- the compound (B) preferably has a dissociation initiation temperature of 80 to 190°C.
- the dissociation initiation temperature is the temperature at which dissociation of the DA addition reaction portion of compound (B) is initiated, and can be measured by the method described in "3. Evaluation of epoxy resin composition" below. If the dissociation starting temperature is too low, the mechanical properties and thermophysical properties tend to deteriorate. Hard to be effective.
- the dissociation start temperature is, for example, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190° C. may be within the range.
- Compound (B) does not have a reactive functional group selected from an amino group, a carboxyl group, a phenolic hydroxyl group, and a thiol group, and is not a carboxylic acid anhydride, so that compound (B) is an epoxy resin (A). does not react with the epoxy groups of
- the curing agent (C) is a compound capable of reacting with a plurality of epoxy groups and linking compounds having epoxy groups.
- the curing agent (C) preferably has a plurality of reactive functional groups selected from amino groups, carboxyl groups, phenolic hydroxyl groups and thiol groups, or is a carboxylic acid anhydride.
- the epoxy resin composition is cured by the curing agent (C) connecting the epoxy resins (A) to each other, the compounds (B) to each other, or the epoxy resin (A) and the compound (B) to each other to increase the molecular weight. It becomes an epoxy resin hardened product.
- the content of the curing agent (C) with respect to 100 parts by mass of the epoxy resin (A) is 10 to 90 parts by mass, preferably 20 to 85 parts by mass, more preferably 30 to 80 parts by mass. If the curing agent (C) is too little or too much, the mechanical properties and thermophysical properties of the epoxy resin cured product tend to deteriorate.
- This content is specifically, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 parts by mass, here may be within a range between any two of the numerical values exemplified in .
- the total epoxy equivalent weight of the epoxy resin (A) and the compound (B) and the curing agent It is preferable that the curing agent (C) is contained in the composition so that the functional group equivalent weight of (C) is close to that of the curing agent (C).
- the value of ⁇ functional group equivalent of curing agent (C) ⁇ / ⁇ total value of epoxy equivalents of epoxy resin (A) and compound (B) ⁇ is, for example, 0.8 to 1.2, specifically For example, 0.8, 0.9, 1.0, 1.1, 1.2, and may be in the range between any two of the numerical values exemplified herein.
- the epoxy resin cured product obtained by curing the epoxy resin composition in which the epoxy resin (A), the compound (B) and the curing agent (C) are blended in the above ratio has the mechanical and thermophysical properties inherent in the epoxy resin. Cracks and peeling due to thermal stress are suppressed while suppressing the deterioration of
- the curing agent (C) is preferably at least one selected from amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and polyvalent carboxylic acid compounds.
- amine curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylylenediamine (MXDA); diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), diaminodiphenyl One or more selected from the group consisting of aromatic polyamines such as sulfone (DDS); and polyamine compounds such as dicyandiamide (DICY) and organic acid dihydralazide. Aliphatic polyamines are particularly preferred as amine-based curing agents.
- amine curing agents examples include as follows. ⁇ Aliphatic polyamine: jER Cure ST12 (Mitsubishi Chemical), ADEKA Hardener EH-6019 (ADEKA)
- phenolic curing agent examples include phenolic novolac resins, cresol novolak resins and other phenols, cresols, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene.
- Novolak resins obtained by condensation or co-condensation of phenols such as phenols and formaldehyde or ketones in the presence of an acidic catalyst; One or more selected from the group consisting of aralkyl resins; phenol aralkyl resins such as phenol aralkyl resins having a biphenylene skeleton; and phenol resins having a trisphenylmethane skeleton.
- the phenolic curing agent preferably contains one or more resins selected from the group consisting of biphenylaralkyl-type phenolic resins and triphenylmethane-type phenolic resins.
- cresol novolak resins and phenol aralkyl resins having a biphenylene skeleton are particularly preferred.
- phenolic curing agents examples include as follows. ⁇ Cresol novolak type: PHENOLITETD-2131 (DIC) ⁇ Biphenyl aralkyl type: KAYAHARDGPH-65 (Nippon Kayaku)
- Acid anhydride curing agents include, for example, hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), alicyclic acid anhydrides such as maleic anhydride; trimellitic anhydride (TMA), pyroanhydride
- HHPA hexahydrophthalic anhydride
- MTHPA methyltetrahydrophthalic anhydride
- TMA trimellitic anhydride
- pyroanhydride One or more selected from the group consisting of aromatic acid anhydrides such as mellitic acid (PMDA), benzophenonetetracarboxylic acid (BTDA), and phthalic anhydride can be used.
- polycarboxylic acid compounds include phthalic acid, hydroxyisophthalic acid, succinic acid, sebacic acid, maleic acid, dodecenylsuccinic acid, chlorendic acid, pyromellitic acid, trimellitic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. , tetrahydrophthalic acid, methyltetrahydrophthalic acid, and methylnadic acid.
- the epoxy resin composition of the present invention may contain a curing catalyst. By containing a curing catalyst, the epoxy resin composition can shorten the curing time.
- the content of the curing catalyst with respect to 100 parts by mass of the epoxy resin (A) is 0.1 to 5 parts by mass, preferably 0.3 to 4.5 parts by mass, more preferably 0.5 to 4.0 parts by mass. .
- this content is, for example, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 , 4.5, and 5.0 parts by mass, and may be within a range between any two of the numerical values exemplified herein.
- Curing catalysts include, for example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or salts thereof; 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or salts thereof tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol and N,N-dimethylcyclohexylamine; and phosphines such as triphenylphosphine and tris(dimethoxy)phosphine.
- DBU 1,8-diazabicyclo[5.4.0]undecene-7
- DBN 1,5-diazabicyclo[4.3.0]nonene-5
- tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol and N,N-dimethylcyclohexylamine
- phosphines such as triphen
- the epoxy resin composition of the present invention may optionally contain ultraviolet absorbers, antioxidants, antiseptics, rust inhibitors, pigments, tackifiers, surface lubricants, brighteners, water repellents, and photosensitizers. , Organic / inorganic fibers, plasticizers, conductive fillers, inorganic fillers, flame retardants, antistatic agents, foam stabilizers, release agents, colorants and foaming agents. good.
- An additive may be used individually by 1 type, and may use 2 or more types.
- the content of the additive with respect to 100 parts by mass of the epoxy resin (A) is, for example, 0 to 50 parts by mass, more preferably 0 to 20 parts by mass. Specifically, this content is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by mass, and ranges between any two of the numerical values illustrated here may be within
- the epoxy resin composition of the present invention may contain a solvent.
- solvents include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane and cyclooctane.
- Ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, 1,2-dichloroethane , halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; N,N-dimethylformamide, N, amides such as N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as
- the content of the solvent in the epoxy resin composition of the present invention is usually 70% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.
- a cured epoxy resin product can be formed by curing the epoxy resin composition of the present invention.
- the epoxy resin composition can be cured by heating or light irradiation, for example.
- the heating temperature (curing temperature) during curing is usually 20 to 300°C, preferably 40 to 250°C, more preferably 60 to 200°C.
- the curing temperature is, for example, 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 250, 260, 280, 300 ° C. Numerical values exemplified here may be in the range between any two of
- the heating time (curing time) for curing is usually 10 to 1440 minutes, preferably 30 to 900 minutes, more preferably 60 to 480 minutes.
- the heating can also be performed in multiple stages.
- light such as ultraviolet light, visible light, and infrared light can be used, and ultraviolet light is preferred.
- the exposure dose is preferably 1 to 10000 mJ/cm 2 , more preferably 10 to 3000 mJ/cm 2 .
- light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, chemical lamps, black light fluorescent lamps, and electrodeless UV lamps.
- the curing reaction can be carried out by coating the epoxy resin composition of the present invention on a substrate, or by injecting it into a mold.
- the shape of the cured product of the present invention is not particularly limited, and examples thereof include plate-like, sheet-like and film-like shapes.
- Their thickness is, for example, usually 0.01 to 1000 mm, preferably 0.1 to 100 mm, more preferably 0.1 to 5 mm.
- the epoxy resin composition may be of a one-component type or a two-component type.
- the first component contains the epoxy resin (A) and the compound (B)
- the second component contains the curing agent (C).
- the curing agent (C) since the curing agent (C) does not react with the epoxy resin (A) or the compound (B) during storage, the storage stability is improved.
- the curing agent (C) can be reacted with the epoxy resin (A) and the compound (B) by mixing the first liquid and the second liquid.
- the epoxy resin composition of the present invention it is possible to form an epoxy resin cured product that suppresses cracks and peeling due to thermal stress while suppressing the deterioration of the mechanical and thermal properties inherent in the epoxy resin.
- the epoxy resin composition of the present invention has the above properties, it can be used for applications such as electronic materials, binders, paints, and adhesives.
- substrate substrates for electronic members such as semiconductor packages, build-up films, solder resist inks, underfill materials, solid sealing materials for packages, binders for paving, binders for carbon fiber reinforced plastics (CFRP), Cationic electrodeposition coating agents, heavy-duty anti-corrosion coatings, powder coatings, infrastructure repair/reinforcing adhesives, general household/industrial adhesives.
- CFRP carbon fiber reinforced plastics
- Production example 4 18.9 g (0.10 mol) of 4-hydroxyphenylmaleimide, 3.22 g (0.01 mol) of tetrabutylammonium bromide, 40% by mass of water were placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. 80 g of an aqueous sodium oxide solution and 80 g of toluene were charged, the temperature was raised to 60° C. while introducing nitrogen gas, 46.3 g (0.50 mol) of epichlorohydrin was added dropwise, and the mixture was stirred for 2 hours.
- Production example 6 50.0 g (0.24 mol) of 9-(hydroxymethyl)anthracene, 7.74 g (0.024 mol) of tetrabutylammonium bromide, 40 masses were placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. % sodium hydroxide aqueous solution and 200 g of toluene were charged, the temperature was raised to 60° C. while introducing nitrogen gas, 111.1 g (1.2 mol) of epichlorohydrin was added dropwise, and the mixture was stirred for 2 hours.
- epoxy resin composition 2-1 100 parts by mass of epoxy resin (A) (jER-828, manufactured by Mitsubishi Chemical) and 10 parts by mass of compound (B1) were placed in a container and left in an environment of 80° C. for 1 hour. Then, using a glass rod, jER-828 and compound (B1) were mixed and allowed to stand until the temperature of the mixture reached 25°C. After that, a mixture of jER-828 and compound (B1) and 52 parts by mass of curing agent (C) (ST-12: manufactured by DIC) were mixed in a mixer (ARE-310: manufactured by Thinky) for 2 minutes to form an epoxy resin composition. got stuff
- Example 2-9 Comparative Examples 1-3, Reference Examples 1-3 Epoxy resin compositions of Examples 2 to 9, Comparative Examples 1 to 3, and Reference Examples 1 to 3 were obtained in the same manner as in Example 1, except that the composition was changed to those shown in Tables 1 and 2.
- the curing agent (C) was heated at 80° C. for 30 minutes before being charged into the mixer.
- jER-828 bisphenol A type epoxy resin
- Mitsubishi Chemical EPICLON830 bisphenol F type epoxy resin
- DIC ST12 aliphatic polyamine curing agent (jER Cure ST12)
- Mitsubishi Chemical TD-2131 cresol novolac type curing agent ( PHENOLITETD-2131); PPh 3 manufactured by DIC: triphenylphosphine
- the examples had higher glass transition temperatures than the comparative examples, and had values close to those of the reference examples that did not contain the compound (B).
- the tensile elastic modulus, the maximum tensile stress, the shear adhesive strength and the storage elastic modulus were also equivalent to those of the reference example.
- the examples were superior to the reference examples in the results of the thermal cycle test. From the above, it was found that according to the examples of the present invention, cracks and peeling due to thermal stress can be suppressed while suppressing the deterioration of the mechanical properties and thermophysical properties inherent in the epoxy resin.
- the details of the evaluation are as follows. [Glass transition temperature/dissociation start temperature]
- the epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours to prepare a dumbbell test piece.
- the test piece is sealed in a simple sealed pan, and a differential scanning calorimeter (DSC) is used to measure the heat change by raising the temperature from 30 ° C. to 200 ° C. at a rate of 10 ° C./min under a nitrogen stream.
- a graph was drawn between calorific value and temperature, and the characteristic inflection observed at this time was taken as the glass transition.
- the glass transition temperature the value obtained by the midpoint method from the DSC curve was used.
- the dissociation start temperature the value of the extrapolated start temperature of the endothermic peak appearing at a temperature higher than the glass transition temperature was used.
- the epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours to prepare a dumbbell test piece.
- the tensile modulus and maximum tensile stress of the obtained test piece were measured according to JIS-K7161 under the following conditions. ⁇ Sample size: Dumbbell size 1BA ⁇ Test speed: 1.0 mm/min ⁇ Measurement environment: Temperature 25°C ⁇ Number of measurements: Measured 3 times and calculated from the average value
- the obtained test piece is left in an environment of 25°C for 24 hours, and a thermal shock device TSA-71L-A (manufactured by Espec) is used to perform a thermal cycle of -40°C x 30 minutes and 200°C x 30 minutes as one cycle. was repeated 150 times, and the presence or absence of peeling of the test piece was visually confirmed. The test was performed three times for the same curable composition, and the numbers in the table indicate the number of times peeling occurred.
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Abstract
Provided is an epoxy resin composition capable of suppressing cracks and peeling due to thermal stress while suppressing deterioration of the mechanical and thermal properties inherent to epoxy resins. According to the present invention, an epoxy resin composition including 100 mass parts of an epoxy resin (A), 5-90 mass parts of a compound (B) represented by formula (1), and 10-90 mass parts of a curing agent (C) is provided.
Description
本発明は、エポキシ樹脂組成物及びエポキシ樹脂硬化物に関する。
The present invention relates to epoxy resin compositions and epoxy resin cured products.
エポキシ樹脂は成形性、電気特性、耐湿性、耐熱性、機械特性等に優れていることから、従来から、成形材料、接着剤用材料、電子部品、インキ材料等の分野において用いられている。また、半導体デバイス等の電子部品素子の封止材料としてもエポキシ樹脂が用いられている。
Epoxy resin has excellent moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, etc., and has been used in fields such as molding materials, adhesive materials, electronic parts, and ink materials. Epoxy resins are also used as sealing materials for electronic components such as semiconductor devices.
例えば、封止材として用いられるエポキシ樹脂硬化物には、熱膨張や熱収縮等の応力による、クラック・剥がれを生じさせないことが求められる。熱応力によるクラック・剥がれを抑制するために、エポキシ樹脂に各種添加剤を配合することが検討されている（例えば特許文献１）。
For example, cured epoxy resins used as sealing materials are required not to crack or peel off due to stress such as thermal expansion or thermal contraction. In order to suppress cracking and peeling due to thermal stress, it has been studied to add various additives to the epoxy resin (for example, Patent Document 1).
しかし、添加剤の配合によりエポキシ樹脂本来の力学物性や熱物性が損なわれる問題があった。
However, there was a problem that the mechanical properties and thermophysical properties inherent in the epoxy resin were impaired due to the addition of additives.
本発明はこのような事情に鑑みてなされたものであり、エポキシ樹脂が本来有する力学物性や熱物性の悪化を抑制しつつ、熱応力によるクラック・剥がれを抑制することのできる、エポキシ樹脂組成物を提供するものである。
The present invention has been made in view of such circumstances, and provides an epoxy resin composition capable of suppressing cracks and peeling due to thermal stress while suppressing the deterioration of the inherent mechanical and thermal properties of epoxy resins. It provides
本発明によれば、エポキシ樹脂（Ａ）１００質量部と、下記式（１）で示される化合物（Ｂ）を５～９０質量部と、硬化剤（Ｃ）１０～９０質量部と、を含むエポキシ樹脂組成物が提供される。
According to the present invention, 100 parts by mass of an epoxy resin (A), 5 to 90 parts by mass of a compound (B) represented by the following formula (1), and 10 to 90 parts by mass of a curing agent (C) are included. An epoxy resin composition is provided.
本発明者が鋭意検討を行ったところ、上記組成物を用いることによって、上記課題が解決可能であることを見出し、本発明の完成に到った。
As a result of diligent studies, the inventors found that the above problems can be solved by using the above composition, and have completed the present invention.
以下、本発明の実施形態について、詳細に説明する。
Hereinafter, embodiments of the present invention will be described in detail.
１．エポキシ樹脂組成物の組成
本発明の一実施形態のエポキシ樹脂組成物は、エポキシ樹脂（Ａ）と、化合物（Ｂ）と、硬化剤（Ｃ）を含有する。 1. Composition of Epoxy Resin Composition The epoxy resin composition of one embodiment of the present invention contains an epoxy resin (A), a compound (B), and a curing agent (C).
本発明の一実施形態のエポキシ樹脂組成物は、エポキシ樹脂（Ａ）と、化合物（Ｂ）と、硬化剤（Ｃ）を含有する。 1. Composition of Epoxy Resin Composition The epoxy resin composition of one embodiment of the present invention contains an epoxy resin (A), a compound (B), and a curing agent (C).
１－１．エポキシ樹脂（Ａ）
エポキシ樹脂（Ａ）は、複数のエポキシ基（好ましくは複数のグリシジル基）を有する、化合物（Ｂ）以外の化合物を意味する。エポキシ樹脂（Ａ）の１分子中のエポキシ基の数は、例えば、２、３、４であり、２又は３が好ましく、２がさらに好ましい。エポキシ樹脂（Ａ）のエポキシ当量は、例えば１２０～４００（ｇ／ｅｑ）であり、具体的には例えば、１２０、１４０、１６０、１８０、２００、２２０、２４０、２６０、２８０、３００（ｇ／ｅｑ）であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。エポキシ当量は、ＪＩＳ Ｋ ７２３６：２００９に従って測定することができる。 1-1. Epoxy resin (A)
Epoxy resin (A) means a compound other than compound (B) having multiple epoxy groups (preferably multiple glycidyl groups). The number of epoxy groups in one molecule of the epoxy resin (A) is, for example, 2, 3 or 4, preferably 2 or 3, more preferably 2. The epoxy equivalent of the epoxy resin (A) is, for example, 120 to 400 (g/eq). eq) and may be in a range between any two of the values exemplified herein. Epoxy equivalent can be measured according to JIS K 7236:2009.
エポキシ樹脂（Ａ）は、複数のエポキシ基（好ましくは複数のグリシジル基）を有する、化合物（Ｂ）以外の化合物を意味する。エポキシ樹脂（Ａ）の１分子中のエポキシ基の数は、例えば、２、３、４であり、２又は３が好ましく、２がさらに好ましい。エポキシ樹脂（Ａ）のエポキシ当量は、例えば１２０～４００（ｇ／ｅｑ）であり、具体的には例えば、１２０、１４０、１６０、１８０、２００、２２０、２４０、２６０、２８０、３００（ｇ／ｅｑ）であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。エポキシ当量は、ＪＩＳ Ｋ ７２３６：２００９に従って測定することができる。 1-1. Epoxy resin (A)
Epoxy resin (A) means a compound other than compound (B) having multiple epoxy groups (preferably multiple glycidyl groups). The number of epoxy groups in one molecule of the epoxy resin (A) is, for example, 2, 3 or 4, preferably 2 or 3, more preferably 2. The epoxy equivalent of the epoxy resin (A) is, for example, 120 to 400 (g/eq). eq) and may be in a range between any two of the values exemplified herein. Epoxy equivalent can be measured according to JIS K 7236:2009.
エポキシ樹脂（Ａ）は、２５℃で液状であることが取り扱い性の観点で好ましい。エポキシ樹脂（Ａ）の重量平均分子量（Ｍｗ）は、例えば、２４０～６００であり、具体的には例えば、２４０、２８０、３２０、３６０、４００、４４０、４８０、５２０、５６０、６００であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。Ｍｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定することができる。
The epoxy resin (A) is preferably liquid at 25°C from the viewpoint of handling. The weight average molecular weight (Mw) of the epoxy resin (A) is, for example, 240 to 600, specifically, for example, 240, 280, 320, 360, 400, 440, 480, 520, 560, 600, It may be in a range between any two of the numerical values exemplified here. Mw can be measured by a gel permeation chromatography (GPC) method.
エポキシ樹脂（Ａ）は、アミノ基、カルボキシ基、フェノール性水酸基、及びチオール基から選択される反応性官能基を有さず、且つカルボン酸無水物でないことが好ましい。このような反応性官能基は、エポキシ基との反応性が高いので、化合物（Ｂ）に含まれるエポキシ基と反応して、エポキシ樹脂（Ａ）と化合物（Ｂ）の間に結合を形成してしまい、エポキシ樹脂が本来有する力学物性や熱物性を悪化させやすいからである。
The epoxy resin (A) preferably does not have a reactive functional group selected from an amino group, a carboxyl group, a phenolic hydroxyl group, and a thiol group, and is not a carboxylic acid anhydride. Since such a reactive functional group has high reactivity with the epoxy group, it reacts with the epoxy group contained in the compound (B) to form a bond between the epoxy resin (A) and the compound (B). This is because the mechanical properties and thermophysical properties inherent in the epoxy resin tend to deteriorate.
本実施形態のエポキシ樹脂組成物では、エポキシ樹脂（Ａ）と化合物（Ｂ）は、硬化剤（Ｃ）を介して結合することが想定されており、エポキシ樹脂（Ａ）と化合物（Ｂ）が直接反応しないことが好ましい。例えば、硬化剤（Ｃ）がない状態でエポキシ樹脂（Ａ）と化合物（Ｂ）を共存させた状態で１２０℃３時間加熱したときにエポキシ樹脂（Ａ）と化合物（Ｂ）が硬化しないことが好ましい。
In the epoxy resin composition of the present embodiment, it is assumed that the epoxy resin (A) and the compound (B) are bonded via the curing agent (C), and the epoxy resin (A) and the compound (B) are It is preferred not to react directly. For example, when the epoxy resin (A) and the compound (B) coexist in the absence of the curing agent (C) and heated at 120° C. for 3 hours, the epoxy resin (A) and the compound (B) may not cure. preferable.
エポキシ樹脂（Ａ）は、共役ジエン構造とジエノフィル構造からディールスアルダー反応によって形成される付加反応部（以下、「ＤＡ反応付加部」）を備えないことが好ましい。このような付加反応部は、エポキシ樹脂が本来有する力学物性や熱物性を悪化させやすいからである。
The epoxy resin (A) preferably does not have an addition reaction site (hereinafter referred to as "DA reaction addition site") formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure. This is because such an addition reaction portion tends to deteriorate the mechanical properties and thermophysical properties inherent in the epoxy resin.
エポキシ樹脂（Ａ）としては、たとえば、ビフェニル型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、スチルベン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂等の２官能性または結晶性エポキシ樹脂；クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；フェニレン骨格含有フェノールアラルキル型エポキシ樹脂、ビフェニレン骨格含有フェノールアラルキル型エポキシ樹脂、フェニレン骨格含有ナフトールアラルキル型エポキシ樹脂等のフェノールアラルキル型エポキシ樹脂；トリフェノールメタン型エポキシ樹脂およびアルキル変性トリフェノールメタン型エポキシ樹脂等の３官能型エポキシ樹脂が好ましく、このうち、ビフェニル型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニレン骨格含有フェノールアラルキル型エポキシ樹脂が特に好ましい。
Examples of the epoxy resin (A) include bifunctional or crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin; Novolac epoxy resins such as epoxy resins, phenol novolak epoxy resins, and naphthol novolak epoxy resins; Aralkyl-type epoxy resins; trifunctional epoxy resins such as triphenolmethane-type epoxy resins and alkyl-modified triphenolmethane-type epoxy resins are preferred. Particularly preferred are cresol novolac type epoxy resins and biphenylene skeleton-containing phenol aralkyl type epoxy resins.
エポキシ樹脂（Ａ）の市販品の例は、以下の通りである。
・ビフェニル型エポキシ樹脂：ＹＸ４０００（三菱ケミカル）
・ビスフェノールＡ型エポキシ樹脂：ｊＥＲ－８２８（三菱ケミカル）
・ビスフェノールＦ型エポキシ樹脂：ＥＰＩＣＬＯＮ ８３０（ＤＩＣ）
・クレゾールノボラック型エポキシ樹脂：ＥＰＩＣＬＯＮ Ｎ－６８０（ＤＩＣ）
・ビフェニレン骨格含有フェノールアラルキル型エポキシ樹脂：ＮＣ３０００（日本化薬） Examples of commercially available epoxy resins (A) are as follows.
・Biphenyl type epoxy resin: YX4000 (Mitsubishi Chemical)
・Bisphenol A type epoxy resin: jER-828 (Mitsubishi Chemical)
・Bisphenol F type epoxy resin: EPICLON 830 (DIC)
・Cresol novolac type epoxy resin: EPICLON N-680 (DIC)
・ Biphenylene skeleton-containing phenol aralkyl type epoxy resin: NC3000 (Nippon Kayaku)
・ビフェニル型エポキシ樹脂：ＹＸ４０００（三菱ケミカル）
・ビスフェノールＡ型エポキシ樹脂：ｊＥＲ－８２８（三菱ケミカル）
・ビスフェノールＦ型エポキシ樹脂：ＥＰＩＣＬＯＮ ８３０（ＤＩＣ）
・クレゾールノボラック型エポキシ樹脂：ＥＰＩＣＬＯＮ Ｎ－６８０（ＤＩＣ）
・ビフェニレン骨格含有フェノールアラルキル型エポキシ樹脂：ＮＣ３０００（日本化薬） Examples of commercially available epoxy resins (A) are as follows.
・Biphenyl type epoxy resin: YX4000 (Mitsubishi Chemical)
・Bisphenol A type epoxy resin: jER-828 (Mitsubishi Chemical)
・Bisphenol F type epoxy resin: EPICLON 830 (DIC)
・Cresol novolac type epoxy resin: EPICLON N-680 (DIC)
・ Biphenylene skeleton-containing phenol aralkyl type epoxy resin: NC3000 (Nippon Kayaku)
１－２．化合物（Ｂ）
化合物（Ｂ）は、下記式（１）で示される化合物である。化合物（Ｂ）は、ＤＡ反応付加部を備える。ＤＡ付加反応部は、エポキシ樹脂硬化物が高温にさらされたときに解離することによって、エポキシ樹脂硬化物の応力が緩和されて、エポキシ樹脂硬化物にクラックや剥がれが発生することが抑制される。 1-2. Compound (B)
Compound (B) is a compound represented by the following formula (1). Compound (B) comprises a DA reaction adduct. The DA addition reaction part dissociates when the cured epoxy resin is exposed to high temperatures, thereby relieving the stress of the cured epoxy resin and suppressing the occurrence of cracks and peeling in the cured epoxy resin. .
化合物（Ｂ）は、下記式（１）で示される化合物である。化合物（Ｂ）は、ＤＡ反応付加部を備える。ＤＡ付加反応部は、エポキシ樹脂硬化物が高温にさらされたときに解離することによって、エポキシ樹脂硬化物の応力が緩和されて、エポキシ樹脂硬化物にクラックや剥がれが発生することが抑制される。 1-2. Compound (B)
Compound (B) is a compound represented by the following formula (1). Compound (B) comprises a DA reaction adduct. The DA addition reaction part dissociates when the cured epoxy resin is exposed to high temperatures, thereby relieving the stress of the cured epoxy resin and suppressing the occurrence of cracks and peeling in the cured epoxy resin. .
エポキシ樹脂（Ａ）１００質量部に対する化合物（Ｂ）の含有量は、５～９０質量部であり、５～８０質量部が好ましく、５～６０質量部がさらに好ましい。化合物（Ｂ）の含有量が少なすぎると応力緩和の効果が十分に発揮されない。化合物（Ｂ）の含有量が多すぎると、力学物性や熱物性の悪化が顕著になりやすい。この含有量は、具体的には例えば、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The content of the compound (B) with respect to 100 parts by mass of the epoxy resin (A) is 5 to 90 parts by mass, preferably 5 to 80 parts by mass, more preferably 5 to 60 parts by mass. If the content of the compound (B) is too small, the stress relaxation effect will not be sufficiently exhibited. If the content of the compound (B) is too large, the mechanical properties and thermophysical properties tend to deteriorate significantly. Specifically, this content is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 parts by mass. , within a range between any two of the numerical values exemplified herein.
Ｘは、－Ｏ－、－Ｓ－、－ＮＲ２－、又は－ＣＯＯ－で表される基であり、Ｒ２は、－ＣＨ３、－Ｃ２Ｈ５、又は－（ＣＨ２）ａ－ＣＨ（Ｏ）ＣＨ２で表される基あり、
Ａｒ１は、未置換のフェニル基、又は１～４（例：１，２，３，４）個のメチル基又はエチル基で置換されたフェニル基であり、
ａは、０～５（例：０，１，２，３，４，５）の整数、ｂは、１～５（例：１，２，３，４，５）の整数であり、
Ｙは、直接結合又は式（２）で表される基であり、式（２）中の＊３及び＊４は、それぞれ、Ｒ１及びＮとの結合部である。）
ｄは、１～８（例：１，２，３，４，５，６，７，８）の整数、ｅは、１～３（例：１，２，３）の整数であり、
Ａｒ２及びＡｒ３は、それぞれ、未置換のフェニル基、１～４（例：１，２，３，４）個のメチル基又はエチル基で置換されたフェニル基、未置換のビフェニル基、又は１～８（例：１，２，３，４，５，６，７，８）個のメチル基又はエチル基で置換されたビフェニル基であり、
Ｒ４は、－（ＣＨ２）ｆ－、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、又は－［（ＣＨ２）ｆ－Ｏ］ｇ－（ＣＨ２）ｆ－で表される基であり、
ｆは、１～８（例：１，２，３，４，５，６，７，８）の整数、ｇは、１～３（例：１，２，３）の整数である。）
X is a group represented by -O-, -S-, -NR 2 - or -COO-, and R 2 is -CH 3 , -C 2 H 5 or -(CH 2 ) a - a group represented by CH(O) CH2 ,
Ar 1 is an unsubstituted phenyl group or a phenyl group substituted with 1 to 4 (eg, 1,2,3,4) methyl or ethyl groups;
a is an integer of 0 to 5 (eg, 0, 1, 2, 3, 4, 5), b is an integer of 1 to 5 (eg, 1, 2, 3, 4, 5),
Y is a direct bond or a group represented by formula (2), and * 3 and * 4 in formula (2) are bonding sites with R1 and N, respectively. )
d is an integer of 1 to 8 (eg, 1,2,3,4,5,6,7,8), e is an integer of 1 to 3 (eg, 1,2,3),
Ar 2 and Ar 3 are each an unsubstituted phenyl group, a phenyl group substituted with 1 to 4 (eg, 1,2,3,4) methyl or ethyl groups, an unsubstituted biphenyl group, or a biphenyl group substituted with 1 to 8 (e.g., 1,2,3,4,5,6,7,8) methyl or ethyl groups,
R 4 is -(CH 2 ) f -, -O-, -S-, -SO-, -SO 2 -, -CO-, or -[(CH 2 ) f -O] g -(CH 2 ) a group represented by f- ,
f is an integer of 1 to 8 (eg 1,2,3,4,5,6,7,8) and g is an integer of 1 to 3 (eg 1,2,3). )
式（１）中のＹは、式（２）で表される基であることが好ましい。この場合、化合物（Ｂ）が２つのＤＡ反応付加部を備えるので、応力緩和の効果が顕著である。前記式（２）のＲ３は、－Ａｒ３－Ｒ４－Ａｒ３－であることが好ましい。
Y in formula (1) is preferably a group represented by formula (2). In this case, the compound (B) has two DA reaction addition sites, so that the stress relaxation effect is remarkable. R 3 in formula (2) is preferably -Ar 3 -R 4 -Ar 3 -.
化合物（Ｂ）は、例えば、式（３）で表される共役ジエン化合物と、式（４）又は式（５）で表されるジエノフィル化合物をディールスアルダー反応させることによって得ることができる。
The compound (B) can be obtained, for example, by subjecting a conjugated diene compound represented by formula (3) and a dienophile compound represented by formula (4) or (5) to Diels-Alder reaction.
化合物（Ｂ）は、解離開始温度が８０～１９０℃であることが好ましい。解離開始温度は、化合物（Ｂ）のＤＡ付加反応部の解離が開始される温度であり、後述の「３．エポキシ樹脂組成物の評価」において説明した方法によって測定可能である。解離開始温度が低すぎると力学物性や熱物性が悪化しやすく、解離開始温度が高すぎると、通常の熱サイクルの際の化合物（Ｂ）のＤＡ付加反応部が解離されずに、応力緩和の効果が発揮されにくい。解離開始温度は、具体的には例えば、８０、９０、１００、１１０、１２０、１３０、１４０、１５０、１６０、１７０、１８０、１９０℃であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The compound (B) preferably has a dissociation initiation temperature of 80 to 190°C. The dissociation initiation temperature is the temperature at which dissociation of the DA addition reaction portion of compound (B) is initiated, and can be measured by the method described in "3. Evaluation of epoxy resin composition" below. If the dissociation starting temperature is too low, the mechanical properties and thermophysical properties tend to deteriorate. Hard to be effective. Specifically, the dissociation start temperature is, for example, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190° C. may be within the range.
化合物（Ｂ）は、アミノ基、カルボキシ基、フェノール性水酸基、及びチオール基から選択される反応性官能基を有さず、カルボン酸無水物でもないので、化合物（Ｂ）がエポキシ樹脂（Ａ）のエポキシ基と反応することがない。
Compound (B) does not have a reactive functional group selected from an amino group, a carboxyl group, a phenolic hydroxyl group, and a thiol group, and is not a carboxylic acid anhydride, so that compound (B) is an epoxy resin (A). does not react with the epoxy groups of
１－３．硬化剤（Ｃ）
硬化剤（Ｃ）は、複数のエポキシ基と反応して、エポキシ基を有する化合物同士を連結可能な化合物である。硬化剤（Ｃ）は、アミノ基、カルボキシ基、フェノール性水酸基、及びチオール基から選択される反応性官能基を複数有するか、又はカルボン酸無水物であることが好ましい。硬化剤（Ｃ）によって、エポキシ樹脂（Ａ）同士、化合物（Ｂ）同士、又はエポキシ樹脂（Ａ）と化合物（Ｂ）が互いに連結されて高分子量化することによって、エポキシ樹脂組成物が硬化して、エポキシ樹脂硬化物となる。 1-3. Curing agent (C)
The curing agent (C) is a compound capable of reacting with a plurality of epoxy groups and linking compounds having epoxy groups. The curing agent (C) preferably has a plurality of reactive functional groups selected from amino groups, carboxyl groups, phenolic hydroxyl groups and thiol groups, or is a carboxylic acid anhydride. The epoxy resin composition is cured by the curing agent (C) connecting the epoxy resins (A) to each other, the compounds (B) to each other, or the epoxy resin (A) and the compound (B) to each other to increase the molecular weight. It becomes an epoxy resin hardened product.
硬化剤（Ｃ）は、複数のエポキシ基と反応して、エポキシ基を有する化合物同士を連結可能な化合物である。硬化剤（Ｃ）は、アミノ基、カルボキシ基、フェノール性水酸基、及びチオール基から選択される反応性官能基を複数有するか、又はカルボン酸無水物であることが好ましい。硬化剤（Ｃ）によって、エポキシ樹脂（Ａ）同士、化合物（Ｂ）同士、又はエポキシ樹脂（Ａ）と化合物（Ｂ）が互いに連結されて高分子量化することによって、エポキシ樹脂組成物が硬化して、エポキシ樹脂硬化物となる。 1-3. Curing agent (C)
The curing agent (C) is a compound capable of reacting with a plurality of epoxy groups and linking compounds having epoxy groups. The curing agent (C) preferably has a plurality of reactive functional groups selected from amino groups, carboxyl groups, phenolic hydroxyl groups and thiol groups, or is a carboxylic acid anhydride. The epoxy resin composition is cured by the curing agent (C) connecting the epoxy resins (A) to each other, the compounds (B) to each other, or the epoxy resin (A) and the compound (B) to each other to increase the molecular weight. It becomes an epoxy resin hardened product.
エポキシ樹脂（Ａ）１００質量部に対する硬化剤（Ｃ）の含有量は、１０～９０質量部であり、２０～８５質量部が好ましく、３０～８０質量部がさらに好ましい。硬化剤（Ｃ）が少なすぎても多すぎても、エポキシ樹脂硬化物の力学物性や熱物性が悪くなりやすい。この含有量は、具体的には例えば、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The content of the curing agent (C) with respect to 100 parts by mass of the epoxy resin (A) is 10 to 90 parts by mass, preferably 20 to 85 parts by mass, more preferably 30 to 80 parts by mass. If the curing agent (C) is too little or too much, the mechanical properties and thermophysical properties of the epoxy resin cured product tend to deteriorate. This content is specifically, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 parts by mass, here may be within a range between any two of the numerical values exemplified in .
特に、化合物（Ｂ）を配合した場合であってもエポキシ樹脂（Ａ）が有する諸物性を大きく変化させない観点から、エポキシ樹脂（Ａ）および化合物（Ｂ）のエポキシ当量の合計値と、硬化剤（Ｃ）の官能基当量とで近い値となるように硬化剤（Ｃ）が組成物中に含有されることが好ましい。｛硬化剤（Ｃ）の官能基当量｝／｛エポキシ樹脂（Ａ）および化合物（Ｂ）のエポキシ当量の合計値｝の値は、例えば、０．８～１．２であり、具体的には例えば、０．８、０．９、１．０、１．１、１．２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
In particular, from the viewpoint of not significantly changing the physical properties of the epoxy resin (A) even when the compound (B) is blended, the total epoxy equivalent weight of the epoxy resin (A) and the compound (B) and the curing agent It is preferable that the curing agent (C) is contained in the composition so that the functional group equivalent weight of (C) is close to that of the curing agent (C). The value of {functional group equivalent of curing agent (C)}/{total value of epoxy equivalents of epoxy resin (A) and compound (B)} is, for example, 0.8 to 1.2, specifically For example, 0.8, 0.9, 1.0, 1.1, 1.2, and may be in the range between any two of the numerical values exemplified herein.
エポキシ樹脂（Ａ）と、化合物（Ｂ）と、硬化剤（Ｃ）を上記割合で配合したエポキシ樹脂組成物を硬化させて得られるエポキシ樹脂硬化物は、エポキシ樹脂が本来有する力学物性や熱物性の悪化を抑制しつつ、熱応力によるクラック・剥がれが抑制される。
The epoxy resin cured product obtained by curing the epoxy resin composition in which the epoxy resin (A), the compound (B) and the curing agent (C) are blended in the above ratio has the mechanical and thermophysical properties inherent in the epoxy resin. Cracks and peeling due to thermal stress are suppressed while suppressing the deterioration of
硬化剤（Ｃ）は、アミン系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、多価カルボン酸化合物から選ばれる少なくとも１つであることが好ましい。
The curing agent (C) is preferably at least one selected from amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and polyvalent carboxylic acid compounds.
（アミン系硬化剤）
アミン系硬化剤としては、たとえば、ジエチレントリアミン（ＤＥＴＡ）、トリエチレンテトラミン（ＴＥＴＡ）、メタキシリレンジアミン（ＭＸＤＡ）などの脂肪族ポリアミン；ジアミノジフェニルメタン（ＤＤＭ）、ｍ－フェニレンジアミン（ＭＰＤＡ）、ジアミノジフェニルスルホン（ＤＤＳ）などの芳香族ポリアミン；ジシアンジアミド（ＤＩＣＹ）や有機酸ジヒドララジドなどのポリアミン化合物からなる群から選択される１種または２種以上が挙げられる。アミン系硬化剤としては、脂肪族ポリアミンが特に好ましい。 (Amine-based curing agent)
Examples of amine curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylylenediamine (MXDA); diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), diaminodiphenyl One or more selected from the group consisting of aromatic polyamines such as sulfone (DDS); and polyamine compounds such as dicyandiamide (DICY) and organic acid dihydralazide. Aliphatic polyamines are particularly preferred as amine-based curing agents.
アミン系硬化剤としては、たとえば、ジエチレントリアミン（ＤＥＴＡ）、トリエチレンテトラミン（ＴＥＴＡ）、メタキシリレンジアミン（ＭＸＤＡ）などの脂肪族ポリアミン；ジアミノジフェニルメタン（ＤＤＭ）、ｍ－フェニレンジアミン（ＭＰＤＡ）、ジアミノジフェニルスルホン（ＤＤＳ）などの芳香族ポリアミン；ジシアンジアミド（ＤＩＣＹ）や有機酸ジヒドララジドなどのポリアミン化合物からなる群から選択される１種または２種以上が挙げられる。アミン系硬化剤としては、脂肪族ポリアミンが特に好ましい。 (Amine-based curing agent)
Examples of amine curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylylenediamine (MXDA); diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), diaminodiphenyl One or more selected from the group consisting of aromatic polyamines such as sulfone (DDS); and polyamine compounds such as dicyandiamide (DICY) and organic acid dihydralazide. Aliphatic polyamines are particularly preferred as amine-based curing agents.
アミン系硬化剤の市販品の例は、以下の通りである。
・脂肪族ポリアミン：ｊＥＲキュアＳＴ１２（三菱ケミカル）、アデカハードナーＥＨ－６０１９（ＡＤＥＫＡ） Examples of commercially available amine curing agents are as follows.
・ Aliphatic polyamine: jER Cure ST12 (Mitsubishi Chemical), ADEKA Hardener EH-6019 (ADEKA)
・脂肪族ポリアミン：ｊＥＲキュアＳＴ１２（三菱ケミカル）、アデカハードナーＥＨ－６０１９（ＡＤＥＫＡ） Examples of commercially available amine curing agents are as follows.
・ Aliphatic polyamine: jER Cure ST12 (Mitsubishi Chemical), ADEKA Hardener EH-6019 (ADEKA)
（フェノール系硬化剤）
フェノール系硬化剤としては、たとえば、フェノールノボラック樹脂、クレゾールノボラック樹脂をはじめとするフェノール、クレゾール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ、フェニルフェノール、アミノフェノール、α－ナフトール、β－ナフトール、ジヒドロキシナフタレン等のフェノール類とホルムアルデヒドやケトン類とを酸性触媒下で縮合または共縮合させて得られるノボラック樹脂；上述のフェノール類とジメトキシパラキシレンまたはビス（メトキシメチル）ビフェニルから合成されるフェニレン骨格を有するフェノールアラルキル樹脂；ビフェニレン骨格を有するフェノールアラルキル樹脂などのフェノールアラルキル樹脂；トリスフェニルメタン骨格を有するフェノール樹脂からなる群から選択される１種または２種以上が挙げられる。フェノール系硬化剤は、好ましくはビフェニルアラルキル型フェノール樹脂およびトリフェニルメタン型フェノール樹脂からなる群から選択される１または２以上の樹脂を含む。 (Phenolic curing agent)
Examples of phenolic curing agents include phenolic novolac resins, cresol novolak resins and other phenols, cresols, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, α-naphthol, β-naphthol, and dihydroxynaphthalene. Novolak resins obtained by condensation or co-condensation of phenols such as phenols and formaldehyde or ketones in the presence of an acidic catalyst; One or more selected from the group consisting of aralkyl resins; phenol aralkyl resins such as phenol aralkyl resins having a biphenylene skeleton; and phenol resins having a trisphenylmethane skeleton. The phenolic curing agent preferably contains one or more resins selected from the group consisting of biphenylaralkyl-type phenolic resins and triphenylmethane-type phenolic resins.
フェノール系硬化剤としては、たとえば、フェノールノボラック樹脂、クレゾールノボラック樹脂をはじめとするフェノール、クレゾール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ、フェニルフェノール、アミノフェノール、α－ナフトール、β－ナフトール、ジヒドロキシナフタレン等のフェノール類とホルムアルデヒドやケトン類とを酸性触媒下で縮合または共縮合させて得られるノボラック樹脂；上述のフェノール類とジメトキシパラキシレンまたはビス（メトキシメチル）ビフェニルから合成されるフェニレン骨格を有するフェノールアラルキル樹脂；ビフェニレン骨格を有するフェノールアラルキル樹脂などのフェノールアラルキル樹脂；トリスフェニルメタン骨格を有するフェノール樹脂からなる群から選択される１種または２種以上が挙げられる。フェノール系硬化剤は、好ましくはビフェニルアラルキル型フェノール樹脂およびトリフェニルメタン型フェノール樹脂からなる群から選択される１または２以上の樹脂を含む。 (Phenolic curing agent)
Examples of phenolic curing agents include phenolic novolac resins, cresol novolak resins and other phenols, cresols, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, α-naphthol, β-naphthol, and dihydroxynaphthalene. Novolak resins obtained by condensation or co-condensation of phenols such as phenols and formaldehyde or ketones in the presence of an acidic catalyst; One or more selected from the group consisting of aralkyl resins; phenol aralkyl resins such as phenol aralkyl resins having a biphenylene skeleton; and phenol resins having a trisphenylmethane skeleton. The phenolic curing agent preferably contains one or more resins selected from the group consisting of biphenylaralkyl-type phenolic resins and triphenylmethane-type phenolic resins.
フェノール系硬化剤としては、クレゾールノボラック樹脂や、ビフェニレン骨格を有するフェノールアラルキル樹脂が特に好ましい。
As the phenol-based curing agent, cresol novolak resins and phenol aralkyl resins having a biphenylene skeleton are particularly preferred.
フェノール系硬化剤の市販品の例は、以下の通りである。
・クレゾールノボラック型：ＰＨＥＮＯＬＩＴＥＴＤ－２１３１（ＤＩＣ）
・ビフェニルアラルキル型：ＫＡＹＡＨＡＲＤＧＰＨ－６５（日本化薬） Examples of commercially available phenolic curing agents are as follows.
・Cresol novolak type: PHENOLITETD-2131 (DIC)
・ Biphenyl aralkyl type: KAYAHARDGPH-65 (Nippon Kayaku)
・クレゾールノボラック型：ＰＨＥＮＯＬＩＴＥＴＤ－２１３１（ＤＩＣ）
・ビフェニルアラルキル型：ＫＡＹＡＨＡＲＤＧＰＨ－６５（日本化薬） Examples of commercially available phenolic curing agents are as follows.
・Cresol novolak type: PHENOLITETD-2131 (DIC)
・ Biphenyl aralkyl type: KAYAHARDGPH-65 (Nippon Kayaku)
（酸無水物系硬化剤）
酸無水物系硬化剤としては、たとえば、ヘキサヒドロ無水フタル酸（ＨＨＰＡ）、メチルテトラヒドロ無水フタル酸（ＭＴＨＰＡ）や無水マレイン酸などの脂環族酸無水物；無水トリメリット酸（ＴＭＡ）、無水ピロメリット酸（ＰＭＤＡ）、ベンゾフェノンテトラカルボン酸（ＢＴＤＡ）、無水フタル酸などの芳香族酸無水物からなる群から選択される１種または２種以上が挙げられる。 (Acid anhydride curing agent)
Acid anhydride curing agents include, for example, hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), alicyclic acid anhydrides such as maleic anhydride; trimellitic anhydride (TMA), pyroanhydride One or more selected from the group consisting of aromatic acid anhydrides such as mellitic acid (PMDA), benzophenonetetracarboxylic acid (BTDA), and phthalic anhydride can be used.
酸無水物系硬化剤としては、たとえば、ヘキサヒドロ無水フタル酸（ＨＨＰＡ）、メチルテトラヒドロ無水フタル酸（ＭＴＨＰＡ）や無水マレイン酸などの脂環族酸無水物；無水トリメリット酸（ＴＭＡ）、無水ピロメリット酸（ＰＭＤＡ）、ベンゾフェノンテトラカルボン酸（ＢＴＤＡ）、無水フタル酸などの芳香族酸無水物からなる群から選択される１種または２種以上が挙げられる。 (Acid anhydride curing agent)
Acid anhydride curing agents include, for example, hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), alicyclic acid anhydrides such as maleic anhydride; trimellitic anhydride (TMA), pyroanhydride One or more selected from the group consisting of aromatic acid anhydrides such as mellitic acid (PMDA), benzophenonetetracarboxylic acid (BTDA), and phthalic anhydride can be used.
（多価カルボン酸化合物）
多価カルボン酸化合物としては、例えば、フタル酸、ヒドロキシイソフタル酸、コハク酸、セバシン酸、マレイン酸、ドデセニルコハク酸、クロレンデック酸、ピロメリット酸、トリメリット酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、メチルナジック酸が挙げられる。 (Polyvalent carboxylic acid compound)
Examples of polycarboxylic acid compounds include phthalic acid, hydroxyisophthalic acid, succinic acid, sebacic acid, maleic acid, dodecenylsuccinic acid, chlorendic acid, pyromellitic acid, trimellitic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. , tetrahydrophthalic acid, methyltetrahydrophthalic acid, and methylnadic acid.
多価カルボン酸化合物としては、例えば、フタル酸、ヒドロキシイソフタル酸、コハク酸、セバシン酸、マレイン酸、ドデセニルコハク酸、クロレンデック酸、ピロメリット酸、トリメリット酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、メチルナジック酸が挙げられる。 (Polyvalent carboxylic acid compound)
Examples of polycarboxylic acid compounds include phthalic acid, hydroxyisophthalic acid, succinic acid, sebacic acid, maleic acid, dodecenylsuccinic acid, chlorendic acid, pyromellitic acid, trimellitic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. , tetrahydrophthalic acid, methyltetrahydrophthalic acid, and methylnadic acid.
１－４．硬化触媒
本発明のエポキシ樹脂組成物は、硬化触媒を含有してもよい。硬化触媒を含有することで、エポキシ樹脂組成物が硬化時間を短縮することができる。
エポキシ樹脂（Ａ）１００質量部に対する硬化触媒の含有量は、０．１～５質量部であり、０．３～４．５質量部が好ましく、０．５～４．０質量部がさらに好ましい。この含有量は、具体的には例えば、０．１、０．３、０．５、１．０、１．５、２．０、２．５、３．０、３．５、４．０、４．５、５．０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 1-4. Curing Catalyst The epoxy resin composition of the present invention may contain a curing catalyst. By containing a curing catalyst, the epoxy resin composition can shorten the curing time.
The content of the curing catalyst with respect to 100 parts by mass of the epoxy resin (A) is 0.1 to 5 parts by mass, preferably 0.3 to 4.5 parts by mass, more preferably 0.5 to 4.0 parts by mass. . Specifically, this content is, for example, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 , 4.5, and 5.0 parts by mass, and may be within a range between any two of the numerical values exemplified herein.
本発明のエポキシ樹脂組成物は、硬化触媒を含有してもよい。硬化触媒を含有することで、エポキシ樹脂組成物が硬化時間を短縮することができる。
エポキシ樹脂（Ａ）１００質量部に対する硬化触媒の含有量は、０．１～５質量部であり、０．３～４．５質量部が好ましく、０．５～４．０質量部がさらに好ましい。この含有量は、具体的には例えば、０．１、０．３、０．５、１．０、１．５、２．０、２．５、３．０、３．５、４．０、４．５、５．０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 1-4. Curing Catalyst The epoxy resin composition of the present invention may contain a curing catalyst. By containing a curing catalyst, the epoxy resin composition can shorten the curing time.
The content of the curing catalyst with respect to 100 parts by mass of the epoxy resin (A) is 0.1 to 5 parts by mass, preferably 0.3 to 4.5 parts by mass, more preferably 0.5 to 4.0 parts by mass. . Specifically, this content is, for example, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 , 4.5, and 5.0 parts by mass, and may be within a range between any two of the numerical values exemplified herein.
硬化触媒としては、例えば、１，８－ジアザビシクロ［５．４．０］ウンデセン－７（ＤＢＵ）またはその塩；１，５－ジアザビシクロ［４．３．０］ノネン－５（ＤＢＮ）またはその塩；ベンジルジメチルアミン、２，４，６－トリス（ジメチルアミノメチル）フェノール、Ｎ，Ｎ－ジメチルシクロヘキシルアミンなどの３級アミン；トリフェニルホスフィン、トリス（ジメトキシ）ホスフィンなどのホスフィン類が挙げられる。
Curing catalysts include, for example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or salts thereof; 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or salts thereof tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol and N,N-dimethylcyclohexylamine; and phosphines such as triphenylphosphine and tris(dimethoxy)phosphine.
１－５．添加剤
本発明のエポキシ樹脂組成物は、必要に応じて、紫外線吸収剤、酸化防止剤、防腐剤、防錆剤、顔料、粘着付与剤、表面潤滑剤、光沢剤、撥水剤、感光剤、有機・無機繊維、可塑剤、導電性フィラー、無機フィラー、難燃剤、帯電防止剤、整泡剤、離型剤、着色剤および発泡剤から選ばれる少なくとも１種の添加剤を含有してもよい。添加剤は１種単独で用いてもよく、２種以上を用いてもよい。エポキシ樹脂（Ａ）１００質量部に対する添加剤の含有量は、例えば０～５０質量部であり、０～２０質量部がさらに好ましい。この含有量は、具体的には例えば、０、５、１０、１５、２０、２５、３０、３５、４０、４５、５０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 1-5. Additives The epoxy resin composition of the present invention may optionally contain ultraviolet absorbers, antioxidants, antiseptics, rust inhibitors, pigments, tackifiers, surface lubricants, brighteners, water repellents, and photosensitizers. , Organic / inorganic fibers, plasticizers, conductive fillers, inorganic fillers, flame retardants, antistatic agents, foam stabilizers, release agents, colorants and foaming agents. good. An additive may be used individually by 1 type, and may use 2 or more types. The content of the additive with respect to 100 parts by mass of the epoxy resin (A) is, for example, 0 to 50 parts by mass, more preferably 0 to 20 parts by mass. Specifically, this content is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by mass, and ranges between any two of the numerical values illustrated here may be within
本発明のエポキシ樹脂組成物は、必要に応じて、紫外線吸収剤、酸化防止剤、防腐剤、防錆剤、顔料、粘着付与剤、表面潤滑剤、光沢剤、撥水剤、感光剤、有機・無機繊維、可塑剤、導電性フィラー、無機フィラー、難燃剤、帯電防止剤、整泡剤、離型剤、着色剤および発泡剤から選ばれる少なくとも１種の添加剤を含有してもよい。添加剤は１種単独で用いてもよく、２種以上を用いてもよい。エポキシ樹脂（Ａ）１００質量部に対する添加剤の含有量は、例えば０～５０質量部であり、０～２０質量部がさらに好ましい。この含有量は、具体的には例えば、０、５、１０、１５、２０、２５、３０、３５、４０、４５、５０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 1-5. Additives The epoxy resin composition of the present invention may optionally contain ultraviolet absorbers, antioxidants, antiseptics, rust inhibitors, pigments, tackifiers, surface lubricants, brighteners, water repellents, and photosensitizers. , Organic / inorganic fibers, plasticizers, conductive fillers, inorganic fillers, flame retardants, antistatic agents, foam stabilizers, release agents, colorants and foaming agents. good. An additive may be used individually by 1 type, and may use 2 or more types. The content of the additive with respect to 100 parts by mass of the epoxy resin (A) is, for example, 0 to 50 parts by mass, more preferably 0 to 20 parts by mass. Specifically, this content is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by mass, and ranges between any two of the numerical values illustrated here may be within
１－６．溶媒
本発明のエポキシ樹脂組成物は、溶媒を含有してもよい。溶媒としては、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素；ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン等の脂環式炭化水素；ジエチルエーテル、ジイソプロピルエーテル、１，２－ジメトキシエタン、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソール、フェニルエチルエーテル、ジフェニルエーテル等のエーテル；クロロホルム、四塩化炭素、１，２－ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素；酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル等のエステル；アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセタミド、Ｎ－メチルピロリドン等のアミド；アセトニトリル、ベンゾニトリル等のニトリル；ジメチルスルホキシド、スルホラン等のスルホキシドが挙げられる。溶媒は１種単独で用いてもよく、２種以上を用いてもよい。 1-6. Solvent The epoxy resin composition of the present invention may contain a solvent. Examples of solvents include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane and cyclooctane. Ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, 1,2-dichloroethane , halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; N,N-dimethylformamide, N, amides such as N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as dimethylsulfoxide and sulfolane. One type of solvent may be used alone, or two or more types may be used.
本発明のエポキシ樹脂組成物は、溶媒を含有してもよい。溶媒としては、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素；ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン等の脂環式炭化水素；ジエチルエーテル、ジイソプロピルエーテル、１，２－ジメトキシエタン、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソール、フェニルエチルエーテル、ジフェニルエーテル等のエーテル；クロロホルム、四塩化炭素、１，２－ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素；酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル等のエステル；アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセタミド、Ｎ－メチルピロリドン等のアミド；アセトニトリル、ベンゾニトリル等のニトリル；ジメチルスルホキシド、スルホラン等のスルホキシドが挙げられる。溶媒は１種単独で用いてもよく、２種以上を用いてもよい。 1-6. Solvent The epoxy resin composition of the present invention may contain a solvent. Examples of solvents include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane and cyclooctane. Ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, 1,2-dichloroethane , halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; N,N-dimethylformamide, N, amides such as N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as dimethylsulfoxide and sulfolane. One type of solvent may be used alone, or two or more types may be used.
本発明のエポキシ樹脂組成物中の溶媒の含有量は、通常は７０質量％以下、好ましくは３０質量％以下、より好ましくは２０質量％以下である。
The content of the solvent in the epoxy resin composition of the present invention is usually 70% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.
２．エポキシ樹脂組成物の使用方法
本発明のエポキシ樹脂組成物を硬化させることによってエポキシ樹脂硬化物を形成することができる。エポキシ樹脂組成物は、一例では、加熱又は光照射によって硬化させることができる。 2. Method of Using Epoxy Resin Composition A cured epoxy resin product can be formed by curing the epoxy resin composition of the present invention. The epoxy resin composition can be cured by heating or light irradiation, for example.
本発明のエポキシ樹脂組成物を硬化させることによってエポキシ樹脂硬化物を形成することができる。エポキシ樹脂組成物は、一例では、加熱又は光照射によって硬化させることができる。 2. Method of Using Epoxy Resin Composition A cured epoxy resin product can be formed by curing the epoxy resin composition of the present invention. The epoxy resin composition can be cured by heating or light irradiation, for example.
熱硬化の場合、硬化時の加熱温度（硬化温度）は、通常は２０～３００℃、好ましくは４０～２５０℃、より好ましくは６０～２００℃である。硬化温度は、具体的には例えば、２０、４０、６０、８０、１００、１２０、１４０、１６０、１８０、２００、２２０、２４０、２５０、２６０、２８０、３００℃であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。また、硬化時の加熱時間（硬化時間）は、通常は１０～１４４０分、好ましくは３０～９００分、より好ましくは６０～４８０分である。前記加熱は、多段階で行うこともできる。
In the case of thermosetting, the heating temperature (curing temperature) during curing is usually 20 to 300°C, preferably 40 to 250°C, more preferably 60 to 200°C. Specifically, the curing temperature is, for example, 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 250, 260, 280, 300 ° C. Numerical values exemplified here may be in the range between any two of The heating time (curing time) for curing is usually 10 to 1440 minutes, preferably 30 to 900 minutes, more preferably 60 to 480 minutes. The heating can also be performed in multiple stages.
光硬化の場合、紫外線、可視光線、赤外線等の光が挙げられ、紫外線が好ましい。露光量は、好ましくは１～１００００ｍＪ／ｃｍ２、より好ましくは１０～３０００ｍＪ／ｃｍ２である。光源としては、例えば、低圧水銀灯、高圧水銀灯、超高圧水銀灯、カーボンアーク灯、キセノン灯、メタルハライドランプ、ケミカルランプ、ブラックライト蛍光灯、無電極ＵＶランプが挙げられる。
In the case of photocuring, light such as ultraviolet light, visible light, and infrared light can be used, and ultraviolet light is preferred. The exposure dose is preferably 1 to 10000 mJ/cm 2 , more preferably 10 to 3000 mJ/cm 2 . Examples of light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, chemical lamps, black light fluorescent lamps, and electrodeless UV lamps.
前記硬化反応は、本発明のエポキシ樹脂組成物を基板上に塗布して行うこともでき、また型枠内に注入して行うこともできる。
The curing reaction can be carried out by coating the epoxy resin composition of the present invention on a substrate, or by injecting it into a mold.
本発明の硬化物の形状は特に限定されず、例えば、板状、シート状、フィルム状が挙げられる。これらの厚さは、例えば、通常は０．０１～１０００ｍｍ、好ましくは０．１～１００ｍｍであり、さらに好ましくは、０．１～５ｍｍである。
The shape of the cured product of the present invention is not particularly limited, and examples thereof include plate-like, sheet-like and film-like shapes. Their thickness is, for example, usually 0.01 to 1000 mm, preferably 0.1 to 100 mm, more preferably 0.1 to 5 mm.
エポキシ樹脂組成物は、一液型であっても二液型であってもよい。二液型である場合、第１液がエポキシ樹脂（Ａ）と化合物（Ｂ）を含み、第２液が硬化剤（Ｃ）を含むことが好ましい。この場合、保存時には、硬化剤（Ｃ）がエポキシ樹脂（Ａ）又は化合物（Ｂ）と反応することが無いので、貯蔵安定性が向上する。使用時には、第１液と第２液を混合することによって、硬化剤（Ｃ）をエポキシ樹脂（Ａ）及び化合物（Ｂ）と反応させることができる。
The epoxy resin composition may be of a one-component type or a two-component type. In the case of the two-component type, it is preferable that the first component contains the epoxy resin (A) and the compound (B), and the second component contains the curing agent (C). In this case, since the curing agent (C) does not react with the epoxy resin (A) or the compound (B) during storage, the storage stability is improved. At the time of use, the curing agent (C) can be reacted with the epoxy resin (A) and the compound (B) by mixing the first liquid and the second liquid.
本発明のエポキシ樹脂組成物を用いることにより、エポキシ樹脂が本来有する力学物性や熱物性の悪化を抑制しつつ、熱応力によるクラック・剥がれが抑制されたエポキシ樹脂硬化物を形成することができる。
By using the epoxy resin composition of the present invention, it is possible to form an epoxy resin cured product that suppresses cracks and peeling due to thermal stress while suppressing the deterioration of the mechanical and thermal properties inherent in the epoxy resin.
本発明のエポキシ樹脂組成物は、前記特性を有することから、例えば、電子材料、バインダー、塗料、接着剤等の用途に使用することができる。具体的には、半導体パッケージ等の電子部材用のサブストレート基板、ビルドアップフィルム、ソルダーレジストインキ、アンダーフィル材、パッケージ用固形封止材、舗装用バインダー、炭素繊維強化プラスチック（ＣＦＲＰ）用バインダー、カチオン電着塗装剤、重防食塗料、粉体塗料、インフラ補修／補強用接着剤、一般家庭／工業用接着剤が挙げられる。本発明のエポキシ樹脂組成物は、それら用途に好適である。
Because the epoxy resin composition of the present invention has the above properties, it can be used for applications such as electronic materials, binders, paints, and adhesives. Specifically, substrate substrates for electronic members such as semiconductor packages, build-up films, solder resist inks, underfill materials, solid sealing materials for packages, binders for paving, binders for carbon fiber reinforced plastics (CFRP), Cationic electrodeposition coating agents, heavy-duty anti-corrosion coatings, powder coatings, infrastructure repair/reinforcing adhesives, general household/industrial adhesives. The epoxy resin composition of the present invention is suitable for those uses.
１．化合物（Ｂ）の製造
１－１．製造例１
撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に３，３'－ジメチル－５，５'－ジエチル－４，４'－ジフェニルメタンビスマレイミド（ＢＭＩ－５１００：大和化成工業製） ６６．４ｇ（０．１５ｍｏｌ）、フルフリルグリシジルエーテル ９２．５ｇ（０．６０ｍｏｌ）を仕込み、窒素ガスを導入しながら８０℃まで昇温し、その後２時間攪拌した。室温まで冷却後、酢酸エチル：ヘキサン＝３：１の混合溶媒で希釈した後、シリカゲルクロマトグラフィーで精製を行い、式（６）で表される化合物（Ｂ１）を得た。 1. Production of compound (B) 1-1. Production example 1
3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide (BMI-5100: manufactured by Daiwa Kasei Kogyo Co., Ltd.) was placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. ) and 92.5 g (0.60 mol) of furfuryl glycidyl ether were charged, heated to 80° C. while introducing nitrogen gas, and then stirred for 2 hours. After cooling to room temperature, the mixture was diluted with a mixed solvent of ethyl acetate:hexane=3:1, and purified by silica gel chromatography to obtain compound (B1) represented by formula (6).
１－１．製造例１
撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に３，３'－ジメチル－５，５'－ジエチル－４，４'－ジフェニルメタンビスマレイミド（ＢＭＩ－５１００：大和化成工業製） ６６．４ｇ（０．１５ｍｏｌ）、フルフリルグリシジルエーテル ９２．５ｇ（０．６０ｍｏｌ）を仕込み、窒素ガスを導入しながら８０℃まで昇温し、その後２時間攪拌した。室温まで冷却後、酢酸エチル：ヘキサン＝３：１の混合溶媒で希釈した後、シリカゲルクロマトグラフィーで精製を行い、式（６）で表される化合物（Ｂ１）を得た。 1. Production of compound (B) 1-1. Production example 1
3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide (BMI-5100: manufactured by Daiwa Kasei Kogyo Co., Ltd.) was placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. ) and 92.5 g (0.60 mol) of furfuryl glycidyl ether were charged, heated to 80° C. while introducing nitrogen gas, and then stirred for 2 hours. After cooling to room temperature, the mixture was diluted with a mixed solvent of ethyl acetate:hexane=3:1, and purified by silica gel chromatography to obtain compound (B1) represented by formula (6).
１－２．製造例２
３，３'－ジメチル－５，５'－ジエチル－４，４'－ジフェニルメタンビスマレイミド０．１５ｍｏｌの代わりに、ｍ－フェニレンビスマレイミド（ＢＭＩ－３０００：大和化成工業製）４０．２ｇ（０．１５ｍｏｌ）を使用したこと以外は、製造例１と同様の方法で、式（７）で表される化合物（Ｂ２）を得た。 1-2. Production example 2
Instead of 0.15 mol of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 40.2 g of m-phenylenebismaleimide (BMI-3000: manufactured by Daiwa Kasei Kogyo Co., Ltd.) (0.15 mol). A compound (B2) represented by formula (7) was obtained in the same manner as in Production Example 1, except that 15 mol) was used.
３，３'－ジメチル－５，５'－ジエチル－４，４'－ジフェニルメタンビスマレイミド０．１５ｍｏｌの代わりに、ｍ－フェニレンビスマレイミド（ＢＭＩ－３０００：大和化成工業製）４０．２ｇ（０．１５ｍｏｌ）を使用したこと以外は、製造例１と同様の方法で、式（７）で表される化合物（Ｂ２）を得た。 1-2. Production example 2
Instead of 0.15 mol of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 40.2 g of m-phenylenebismaleimide (BMI-3000: manufactured by Daiwa Kasei Kogyo Co., Ltd.) (0.15 mol). A compound (B2) represented by formula (7) was obtained in the same manner as in Production Example 1, except that 15 mol) was used.
１－３．製造例３
３，３'－ジメチル－５，５'－ジエチル－４，４'－ジフェニルメタンビスマレイミド０．１５ｍｏｌの代わりに、１,２－ビス(マレイミド)エタン３３．０ｇ（０．１５ｍｏｌ）を使用したこと以外は、製造例１と同様の方法で、式（８）で表される化合物（Ｂ３）を得た。 1-3. Production example 3
Using 33.0 g (0.15 mol) of 1,2-bis(maleimido)ethane instead of 0.15 mol of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide A compound (B3) represented by the formula (8) was obtained in the same manner as in Production Example 1, except for the above.
３，３'－ジメチル－５，５'－ジエチル－４，４'－ジフェニルメタンビスマレイミド０．１５ｍｏｌの代わりに、１,２－ビス(マレイミド)エタン３３．０ｇ（０．１５ｍｏｌ）を使用したこと以外は、製造例１と同様の方法で、式（８）で表される化合物（Ｂ３）を得た。 1-3. Production example 3
Using 33.0 g (0.15 mol) of 1,2-bis(maleimido)ethane instead of 0.15 mol of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide A compound (B3) represented by the formula (8) was obtained in the same manner as in Production Example 1, except for the above.
１－４．製造例４
撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に４－ヒドロキシフェニルマレイミド１８．９ｇ（０．１０ｍｏｌ）、テトラブチルアンモニウムブロミド３．２２ｇ（０．０１ｍｏｌ）、４０質量％水酸化ナトリウム水溶液８０ｇ、トルエン８０ｇを仕込み、窒素ガスを導入しながら６０℃まで昇温し、エピクロロヒドリン４６．３ｇ（０．５０ｍｏｌ）を滴下後、２時間攪拌した。反応終了後、水層を分離し、有機層をイオン交換水で３回洗浄し、硫酸マグネシウムで乾燥後、濃縮した。ついで撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に濃縮残渣、フルフリルグリシジルエーテル３０．８ｇ（０．２０ｍｏｌ）を仕込み、窒素ガスを導入しながら８０℃まで昇温し、その後２時間攪拌した。室温まで冷却後、酢酸エチル：ヘキサン＝３：１の混合溶媒で希釈した後、シリカゲルクロマトグラフィーで精製を行い、式（９）で表される化合物（Ｂ４）を得た。 1-4. Production example 4
18.9 g (0.10 mol) of 4-hydroxyphenylmaleimide, 3.22 g (0.01 mol) of tetrabutylammonium bromide, 40% by mass of water were placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. 80 g of an aqueous sodium oxide solution and 80 g of toluene were charged, the temperature was raised to 60° C. while introducing nitrogen gas, 46.3 g (0.50 mol) of epichlorohydrin was added dropwise, and the mixture was stirred for 2 hours. After completion of the reaction, the aqueous layer was separated, and the organic layer was washed with ion-exchanged water three times, dried over magnesium sulfate, and concentrated. Then, 30.8 g (0.20 mol) of the concentrated residue and furfuryl glycidyl ether were introduced into a reactor equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, and the temperature was raised to 80° C. while introducing nitrogen gas. and then stirred for 2 hours. After cooling to room temperature, it was diluted with a mixed solvent of ethyl acetate:hexane=3:1, and purified by silica gel chromatography to obtain a compound (B4) represented by the formula (9).
撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に４－ヒドロキシフェニルマレイミド１８．９ｇ（０．１０ｍｏｌ）、テトラブチルアンモニウムブロミド３．２２ｇ（０．０１ｍｏｌ）、４０質量％水酸化ナトリウム水溶液８０ｇ、トルエン８０ｇを仕込み、窒素ガスを導入しながら６０℃まで昇温し、エピクロロヒドリン４６．３ｇ（０．５０ｍｏｌ）を滴下後、２時間攪拌した。反応終了後、水層を分離し、有機層をイオン交換水で３回洗浄し、硫酸マグネシウムで乾燥後、濃縮した。ついで撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に濃縮残渣、フルフリルグリシジルエーテル３０．８ｇ（０．２０ｍｏｌ）を仕込み、窒素ガスを導入しながら８０℃まで昇温し、その後２時間攪拌した。室温まで冷却後、酢酸エチル：ヘキサン＝３：１の混合溶媒で希釈した後、シリカゲルクロマトグラフィーで精製を行い、式（９）で表される化合物（Ｂ４）を得た。 1-4. Production example 4
18.9 g (0.10 mol) of 4-hydroxyphenylmaleimide, 3.22 g (0.01 mol) of tetrabutylammonium bromide, 40% by mass of water were placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. 80 g of an aqueous sodium oxide solution and 80 g of toluene were charged, the temperature was raised to 60° C. while introducing nitrogen gas, 46.3 g (0.50 mol) of epichlorohydrin was added dropwise, and the mixture was stirred for 2 hours. After completion of the reaction, the aqueous layer was separated, and the organic layer was washed with ion-exchanged water three times, dried over magnesium sulfate, and concentrated. Then, 30.8 g (0.20 mol) of the concentrated residue and furfuryl glycidyl ether were introduced into a reactor equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, and the temperature was raised to 80° C. while introducing nitrogen gas. and then stirred for 2 hours. After cooling to room temperature, it was diluted with a mixed solvent of ethyl acetate:hexane=3:1, and purified by silica gel chromatography to obtain a compound (B4) represented by the formula (9).
１－５．製造例５
フルフリルグリシジルエーテル０．６０ｍｏｌの代わりにフルフリルアルコール５８．９ｇ（０．６０ｍｏｌ）を使用したこと以外は、製造例１と同様の方法で、式（１０）で表される比較化合物１を得た。 1-5. Production example 5
Comparative compound 1 represented by formula (10) was obtained in the same manner as in Production Example 1, except that 58.9 g (0.60 mol) of furfuryl alcohol was used instead of 0.60 mol of furfuryl glycidyl ether. rice field.
フルフリルグリシジルエーテル０．６０ｍｏｌの代わりにフルフリルアルコール５８．９ｇ（０．６０ｍｏｌ）を使用したこと以外は、製造例１と同様の方法で、式（１０）で表される比較化合物１を得た。 1-5. Production example 5
Comparative compound 1 represented by formula (10) was obtained in the same manner as in Production Example 1, except that 58.9 g (0.60 mol) of furfuryl alcohol was used instead of 0.60 mol of furfuryl glycidyl ether. rice field.
１－６．製造例６
撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に９－（ヒドロキシメチル）アントラセン５０．０ｇ（０．２４ｍｏｌ）、テトラブチルアンモニウムブロミド７．７４ｇ（０．０２４ｍｏｌ）、４０質量％水酸化ナトリウム水溶液２００ｇ、トルエン２００ｇを仕込み、窒素ガスを導入しながら６０℃まで昇温し、エピクロロヒドリン１１１．１ｇ（１．２ｍｏｌ）を滴下後、２時間攪拌した。反応終了後、水層を分離し、有機層をイオン交換水で３回洗浄し、硫酸マグネシウムで乾燥後、濃縮した。ついで撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に濃縮残渣、３，３'－ジメチル－５，５'－ジエチル－４，４'－ジフェニルメタンビスマレイミド（ＢＭＩ－５１００：大和化成工業製）２６．６ｇ（０．０６ｍｏｌ）を仕込み、窒素ガスを導入しながら１８０℃まで昇温し、その後２時間攪拌した。室温まで冷却後、酢酸エチルで希釈した後、シリカゲルクロマトグラフィーで精製を行い、式（１１）で表される比較化合物２を得た。 1-6. Production example 6
50.0 g (0.24 mol) of 9-(hydroxymethyl)anthracene, 7.74 g (0.024 mol) of tetrabutylammonium bromide, 40 masses were placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. % sodium hydroxide aqueous solution and 200 g of toluene were charged, the temperature was raised to 60° C. while introducing nitrogen gas, 111.1 g (1.2 mol) of epichlorohydrin was added dropwise, and the mixture was stirred for 2 hours. After completion of the reaction, the aqueous layer was separated, and the organic layer was washed with ion-exchanged water three times, dried over magnesium sulfate, and concentrated. The concentrated residue, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide (BMI-5100: 26.6 g (0.06 mol) of Daiwa Kasei Kogyo Co., Ltd.) was added, and the temperature was raised to 180° C. while introducing nitrogen gas, followed by stirring for 2 hours. After cooling to room temperature, the mixture was diluted with ethyl acetate and purified by silica gel chromatography to obtain comparative compound 2 represented by formula (11).
撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に９－（ヒドロキシメチル）アントラセン５０．０ｇ（０．２４ｍｏｌ）、テトラブチルアンモニウムブロミド７．７４ｇ（０．０２４ｍｏｌ）、４０質量％水酸化ナトリウム水溶液２００ｇ、トルエン２００ｇを仕込み、窒素ガスを導入しながら６０℃まで昇温し、エピクロロヒドリン１１１．１ｇ（１．２ｍｏｌ）を滴下後、２時間攪拌した。反応終了後、水層を分離し、有機層をイオン交換水で３回洗浄し、硫酸マグネシウムで乾燥後、濃縮した。ついで撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に濃縮残渣、３，３'－ジメチル－５，５'－ジエチル－４，４'－ジフェニルメタンビスマレイミド（ＢＭＩ－５１００：大和化成工業製）２６．６ｇ（０．０６ｍｏｌ）を仕込み、窒素ガスを導入しながら１８０℃まで昇温し、その後２時間攪拌した。室温まで冷却後、酢酸エチルで希釈した後、シリカゲルクロマトグラフィーで精製を行い、式（１１）で表される比較化合物２を得た。 1-6. Production example 6
50.0 g (0.24 mol) of 9-(hydroxymethyl)anthracene, 7.74 g (0.024 mol) of tetrabutylammonium bromide, 40 masses were placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. % sodium hydroxide aqueous solution and 200 g of toluene were charged, the temperature was raised to 60° C. while introducing nitrogen gas, 111.1 g (1.2 mol) of epichlorohydrin was added dropwise, and the mixture was stirred for 2 hours. After completion of the reaction, the aqueous layer was separated, and the organic layer was washed with ion-exchanged water three times, dried over magnesium sulfate, and concentrated. The concentrated residue, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide (BMI-5100: 26.6 g (0.06 mol) of Daiwa Kasei Kogyo Co., Ltd.) was added, and the temperature was raised to 180° C. while introducing nitrogen gas, followed by stirring for 2 hours. After cooling to room temperature, the mixture was diluted with ethyl acetate and purified by silica gel chromatography to obtain comparative compound 2 represented by formula (11).
２．エポキシ樹脂組成物の製造
２－１．実施例１
エポキシ樹脂（Ａ）（ｊＥＲ－８２８：三菱ケミカル製）１００質量部、化合物（Ｂ１）１０質量部を容器に入れ、８０℃環境下で１時間放置した。その後、ガラス棒を用い、ｊＥＲ－８２８と化合物（Ｂ１）を混合し、混合物の温度が２５℃になるまで放置した。その後、ｊＥＲ－８２８と化合物（Ｂ１）の混合物と、硬化剤（Ｃ）（ＳＴ－１２：ＤＩＣ製）５２質量部とをミキサー（ＡＲＥ－３１０：シンキー製）で２分間混合し、エポキシ樹脂組成物を得た。 2. Production of epoxy resin composition 2-1. Example 1
100 parts by mass of epoxy resin (A) (jER-828, manufactured by Mitsubishi Chemical) and 10 parts by mass of compound (B1) were placed in a container and left in an environment of 80° C. for 1 hour. Then, using a glass rod, jER-828 and compound (B1) were mixed and allowed to stand until the temperature of the mixture reached 25°C. After that, a mixture of jER-828 and compound (B1) and 52 parts by mass of curing agent (C) (ST-12: manufactured by DIC) were mixed in a mixer (ARE-310: manufactured by Thinky) for 2 minutes to form an epoxy resin composition. got stuff
２－１．実施例１
エポキシ樹脂（Ａ）（ｊＥＲ－８２８：三菱ケミカル製）１００質量部、化合物（Ｂ１）１０質量部を容器に入れ、８０℃環境下で１時間放置した。その後、ガラス棒を用い、ｊＥＲ－８２８と化合物（Ｂ１）を混合し、混合物の温度が２５℃になるまで放置した。その後、ｊＥＲ－８２８と化合物（Ｂ１）の混合物と、硬化剤（Ｃ）（ＳＴ－１２：ＤＩＣ製）５２質量部とをミキサー（ＡＲＥ－３１０：シンキー製）で２分間混合し、エポキシ樹脂組成物を得た。 2. Production of epoxy resin composition 2-1. Example 1
100 parts by mass of epoxy resin (A) (jER-828, manufactured by Mitsubishi Chemical) and 10 parts by mass of compound (B1) were placed in a container and left in an environment of 80° C. for 1 hour. Then, using a glass rod, jER-828 and compound (B1) were mixed and allowed to stand until the temperature of the mixture reached 25°C. After that, a mixture of jER-828 and compound (B1) and 52 parts by mass of curing agent (C) (ST-12: manufactured by DIC) were mixed in a mixer (ARE-310: manufactured by Thinky) for 2 minutes to form an epoxy resin composition. got stuff
２－２．実施例２～９、比較例１～３、参考例１～３
表１～表２に記載の配合組成に変更した以外は実施例１と同様の方法によって、実施例２～９、比較例１～３、参考例１～３のエポキシ樹脂組成物を得た。
なお、実施例５、参考例２については、硬化剤（Ｃ）をミキサーに投入する前に８０℃で３０分間加熱した。 2-2. Examples 2-9, Comparative Examples 1-3, Reference Examples 1-3
Epoxy resin compositions of Examples 2 to 9, Comparative Examples 1 to 3, and Reference Examples 1 to 3 were obtained in the same manner as in Example 1, except that the composition was changed to those shown in Tables 1 and 2.
In Example 5 and Reference Example 2, the curing agent (C) was heated at 80° C. for 30 minutes before being charged into the mixer.
表１～表２に記載の配合組成に変更した以外は実施例１と同様の方法によって、実施例２～９、比較例１～３、参考例１～３のエポキシ樹脂組成物を得た。
なお、実施例５、参考例２については、硬化剤（Ｃ）をミキサーに投入する前に８０℃で３０分間加熱した。 2-2. Examples 2-9, Comparative Examples 1-3, Reference Examples 1-3
Epoxy resin compositions of Examples 2 to 9, Comparative Examples 1 to 3, and Reference Examples 1 to 3 were obtained in the same manner as in Example 1, except that the composition was changed to those shown in Tables 1 and 2.
In Example 5 and Reference Example 2, the curing agent (C) was heated at 80° C. for 30 minutes before being charged into the mixer.
表中の成分の詳細は、以下の通りである。
ｊＥＲ－８２８：ビスフェノールＡ型エポキシ樹脂；三菱ケミカル製
ＥＰＩＣＬＯＮ８３０：ビスフェノールＦ型エポキシ樹脂；ＤＩＣ製
ＳＴ１２：脂肪族ポリアミン系硬化剤（ｊＥＲキュアＳＴ１２）；三菱ケミカル製
ＴＤ－２１３１：クレゾールノボラック型硬化剤（ＰＨＥＮＯＬＩＴＥＴＤ－２１３１）；ＤＩＣ製
ＰＰｈ３：トリフェニルホスフィン The details of the components in the table are as follows.
jER-828: bisphenol A type epoxy resin; Mitsubishi Chemical EPICLON830: bisphenol F type epoxy resin; DIC ST12: aliphatic polyamine curing agent (jER Cure ST12); Mitsubishi Chemical TD-2131: cresol novolac type curing agent ( PHENOLITETD-2131); PPh 3 manufactured by DIC: triphenylphosphine
ｊＥＲ－８２８：ビスフェノールＡ型エポキシ樹脂；三菱ケミカル製
ＥＰＩＣＬＯＮ８３０：ビスフェノールＦ型エポキシ樹脂；ＤＩＣ製
ＳＴ１２：脂肪族ポリアミン系硬化剤（ｊＥＲキュアＳＴ１２）；三菱ケミカル製
ＴＤ－２１３１：クレゾールノボラック型硬化剤（ＰＨＥＮＯＬＩＴＥＴＤ－２１３１）；ＤＩＣ製
ＰＰｈ３：トリフェニルホスフィン The details of the components in the table are as follows.
jER-828: bisphenol A type epoxy resin; Mitsubishi Chemical EPICLON830: bisphenol F type epoxy resin; DIC ST12: aliphatic polyamine curing agent (jER Cure ST12); Mitsubishi Chemical TD-2131: cresol novolac type curing agent ( PHENOLITETD-2131); PPh 3 manufactured by DIC: triphenylphosphine
３．エポキシ樹脂組成物の評価
実施例・比較例・参考例のエポキシ樹脂組成物について、各種評価を実施した。その結果を表１～表２に示す。 3. Evaluation of Epoxy Resin Composition Various evaluations were performed on the epoxy resin compositions of Examples, Comparative Examples, and Reference Examples. The results are shown in Tables 1 and 2.
実施例・比較例・参考例のエポキシ樹脂組成物について、各種評価を実施した。その結果を表１～表２に示す。 3. Evaluation of Epoxy Resin Composition Various evaluations were performed on the epoxy resin compositions of Examples, Comparative Examples, and Reference Examples. The results are shown in Tables 1 and 2.
表１～表２に示すように、実施例は、比較例に比べて、ガラス転移温度が高く、化合物（Ｂ）を含まない参考例に近い値を有していた。また、実施例は、引張り弾性率、最大引張応力、せん断接着力及び貯蔵弾性率も参考例と同等であった。さらに、実施例は、冷熱サイクル試験の結果が参考例よりも優れていた。以上より、本発明の実施例によれば、エポキシ樹脂が本来有する力学物性や熱物性の悪化を抑制しつつ、熱応力によるクラック・剥がれを抑制することのできることが分かった。
As shown in Tables 1 and 2, the examples had higher glass transition temperatures than the comparative examples, and had values close to those of the reference examples that did not contain the compound (B). In addition, in the example, the tensile elastic modulus, the maximum tensile stress, the shear adhesive strength and the storage elastic modulus were also equivalent to those of the reference example. Furthermore, the examples were superior to the reference examples in the results of the thermal cycle test. From the above, it was found that according to the examples of the present invention, cracks and peeling due to thermal stress can be suppressed while suppressing the deterioration of the mechanical properties and thermophysical properties inherent in the epoxy resin.
評価の詳細は、以下の通りである。
［ガラス転移温度・解離開始温度］
評価対象のエポキシ樹脂組成物をフッ素系離型剤で処理した成形型に流し込み、８０℃で３時間加熱した後、さらに１２０℃３時間加熱硬化し、ダンベル試験片を作製した。 The details of the evaluation are as follows.
[Glass transition temperature/dissociation start temperature]
The epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours to prepare a dumbbell test piece.
［ガラス転移温度・解離開始温度］
評価対象のエポキシ樹脂組成物をフッ素系離型剤で処理した成形型に流し込み、８０℃で３時間加熱した後、さらに１２０℃３時間加熱硬化し、ダンベル試験片を作製した。 The details of the evaluation are as follows.
[Glass transition temperature/dissociation start temperature]
The epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours to prepare a dumbbell test piece.
前記試験片を簡易密閉パンに封入し、示差走査熱量計（ＤＳＣ）を用いて、窒素気流下、３０℃から２００℃まで１０℃／分で昇温して熱変化を測定して、「吸発熱量」と「温度」とのグラフを描き、このとき観測される特徴的な変曲をガラス転移とした。なお、ガラス転移温度は、ＤＳＣ曲線からミッドポイント法によって得た値を使用した。解離開始温度は、ガラス転移温度より高温に現れる吸熱ピークの補外開始温度の値を使用した。
The test piece is sealed in a simple sealed pan, and a differential scanning calorimeter (DSC) is used to measure the heat change by raising the temperature from 30 ° C. to 200 ° C. at a rate of 10 ° C./min under a nitrogen stream. A graph was drawn between calorific value and temperature, and the characteristic inflection observed at this time was taken as the glass transition. As the glass transition temperature, the value obtained by the midpoint method from the DSC curve was used. As the dissociation start temperature, the value of the extrapolated start temperature of the endothermic peak appearing at a temperature higher than the glass transition temperature was used.
［引張り弾性率・最大引張応力］
評価対象のエポキシ樹脂組成物をフッ素系離型剤で処理した成形型に流し込み、８０℃で３時間加熱した後、さらに１２０℃３時間加熱硬化し、ダンベル試験片を作製した。 [Tensile modulus/maximum tensile stress]
The epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours to prepare a dumbbell test piece.
評価対象のエポキシ樹脂組成物をフッ素系離型剤で処理した成形型に流し込み、８０℃で３時間加熱した後、さらに１２０℃３時間加熱硬化し、ダンベル試験片を作製した。 [Tensile modulus/maximum tensile stress]
The epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours to prepare a dumbbell test piece.
得られた試験片について、ＪＩＳ－Ｋ７１６１に準拠し、下記条件で引張り弾性率および最大引張応力を測定した。
・試料サイズ：ダンベル寸法１ＢＡ
・試験速度：１．０ｍｍ／ｍｉｎ
・測定環境：温度２５℃
・測定回数：３回測定し、平均値から算出 The tensile modulus and maximum tensile stress of the obtained test piece were measured according to JIS-K7161 under the following conditions.
・Sample size: Dumbbell size 1BA
・Test speed: 1.0 mm/min
・Measurement environment: Temperature 25℃
・Number of measurements: Measured 3 times and calculated from the average value
・試料サイズ：ダンベル寸法１ＢＡ
・試験速度：１．０ｍｍ／ｍｉｎ
・測定環境：温度２５℃
・測定回数：３回測定し、平均値から算出 The tensile modulus and maximum tensile stress of the obtained test piece were measured according to JIS-K7161 under the following conditions.
・Sample size: Dumbbell size 1BA
・Test speed: 1.0 mm/min
・Measurement environment: Temperature 25℃
・Number of measurements: Measured 3 times and calculated from the average value
［せん断接着力］
幅２５ｍｍ×長さ１００ｍｍ×厚さ１．０ｍｍのＳＵＳ板に、評価対象のエポキシ樹脂組成物を塗布し、硬化性組成物が塗布されたＳＵＳ板を得た。その後、別の幅２５ｍｍ×長さ１００ｍｍ×厚さ１．０ｍｍのＳＵＳ板を貼り付け面積が２５ｍｍ×１２．５ｍｍ、硬化物の厚さが０．２０ｍｍとなるように、前記エポキシ樹脂組成物が塗布されたＳＵＳ板の硬化性組成物が塗布された側に貼り合わせ、クリップで固定した。その後、８０℃で３時間加熱後、さらに１２０℃で３時間加熱し試験片を得た。得られた試験片について、万能引張試験機にてせん断接着力をＪＩＳ Ｋ ６８５０：１９９９に従い測定した（引っ張り速度２．０ｍｍ／ｍｉｎ．、試験環境温度２５℃）。 [Shear adhesive strength]
An epoxy resin composition to be evaluated was applied to a SUS plate having a width of 25 mm, a length of 100 mm, and a thickness of 1.0 mm to obtain a SUS plate coated with the curable composition. After that, another SUS plate having a width of 25 mm, a length of 100 mm, and a thickness of 1.0 mm was adhered so that the area of the cured product was 25 mm × 12.5 mm, and the thickness of the cured product was 0.20 mm. The coated SUS plate was attached to the curable composition-coated side and fixed with a clip. Then, after heating at 80° C. for 3 hours, it was further heated at 120° C. for 3 hours to obtain a test piece. The obtained test piece was measured for shear adhesive strength using a universal tensile tester according to JIS K 6850:1999 (pulling speed 2.0 mm/min., test environment temperature 25° C.).
幅２５ｍｍ×長さ１００ｍｍ×厚さ１．０ｍｍのＳＵＳ板に、評価対象のエポキシ樹脂組成物を塗布し、硬化性組成物が塗布されたＳＵＳ板を得た。その後、別の幅２５ｍｍ×長さ１００ｍｍ×厚さ１．０ｍｍのＳＵＳ板を貼り付け面積が２５ｍｍ×１２．５ｍｍ、硬化物の厚さが０．２０ｍｍとなるように、前記エポキシ樹脂組成物が塗布されたＳＵＳ板の硬化性組成物が塗布された側に貼り合わせ、クリップで固定した。その後、８０℃で３時間加熱後、さらに１２０℃で３時間加熱し試験片を得た。得られた試験片について、万能引張試験機にてせん断接着力をＪＩＳ Ｋ ６８５０：１９９９に従い測定した（引っ張り速度２．０ｍｍ／ｍｉｎ．、試験環境温度２５℃）。 [Shear adhesive strength]
An epoxy resin composition to be evaluated was applied to a SUS plate having a width of 25 mm, a length of 100 mm, and a thickness of 1.0 mm to obtain a SUS plate coated with the curable composition. After that, another SUS plate having a width of 25 mm, a length of 100 mm, and a thickness of 1.0 mm was adhered so that the area of the cured product was 25 mm × 12.5 mm, and the thickness of the cured product was 0.20 mm. The coated SUS plate was attached to the curable composition-coated side and fixed with a clip. Then, after heating at 80° C. for 3 hours, it was further heated at 120° C. for 3 hours to obtain a test piece. The obtained test piece was measured for shear adhesive strength using a universal tensile tester according to JIS K 6850:1999 (pulling speed 2.0 mm/min., test environment temperature 25° C.).
［貯蔵弾性率］
評価対象のエポキシ樹脂組成物をフッ素系離型剤で処理した成形型に流し込み、８０℃で３時間加熱した後、さらに１２０℃３時間加熱硬化し、長さ５．０ｃｍ、幅１．０ｃｍ、厚さ１．０ｍｍの試験片を作製した。得られた試験片について、動的粘弾性測定装置ＲＳＡ３（ＴＡＩｎｓｔｒｕｍｅｎｔｓ製）を用いて、貯蔵弾性率を下記の条件で測定した。なお、表に記載の貯蔵弾性率の値は、２００℃における貯蔵弾性率の値である。
・昇温速度５℃／ｍｉｎ
・周波数１．０Ｈｚ
・測定温度範囲：３０～３００℃ [Storage modulus]
The epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours. A test piece with a thickness of 1.0 mm was produced. The storage modulus of the obtained test piece was measured using a dynamic viscoelasticity measuring device RSA3 (manufactured by TAInstruments) under the following conditions. In addition, the value of the storage elastic modulus described in the table is the value of the storage elastic modulus at 200°C.
・Temperature increase rate 5°C/min
・Frequency 1.0Hz
・Measurement temperature range: 30 to 300°C
評価対象のエポキシ樹脂組成物をフッ素系離型剤で処理した成形型に流し込み、８０℃で３時間加熱した後、さらに１２０℃３時間加熱硬化し、長さ５．０ｃｍ、幅１．０ｃｍ、厚さ１．０ｍｍの試験片を作製した。得られた試験片について、動的粘弾性測定装置ＲＳＡ３（ＴＡＩｎｓｔｒｕｍｅｎｔｓ製）を用いて、貯蔵弾性率を下記の条件で測定した。なお、表に記載の貯蔵弾性率の値は、２００℃における貯蔵弾性率の値である。
・昇温速度５℃／ｍｉｎ
・周波数１．０Ｈｚ
・測定温度範囲：３０～３００℃ [Storage modulus]
The epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours. A test piece with a thickness of 1.0 mm was produced. The storage modulus of the obtained test piece was measured using a dynamic viscoelasticity measuring device RSA3 (manufactured by TAInstruments) under the following conditions. In addition, the value of the storage elastic modulus described in the table is the value of the storage elastic modulus at 200°C.
・Temperature increase rate 5°C/min
・Frequency 1.0Hz
・Measurement temperature range: 30 to 300°C
［冷熱サイクル試験］
幅２５ｍｍ×長さ１００ｍｍ×厚さ１．０ｍｍのＳＵＳ板に、評価対象のエポキシ樹脂組成物を塗布し、硬化性組成物が塗布されたＳＵＳ板を得た。その後、別の幅２５ｍｍ×長さ１００ｍｍ×厚さ１．０ｍｍのＳＵＳ板を貼り付け面積が２５ｍｍ×１２．５ｍｍ、硬化物の厚さが０．２０ｍｍとなるように前記エポキシ樹脂組成物が塗布されたＳＵＳ板の硬化性組成物が塗布された側に貼り合わせ、クリップで固定した。その後、８０℃で３時間加熱後、さらに１２０℃で３時間加熱し試験片を得た。得られた試験片を２５℃環境下に２４時間放置し、冷熱衝撃装置ＴＳＡ－７１Ｌ－Ａ（エスペック製）を用い、－４０℃×３０分、２００℃×３０分を１サイクルとする冷熱サイクルを１５０回繰り返した後の試験片の剥がれの有無を目視で確認した。試験は同一硬化性組成物につき３回実施し、表中の数値は剥がれが生じた回数を示す。 [Cold-heat cycle test]
An epoxy resin composition to be evaluated was applied to a SUS plate having a width of 25 mm, a length of 100 mm, and a thickness of 1.0 mm to obtain a SUS plate coated with the curable composition. After that, another SUS plate of width 25 mm × length 100 mm × thickness 1.0 mm is attached, and the epoxy resin composition is applied so that the area is 25 mm × 12.5 mm and the thickness of the cured product is 0.20 mm. The side of the SUS plate coated with the curable composition was pasted together and fixed with a clip. Then, after heating at 80° C. for 3 hours, it was further heated at 120° C. for 3 hours to obtain a test piece. The obtained test piece is left in an environment of 25°C for 24 hours, and a thermal shock device TSA-71L-A (manufactured by Espec) is used to perform a thermal cycle of -40°C x 30 minutes and 200°C x 30 minutes as one cycle. was repeated 150 times, and the presence or absence of peeling of the test piece was visually confirmed. The test was performed three times for the same curable composition, and the numbers in the table indicate the number of times peeling occurred.
幅２５ｍｍ×長さ１００ｍｍ×厚さ１．０ｍｍのＳＵＳ板に、評価対象のエポキシ樹脂組成物を塗布し、硬化性組成物が塗布されたＳＵＳ板を得た。その後、別の幅２５ｍｍ×長さ１００ｍｍ×厚さ１．０ｍｍのＳＵＳ板を貼り付け面積が２５ｍｍ×１２．５ｍｍ、硬化物の厚さが０．２０ｍｍとなるように前記エポキシ樹脂組成物が塗布されたＳＵＳ板の硬化性組成物が塗布された側に貼り合わせ、クリップで固定した。その後、８０℃で３時間加熱後、さらに１２０℃で３時間加熱し試験片を得た。得られた試験片を２５℃環境下に２４時間放置し、冷熱衝撃装置ＴＳＡ－７１Ｌ－Ａ（エスペック製）を用い、－４０℃×３０分、２００℃×３０分を１サイクルとする冷熱サイクルを１５０回繰り返した後の試験片の剥がれの有無を目視で確認した。試験は同一硬化性組成物につき３回実施し、表中の数値は剥がれが生じた回数を示す。 [Cold-heat cycle test]
An epoxy resin composition to be evaluated was applied to a SUS plate having a width of 25 mm, a length of 100 mm, and a thickness of 1.0 mm to obtain a SUS plate coated with the curable composition. After that, another SUS plate of width 25 mm × length 100 mm × thickness 1.0 mm is attached, and the epoxy resin composition is applied so that the area is 25 mm × 12.5 mm and the thickness of the cured product is 0.20 mm. The side of the SUS plate coated with the curable composition was pasted together and fixed with a clip. Then, after heating at 80° C. for 3 hours, it was further heated at 120° C. for 3 hours to obtain a test piece. The obtained test piece is left in an environment of 25°C for 24 hours, and a thermal shock device TSA-71L-A (manufactured by Espec) is used to perform a thermal cycle of -40°C x 30 minutes and 200°C x 30 minutes as one cycle. was repeated 150 times, and the presence or absence of peeling of the test piece was visually confirmed. The test was performed three times for the same curable composition, and the numbers in the table indicate the number of times peeling occurred.
Claims (6)
- エポキシ樹脂（Ａ）１００質量部と、
下記式（１）で示される化合物（Ｂ）を５～９０質量部と、
硬化剤（Ｃ）１０～９０質量部と、
を含むエポキシ樹脂組成物。
Ｘは、－Ｏ－、－Ｓ－、－ＮＲ２－、又は－ＣＯＯ－で表される基であり、Ｒ２は、－ＣＨ３、－Ｃ２Ｈ５、又は－（ＣＨ２）ａ－ＣＨ（Ｏ）ＣＨ２で表される基あり、
Ａｒ１は、未置換のフェニル基、又は１～４個のメチル基又はエチル基で置換されたフェニル基であり、
ａは、０～５の整数、ｂは、１～５の整数であり、
Ｙは、直接結合又は式（２）で表される基であり、式（２）中の＊３及び＊４は、それぞれ、Ｒ１及びＮとの結合部である。）
ｄは、１～８の整数、ｅは、１～３の整数であり、
Ａｒ２及びＡｒ３は、それぞれ、未置換のフェニル基、１～４個のメチル基又はエチル基で置換されたフェニル基、未置換のビフェニル基、又は１～８個のメチル基又はエチル基で置換されたビフェニル基であり、
Ｒ４は、－（ＣＨ２）ｆ－、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、又は－［（ＣＨ２）ｆ－Ｏ］ｇ－（ＣＨ２）ｆ－で表される基であり、
ｆは、１～８の整数、ｇは、１～３の整数である。） 100 parts by mass of epoxy resin (A);
5 to 90 parts by mass of the compound (B) represented by the following formula (1),
Curing agent (C) 10 to 90 parts by mass,
An epoxy resin composition comprising:
X is a group represented by -O-, -S-, -NR 2 - or -COO-, and R 2 is -CH 3 , -C 2 H 5 or -(CH 2 ) a - a group represented by CH(O) CH2 ,
Ar 1 is an unsubstituted phenyl group or a phenyl group substituted with 1 to 4 methyl or ethyl groups;
a is an integer of 0 to 5, b is an integer of 1 to 5,
Y is a direct bond or a group represented by formula (2), and * 3 and * 4 in formula (2) are bonding sites with R1 and N, respectively. )
d is an integer of 1 to 8, e is an integer of 1 to 3,
Ar 2 and Ar 3 are each an unsubstituted phenyl group, a phenyl group substituted with 1 to 4 methyl or ethyl groups, an unsubstituted biphenyl group, or 1 to 8 methyl or ethyl groups; a substituted biphenyl group,
R 4 is -(CH 2 ) f -, -O-, -S-, -SO-, -SO 2 -, -CO-, or -[(CH 2 ) f -O] g -(CH 2 ) a group represented by f- ,
f is an integer of 1-8, g is an integer of 1-3. ) - 請求項１に記載のエポキシ樹脂組成物であって、
前記式（１）中のＹは、式（２）で表される基である、エポキシ樹脂組成物。 The epoxy resin composition according to claim 1,
The epoxy resin composition, wherein Y in the formula (1) is a group represented by the formula (2). - 請求項２に記載のエポキシ樹脂組成物であって、
前記式（２）のＲ３は、－Ａｒ３－Ｒ４－Ａｒ３－である、エポキシ樹脂組成物。 The epoxy resin composition according to claim 2,
The epoxy resin composition wherein R 3 in the formula (2) is -Ar 3 -R 4 -Ar 3 -. - 請求項１～請求項３の何れか１つに記載のエポキシ樹脂組成物であって、
前記硬化剤が、アミン系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、多価カルボン酸化合物から選ばれる少なくとも１つである、エポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 3,
The epoxy resin composition, wherein the curing agent is at least one selected from amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and polyvalent carboxylic acid compounds. - 請求項１～請求項４の何れか１つに記載のエポキシ樹脂組成物であって、
前記エポキシ樹脂（Ａ）１００質量部に対して、前記化合物（Ｂ）を５～８０質量部含む、エポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 4,
An epoxy resin composition containing 5 to 80 parts by mass of the compound (B) with respect to 100 parts by mass of the epoxy resin (A). - 請求項１～請求項５の何れか１つに記載のエポキシ樹脂組成物を硬化させて得られるエポキシ樹脂硬化物。 A cured epoxy resin obtained by curing the epoxy resin composition according to any one of claims 1 to 5.
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| WO2022202610A1 true WO2022202610A1 (en) | 2022-09-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2022/012297 WO2022202610A1 (en) | 2021-03-23 | 2022-03-17 | Epoxy resin composition, epoxy resin cured product |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2022202610A1 (en) |
| CN (1) | CN116981710A (en) |
| TW (1) | TW202248270A (en) |
| WO (1) | WO2022202610A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024053402A1 (en) * | 2022-09-06 | 2024-03-14 | Dic株式会社 | Glycidyl group-containing compound, curable resin composition, cured product and multilayer body |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194038A (en) * | 2014-08-29 | 2014-12-10 | 浙江大学 | Epoxy resin composition, and wet-process ultrasonic degradation method and application thereof |
| CN105694790A (en) * | 2016-02-29 | 2016-06-22 | 中国工程物理研究院材料研究所 | Epoxy adhesive capable of being removed quickly and preparing and removing methods thereof |
| CN108219111A (en) * | 2018-01-03 | 2018-06-29 | 中国工程物理研究院化工材料研究所 | Selfreparing, the thermosets that can be reprocessed and can be recycled and its processing method under a kind of temperate condition |
| WO2021251099A1 (en) * | 2020-06-12 | 2021-12-16 | 国立大学法人九州大学 | Easily disintegrable adhesive material, article and disintegration method |
-
2022
- 2022-03-17 CN CN202280016326.6A patent/CN116981710A/en active Pending
- 2022-03-17 WO PCT/JP2022/012297 patent/WO2022202610A1/en active Application Filing
- 2022-03-17 JP JP2023509101A patent/JPWO2022202610A1/ja active Pending
- 2022-03-18 TW TW111109990A patent/TW202248270A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194038A (en) * | 2014-08-29 | 2014-12-10 | 浙江大学 | Epoxy resin composition, and wet-process ultrasonic degradation method and application thereof |
| CN105694790A (en) * | 2016-02-29 | 2016-06-22 | 中国工程物理研究院材料研究所 | Epoxy adhesive capable of being removed quickly and preparing and removing methods thereof |
| CN108219111A (en) * | 2018-01-03 | 2018-06-29 | 中国工程物理研究院化工材料研究所 | Selfreparing, the thermosets that can be reprocessed and can be recycled and its processing method under a kind of temperate condition |
| WO2021251099A1 (en) * | 2020-06-12 | 2021-12-16 | 国立大学法人九州大学 | Easily disintegrable adhesive material, article and disintegration method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024053402A1 (en) * | 2022-09-06 | 2024-03-14 | Dic株式会社 | Glycidyl group-containing compound, curable resin composition, cured product and multilayer body |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202248270A (en) | 2022-12-16 |
| CN116981710A (en) | 2023-10-31 |
| JPWO2022202610A1 (en) | 2022-09-29 |
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