JP7404127B2 - epoxy resin composition - Google Patents
epoxy resin composition Download PDFInfo
- Publication number
- JP7404127B2 JP7404127B2 JP2020055058A JP2020055058A JP7404127B2 JP 7404127 B2 JP7404127 B2 JP 7404127B2 JP 2020055058 A JP2020055058 A JP 2020055058A JP 2020055058 A JP2020055058 A JP 2020055058A JP 7404127 B2 JP7404127 B2 JP 7404127B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- epoxy resin
- resin composition
- curing agent
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims description 178
- 229920000647 polyepoxide Polymers 0.000 title claims description 178
- 239000000203 mixture Substances 0.000 title claims description 113
- 239000003795 chemical substances by application Substances 0.000 claims description 72
- 150000001875 compounds Chemical class 0.000 claims description 55
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000003094 microcapsule Substances 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims 2
- -1 polyol compound Chemical class 0.000 description 20
- 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 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 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 13
- 229920003986 novolac Polymers 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 230000008719 thickening Effects 0.000 description 9
- 125000003700 epoxy group Chemical group 0.000 description 8
- 238000004904 shortening Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007142 ring opening reaction Methods 0.000 description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 5
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 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 4
- YFBMUIMQJYESPZ-UHFFFAOYSA-N 3-phenoxy-1,2-propanediol Natural products C1C(OC(C)=O)CCC2(C)C3=CCC4(C)C(C(C)CCC(CC)C(C)C)CCC4(C)C3CCC21 YFBMUIMQJYESPZ-UHFFFAOYSA-N 0.000 description 4
- FNQIYTUXOKTMDM-UHFFFAOYSA-N 3-phenoxypropane-1,2-diol Chemical compound OCC(O)COC1=CC=CC=C1 FNQIYTUXOKTMDM-UHFFFAOYSA-N 0.000 description 4
- JHWQMXKQJVAWKI-UHFFFAOYSA-N UNPD187286 Natural products OCC(O)CC1=CC=CC=C1 JHWQMXKQJVAWKI-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000012766 organic filler Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- NBLIPZBCGXIEFO-UHFFFAOYSA-N 3-(4-(1-(4-(2,3-Epoxypropoxy)phenyl)-1-methylethyl)phenoxy)propane-1,2-diol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(OCC(O)CO)C=C1 NBLIPZBCGXIEFO-UHFFFAOYSA-N 0.000 description 3
- GVBRFUJHRRZUHG-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propan-1-ol Chemical compound OCCCOCC1CO1 GVBRFUJHRRZUHG-UHFFFAOYSA-N 0.000 description 3
- AWVDYRFLCAZENH-UHFFFAOYSA-N 3-phenoxypropan-1-ol Chemical compound OCCCOC1=CC=CC=C1 AWVDYRFLCAZENH-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- JWDYCNIAQWPBHD-UHFFFAOYSA-N 1-(2-methylphenyl)glycerol Chemical compound CC1=CC=CC=C1OCC(O)CO JWDYCNIAQWPBHD-UHFFFAOYSA-N 0.000 description 2
- RUFZNDNBXKOZQV-UHFFFAOYSA-N 2,3-dihydro-1h-pyrrolo[1,2-a]benzimidazole Chemical compound C1=CC=C2N(CCC3)C3=NC2=C1 RUFZNDNBXKOZQV-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 description 2
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Chemical class 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- 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 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- LPVHVQFTYXQKAP-YFKPBYRVSA-N (4r)-3-formyl-2,2-dimethyl-1,3-thiazolidine-4-carboxylic acid Chemical compound CC1(C)SC[C@@H](C(O)=O)N1C=O LPVHVQFTYXQKAP-YFKPBYRVSA-N 0.000 description 1
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-N 0.000 description 1
- NQOFYFRKWDXGJP-UHFFFAOYSA-N 1,1,2-trimethylguanidine Chemical compound CN=C(N)N(C)C NQOFYFRKWDXGJP-UHFFFAOYSA-N 0.000 description 1
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 1
- NYSAPLQZKHQBSO-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-phenylbenzene Chemical group BrC1=C(Br)C(Br)=CC(C=2C=CC=CC=2)=C1Br NYSAPLQZKHQBSO-UHFFFAOYSA-N 0.000 description 1
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N 1,2-dimethylguanidine Chemical compound CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- 150000000180 1,2-diols Chemical group 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- XBPWJDSOUOAUQN-UHFFFAOYSA-N 1-phenoxypropane-1,3-diol Chemical compound OCCC(O)OC1=CC=CC=C1 XBPWJDSOUOAUQN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- ZUZAETTVAMCNTO-UHFFFAOYSA-N 2,3-dibutylbenzene-1,4-diol Chemical compound CCCCC1=C(O)C=CC(O)=C1CCCC ZUZAETTVAMCNTO-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- NKVZFNUCUPOCQJ-UHFFFAOYSA-N 2-anilinopropanehydrazide Chemical compound NNC(=O)C(C)NC1=CC=CC=C1 NKVZFNUCUPOCQJ-UHFFFAOYSA-N 0.000 description 1
- CGWBIHLHAGNJCX-UHFFFAOYSA-N 2-butylguanidine Chemical compound CCCCNC(N)=N CGWBIHLHAGNJCX-UHFFFAOYSA-N 0.000 description 1
- KEWLVUBYGUZFKX-UHFFFAOYSA-N 2-ethylguanidine Chemical compound CCNC(N)=N KEWLVUBYGUZFKX-UHFFFAOYSA-N 0.000 description 1
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 1
- QRJZGVVKGFIGLI-UHFFFAOYSA-N 2-phenylguanidine Chemical compound NC(=N)NC1=CC=CC=C1 QRJZGVVKGFIGLI-UHFFFAOYSA-N 0.000 description 1
- BWMDMTSNSXYYSP-UHFFFAOYSA-N 2-propylguanidine Chemical compound CCCNC(N)=N BWMDMTSNSXYYSP-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- LNYFNDSFIABLEP-UHFFFAOYSA-N 3-[4-[[4-(oxiran-2-ylmethoxy)phenyl]methyl]phenoxy]propane-1,2-diol Chemical compound C1=CC(OCC(O)CO)=CC=C1CC(C=C1)=CC=C1OCC1OC1 LNYFNDSFIABLEP-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Chemical class 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- IKWQWOFXRCUIFT-UHFFFAOYSA-N benzene-1,2-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C(=O)NN IKWQWOFXRCUIFT-UHFFFAOYSA-N 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-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
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- OYOFUEDXAMRQBB-UHFFFAOYSA-N cyclohexylmethanediamine Chemical compound NC(N)C1CCCCC1 OYOFUEDXAMRQBB-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-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
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant 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
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229960002146 guaifenesin Drugs 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229960003861 mephenesin Drugs 0.000 description 1
- ASHGTJPOSUFTGB-UHFFFAOYSA-N methyl resorcinol Natural products COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
本発明は、エポキシ樹脂組成物に関する。 The present invention relates to epoxy resin compositions.
エポキシ樹脂は、電気電子部品の絶縁材料、封止材料、接着剤、導電性材料や繊維強化プラスチックのマトリックス樹脂等の幅広い用途に利用されている。 Epoxy resins are used in a wide range of applications, such as insulating materials for electrical and electronic components, sealing materials, adhesives, conductive materials, and matrix resins for fiber-reinforced plastics.
昨今の電子デバイス機器に対する要求は小型化、高機能化、軽量化、多機能化、と多岐にわたっており、半導体のチップの実装技術においても電極パッドとパッドピッチとのファインピッチ化による一層の微細化、小型化、高密度化が進んでいる。チップと基板との隙間にバンプ接続部とチップの回路面とを保護する接着剤としてエポキシ樹脂を用いた熱硬化性樹脂であるアンダーフィル材がある。 Recent demands for electronic devices are diverse, including miniaturization, high functionality, weight reduction, and multifunctionality.Semiconductor chip mounting technology is also undergoing further miniaturization through finer pitch between electrode pads and pad pitches. , miniaturization and higher density are progressing. In the gap between the chip and the substrate, there is an underfill material that is a thermosetting resin using epoxy resin as an adhesive that protects the bump connection portion and the circuit surface of the chip.
繊維強化プラスチックは、強化繊維とマトリックス樹脂とを用いて製造される。マトリックス樹脂としては、エポキシ樹脂を用いた熱硬化性樹脂が多く使用される。例えば、特許文献１には、加水分解性塩素と、アルコール性水酸基を２つ以上有する成分とを含むことで、十分な保存安定性、硬化速度、機械強度、耐熱性を得ることが可能なエポキシ樹脂組成物が開示されている。また、例えば、特許文献２には、酸無水物と芳香環を有するポリオール化合物とを含むことで、７０℃以下の低温において、短時間硬化可能なエポキシ樹脂組成物が開示されている。 Fiber-reinforced plastics are manufactured using reinforcing fibers and matrix resin. As the matrix resin, thermosetting resins using epoxy resins are often used. For example, Patent Document 1 describes an epoxy resin that can obtain sufficient storage stability, curing speed, mechanical strength, and heat resistance by containing hydrolyzable chlorine and a component having two or more alcoholic hydroxyl groups. A resin composition is disclosed. Further, for example, Patent Document 2 discloses an epoxy resin composition that contains an acid anhydride and a polyol compound having an aromatic ring and can be cured for a short time at a low temperature of 70° C. or lower.
近年、上述したアンダーフィル材は、ファインピッチ化に伴う狭ギャップ間への浸透を可能にするために低粘度化が求められている。また、生産性向上のための硬化温度の低温化や硬化時間の短縮、もアンダーフィル材に対して強く求められている。
しかしながら、特許文献１及び特許文献２に記載されたエポキシ樹脂組成物は、低粘度化、低温硬化性、硬化時間の短縮、熱の伝わり方が不均一な場合での十分な硬化領域の確保、において改善の余地が残る。
本発明は、上述の現状を鑑みてなされたものである。即ち、本発明の目的は、低粘度化、低温硬化性の向上、硬化時間の短縮、熱の伝わり方が不十分な場合での十分な硬化領域の確保、が可能なエポキシ樹脂組成物を提供することである。
In recent years, the above-mentioned underfill materials are required to have lower viscosity in order to enable penetration into narrow gaps associated with finer pitch. In addition, there is a strong demand for underfill materials to lower the curing temperature and shorten the curing time in order to improve productivity.
However, the epoxy resin compositions described in Patent Document 1 and Patent Document 2 have low viscosity, low-temperature curability, shortening of curing time, securing a sufficient curing area even when heat transfer is uneven, There remains room for improvement.
The present invention has been made in view of the above-mentioned current situation. That is, an object of the present invention is to provide an epoxy resin composition that can reduce viscosity, improve low-temperature curability, shorten curing time, and secure a sufficient curing area even when heat transfer is insufficient. It is to be.
本発明者は、鋭意検討した結果、以下の技術的手段によって、上記の目的を達成できることを見出し、本発明に至った。
なお、特許文献１に記載のアルコール性水酸基を２つ以上有する成分は、下記式（１）で示される構造を有していない。
本発明は以下のとおりのものである。
［１］
下記成分（Ａ）、下記成分（Ｂ）及び下記成分（Ｃ）を含むエポキシ樹脂組成物。
（Ａ）エポキシ樹脂
（Ｂ）硬化剤
（Ｃ）下記式（１）で示される化合物
［２］
前記成分（Ｂ）が固体の硬化剤を含む、［１］に記載のエポキシ樹脂組成物。
［３］
前記式（１）のＲ1がヒドロキシル基である、［１］又は［２］に記載のエポキシ樹脂組成物。
［４］
前記式（１）のＲ2、Ｒ3及びＲ4が水素である、［１］～［３］のいずれかに記載のエポキシ樹脂組成物。
［５］
前記成分（Ｂ）として、活性水素を４つ以上含む化合物を含む、［１］～［４］のいずれかに記載のエポキシ樹脂組成物。
［６］
前記成分（Ｂ）が、イミダゾール系硬化剤を含む、［１］～［４］のいずれかに記載のエポキシ樹脂組成物。
［７］
前記成分（Ｂ）が、マイクロカプセル型硬化剤を含む、［１］～［４］のいずれかに記載のエポキシ樹脂組成物。
［８］
前記成分（Ｄ）として、硬化促進剤をさらに含む、［１］～［７］のいずれかに記載のエポキシ樹脂組成物。
［９］
下記成分（Ａ）、下記成分（Ｂ）及び下記成分（Ｃ）を含むエポキシ樹脂組成物の製造方法であって、成分（Ａ）及び成分（Ｂ）の群から選ばれる少なくとも一つを有する化合物又は組成物に成分（Ｃ）を添加する工程を含む、エポキシ樹脂組成物の製造方法。
（Ａ）エポキシ樹脂
（Ｂ）硬化剤
（Ｃ）下記式（１）で示される化合物
［１０］
エポキシ樹脂組成物がさらに下記成分（Ｄ）を含み、
成分（Ａ）、成分（Ｂ）、及び成分（Ｄ）の群から選ばれる少なくとも一つを有する化合物又は組成物に成分（Ｃ）を添加する工程を含む、［９］に記載のエポキシ樹脂組成物の製造方法。
（Ｄ）硬化促進剤
［１１］
エポキシ樹脂組成物がさらに下記成分（Ｅ）を含み、
成分（Ａ）、成分（Ｂ）、及び成分（Ｅ）の群から選ばれる少なくとも一つを有する化合物又は組成物に成分（Ｃ）を添加する工程を含む、［９］又は［１０］に記載のエポキシ樹脂組成物の製造方法。
（Ｅ）フィラー
As a result of intensive studies, the inventors have found that the above object can be achieved by the following technical means, and have arrived at the present invention.
Note that the component having two or more alcoholic hydroxyl groups described in Patent Document 1 does not have a structure represented by the following formula (1).
The present invention is as follows.
[1]
An epoxy resin composition comprising the following component (A), the following component (B), and the following component (C).
(A) Epoxy resin (B) Curing agent (C) Compound represented by the following formula (1)
[2]
The epoxy resin composition according to [1], wherein the component (B) contains a solid curing agent.
[3]
The epoxy resin composition according to [1] or [2], wherein R 1 in the formula (1) is a hydroxyl group.
[4]
The epoxy resin composition according to any one of [1] to [3], wherein R 2 , R 3 and R 4 in the formula (1) are hydrogen.
[5]
The epoxy resin composition according to any one of [1] to [4], which contains a compound containing four or more active hydrogens as the component (B).
[6]
The epoxy resin composition according to any one of [1] to [4], wherein the component (B) contains an imidazole curing agent.
[7]
The epoxy resin composition according to any one of [1] to [4], wherein the component (B) contains a microcapsule type curing agent.
[8]
The epoxy resin composition according to any one of [1] to [7], further comprising a curing accelerator as the component (D).
[9]
A method for producing an epoxy resin composition containing the following component (A), the following component (B), and the following component (C), the compound having at least one selected from the group of component (A) and component (B). Or a method for producing an epoxy resin composition, which includes the step of adding component (C) to the composition.
(A) Epoxy resin (B) Curing agent (C) Compound represented by the following formula (1)
[10]
The epoxy resin composition further contains the following component (D),
The epoxy resin composition according to [9], which includes the step of adding component (C) to a compound or composition having at least one selected from the group of component (A), component (B), and component (D). How things are manufactured.
(D) Curing accelerator [11]
The epoxy resin composition further contains the following component (E),
The method described in [9] or [10], which includes the step of adding component (C) to a compound or composition having at least one selected from the group of component (A), component (B), and component (E). A method for producing an epoxy resin composition.
(E) Filler
本発明によれば、低粘度化、低温硬化性の向上、硬化時間の短縮、熱の伝わり方が不十分な場合での十分な硬化領域の確保、が可能なエポキシ樹脂組成物を提供される。 According to the present invention, an epoxy resin composition is provided that can reduce viscosity, improve low-temperature curability, shorten curing time, and secure a sufficient curing area even when heat transfer is insufficient. .
以下、本発明を実施するための形態（以下、単に「本実施形態」という。）について詳細に説明する。以下の本実施形態は、本発明を説明するための例示であり、本発明を以下の内容に限定する趣旨ではない。本発明は、その要旨の範囲内で適宜に変形して実施できる。 Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. The present embodiment below is an illustration for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be implemented with appropriate modifications within the scope of its gist.
＜エポキシ樹脂組成物＞
本実施形態のエポキシ樹脂組成物は、（Ａ）エポキシ樹脂（以下「成分（Ａ）」とも記す。）、（Ｂ）硬化剤（以下「成分（Ｂ）」とも記す。）、及び（Ｃ）下記式（１）で示される化合物（以下「成分（Ｃ）」とも記す。）を含む。
本実施形態のエポキシ樹脂組成物は、成分（Ａ）～（Ｃ）を含むことにより、低粘度化、低温硬化性の向上、硬化時間の短縮、熱の伝わり方が不十分な場合での十分な硬化領域の確保が可能となる。
<Epoxy resin composition>
The epoxy resin composition of this embodiment includes (A) an epoxy resin (hereinafter also referred to as "component (A)"), (B) a curing agent (hereinafter also referred to as "component (B)"), and (C) It contains a compound represented by the following formula (1) (hereinafter also referred to as "component (C)").
By containing components (A) to (C), the epoxy resin composition of the present embodiment can reduce viscosity, improve low-temperature curability, shorten curing time, and provide sufficient heat transfer in cases where heat transfer is insufficient. It is possible to secure a hardened area.
＜成分（Ａ）エポキシ樹脂＞
成分（Ａ）エポキシ樹脂としては、以下に限定されるわけではないが、例えば、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、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＭ型エポキシ樹脂、ビスフェノールＰ型エポキシ樹脂、テトラブロモビスフェノールＡ型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂、テトラブロモビフェニル型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ベンゾフェノン型エポキシ樹脂、フェニルベンゾエート型エポキシ樹脂、ジフェニルスルフィド型エポキシ樹脂、ジフェニルスルホキシド型エポキシ樹脂、ジフェニルスルホン型エポキシ樹脂、ジフェニルジスルフィド型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂、ヒドロキノン型エポキシ樹脂、メチルヒドロキノン型エポキシ樹脂、ジブチルヒドロキノン型エポキシ樹脂、レゾルシン型エポキシ樹脂、メチルレゾルシン型エポキシ樹脂、カテコール型エポキシ樹脂、Ｎ，Ｎ－ジグリシジルアニリン型エポキシ樹脂等の２官能型エポキシ樹脂類；Ｎ，Ｎ－ジグリシジルアミノベンゼン型エポキシ樹脂、ｏ－（Ｎ，Ｎ－ジグリシジルアミノ）トルエン型エポキシ樹脂、トリアジン型エポキシ樹脂等の３官能型エポキシ樹脂類；テトラグリシジルジアミノジフェニルメタン型エポキシ樹脂、ジアミノベンゼン型エポキシ樹脂等の４官能型エポキシ樹脂類；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ブロモ化フェノールノボラック型エポキシ樹脂等の多官能型エポキシ樹脂類；及び脂環式エポキシ樹脂類が挙げられる。これらは１種単独で用いてもよく、２種以上併用してもよい。さらに、これらをイソシアネート等で変性したエポキシ樹脂等も併用することができる。本実施形態のエポキシ樹脂組成物は、取り扱い性と耐熱性の観点から、ビスフェノール型エポキシ樹脂を含むことが好ましい。
<Component (A) epoxy resin>
Component (A) epoxy resins include, but are not limited to, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AD epoxy resins, bisphenol M epoxy resins, and bisphenol P epoxy resins. , tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenylbenzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, resorcin type epoxy resin, Bifunctional epoxy resins such as methylresorcinol epoxy resin, catechol epoxy resin, N,N-diglycidylaniline epoxy resin; N,N-diglycidylaminobenzene epoxy resin, o-(N,N-di Trifunctional epoxy resins such as glycidylamino) toluene type epoxy resins and triazine type epoxy resins; Tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resins and diaminobenzene type epoxy resins; Phenol novolac type epoxy resins and cresols Multifunctional epoxy resins such as novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, naphthol aralkyl type epoxy resin, brominated phenol novolac type epoxy resin; and resins Examples include cyclic epoxy resins. These may be used alone or in combination of two or more. Furthermore, epoxy resins obtained by modifying these with isocyanates or the like can also be used in combination. The epoxy resin composition of this embodiment preferably contains a bisphenol-type epoxy resin from the viewpoints of handleability and heat resistance.
（Ａ）エポキシ樹脂の含有量は、エポキシ樹脂組成物全体の質量に対して、硬化物に十分な強度を付与する点から、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、１５質量％以上であることがさらに好ましく、２０質量％以上であることがさらにより好ましい。また、（Ａ）エポキシ樹脂の含有量は、十分な硬化性を付与するために成分（Ｂ）及び成分（Ｃ）を加えられることから、エポキシ樹脂組成物全体の質量に対して、９８質量％以下であることが好ましく、９５質量％以下であることがより好ましく、９２％質量以下であることがさらに好ましい。 (A) The content of the epoxy resin is preferably 5% by mass or more, and preferably 10% by mass or more, based on the mass of the entire epoxy resin composition, from the viewpoint of imparting sufficient strength to the cured product. The content is more preferably 15% by mass or more, even more preferably 20% by mass or more. In addition, the content of the epoxy resin (A) is 98% by mass based on the mass of the entire epoxy resin composition, since components (B) and (C) are added to impart sufficient curability. It is preferably at most 95% by mass, more preferably at most 92% by mass.
＜成分（Ｂ）硬化剤＞
本実施形態のエポキシ樹脂組成物に含まれる成分（Ｂ）硬化剤としては、以下に限定されないが、アミン系硬化剤、アミド系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、潜在性硬化剤、触媒型硬化剤等が挙げられる。硬化剤は、これらに限定されるものではない。
<Component (B) curing agent>
The component (B) curing agent contained in the epoxy resin composition of this embodiment includes, but is not limited to, an amine curing agent, an amide curing agent, a phenol curing agent, an acid anhydride curing agent, and a latent curing agent. Examples include curing agents, catalytic curing agents, and the like. The curing agent is not limited to these.
アミン系硬化剤としては、以下に限定されないが、例えば、脂肪族アミン、芳香族アミン等が挙げられる。
脂肪族アミンとしては、以下に限定されないが、例えば、ジエチレントリアミン、トリエチレンテトラアミン、テトラエチレンペンタミン、ｍ－キシレンジアミン、トリメチルへキサメチレンジアミン、２－メチルペンタメチレンジアミン、イソフォロンジアミン、１，３－ビスアミノメチルシクロヘキサン、ビス（４－アミノシクロヘキシル）メタン、ノルボルネンジアミン、１，２－ジアミノシクロヘキサン等が挙げられる。
芳香族アミンとしては、以下に限定されないが、例えば、ジアミノジフェニルメタン、ｍ－フェニレンジアミン、ジアミノジフェニルスルホン、ジエチルトルエンジアミン、トリメチレンビス（４－アミノベンゾエート）、ポリテトラメチレンオキシド－ジ－ｐ－アミノベンゾエート、ＫＡＹＡＨＡＲＤ Ａ－Ａ（日本化薬製）、エタキュア１００（三井化学ファイン製）等が挙げられる。
Examples of the amine curing agent include, but are not limited to, aliphatic amines, aromatic amines, and the like.
Examples of aliphatic amines include, but are not limited to, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1, Examples include 3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane.
Examples of aromatic amines include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylene bis(4-aminobenzoate), polytetramethylene oxide-di-p-amino Examples include benzoate, KAYAHARD AA (manufactured by Nippon Kayaku), and Etacure 100 (manufactured by Mitsui Chemicals Fine).
アミド系硬化剤としては、以下に限定されるものではないが、例えば、活性水素を４つもつジシアンジアミド及びその誘導体であるグアニジン化合物、又はアミン系硬化剤に酸無水物を付加させたもの、並びにヒドラジド系化合物が挙げられる。 Examples of amide curing agents include, but are not limited to, dicyandiamide having four active hydrogen atoms and guanidine compounds that are derivatives thereof, or amine curing agents to which acid anhydrides are added; Examples include hydrazide compounds.
ヒドラジド系化合物からなるヒドラジド系硬化剤としては、以下に限定されるものではないが、例えば、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、フタル酸ジヒドラジド、イソフタル酸ジヒドラジドテレフタル酸ジヒドラジド、ｐ－オキシ安息香酸ヒドラジド、サリチル酸ヒドラジド、フェニルアミノプロピオン酸ヒドラジド、マレイン酸ジヒドラジド等が挙げられる。 Examples of the hydrazide curing agent made of a hydrazide compound include, but are not limited to, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide, Examples include salicylic acid hydrazide, phenylaminopropionic acid hydrazide, maleic acid dihydrazide, and the like.
グアニジン化合物からなるグアニジン系硬化剤としては、以下に限定されるものではないが、例えば、ジシアンジアミド、メチルグアニジン、エチルグアニジン、プロピルグアニジン、ブチルグアニジン、ジメチルグアニジン、トリメチルグアニジン、フェニルグアニジン、ジフェニルグアニジン、トルイルグアニジン等が挙げられる。 Examples of guanidine-based curing agents made of guanidine compounds include, but are not limited to, dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, and toluyl. Examples include guanidine.
酸無水物系硬化剤としては、以下に限定されないが、例えば、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。 Examples of acid anhydride curing agents include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic anhydride. , hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.
フェノール系硬化剤としては、以下に限定されないが、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、フェノールアラルキル樹脂、クレゾールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニル変性フェノール樹脂、ビフェニル変性フェノールアラルキル樹脂、ジシクロペンタジエン変性フェノール樹脂、アミノトリアジン変性フェノール樹脂、ナフトールノボラック樹脂、ナフトール－フェノール共縮合ノボラック樹脂、ナフトール－クレゾール共縮合ノボラック樹脂、アリルアクリルフェノール樹脂等が挙げられる。 Examples of the phenolic curing agent include, but are not limited to, phenol novolac resins, cresol novolak resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, biphenyl-modified phenol resins, biphenyl-modified phenol aralkyl resins, and dicyclopentadiene-modified resins. Examples include phenol resin, aminotriazine modified phenol resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, allyl acrylic phenol resin.
潜在性硬化剤としては、以下に限定されないが、例えば、イミダゾール化合物、ポリアミン化合物、アミン－エポキシアダクト類、アミン－尿素アダクト類、又はこれらを被覆してなるマイクロカプセル型硬化剤、多孔質体に吸着させてなる硬化剤などが挙げられる。その具体例としては、以下に限定されないが、ノバキュア ＨＸ－３７２１、ＨＸ－３７２２、ＨＸ－３６１３、ＨＸ－３９２１ＨＰ、ＨＸＡ９３２２ＨＰ（旭化成株式会社製）、アミキュア ＰＮ－２３Ｊ、ＰＮ－４０Ｊ、ＭＹ－２４（味の素ファインテクノ株式会社製）、フジキュアー ＦＸＲ－１０２０、ＦＸＲ－１０３０（富士化成工業株式会社製）などが挙げられる。これらは１種単独で用いてもよく、２種以上併用してもよい。
低温での良好な硬化性、少量の添加で樹脂硬化が可能であること、短時間硬化で高いガラス転移温度を持つ硬化物を得らえる観点からは、硬化剤としてイミダゾール系硬化剤を含むことが好ましい。イミダゾール系硬化剤に含まれるイミダゾール化合物としては、特に限定されないが、例えば、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、１－（２－シアノエチル）－２－エチル―４－メチルイミダゾール、２，４－ジアミノ－６－［２－メチルイミダゾリル‐（１）］エチル－ｓ－トリアジン、２－フェニルイミダゾリン、２，３－ジヒドロ―１Ｈ－ピロロ［１，２－ａ］ベンズイミダゾールが挙げられる。また、イミダゾール系硬化剤としては、特に限定されないが、例えば、ノバキュア ＨＸ－３７２１、ＨＸ－３７２２、ＨＸ－３６１３、ＨＸ－３９２１ＨＰ、ＨＸＡ９３２２ＨＰ（旭化成株式会社製）が挙げられる。
Examples of latent curing agents include, but are not limited to, imidazole compounds, polyamine compounds, amine-epoxy adducts, amine-urea adducts, microcapsule-type curing agents coated with these, and porous materials. Examples include curing agents obtained by adsorption. Specific examples include, but are not limited to, Novacure HX-3721, HX-3722, HX-3613, HX-3921HP, HXA9322HP (manufactured by Asahi Kasei Corporation), Amicure PN-23J, PN-40J, MY-24 ( (manufactured by Ajinomoto Fine Techno Co., Ltd.), FujiCure FXR-1020, and FXR-1030 (manufactured by Fuji Chemical Industries, Ltd.). These may be used alone or in combination of two or more.
From the viewpoints of good curability at low temperatures, the ability to cure the resin with a small amount of addition, and the ability to obtain a cured product with a high glass transition temperature in a short period of time, an imidazole-based curing agent is included as a curing agent. is preferred. The imidazole compound contained in the imidazole curing agent is not particularly limited, but examples include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, Examples include 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2-phenylimidazoline, and 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole. . Further, the imidazole curing agent is not particularly limited, and examples thereof include Novacure HX-3721, HX-3722, HX-3613, HX-3921HP, and HXA9322HP (manufactured by Asahi Kasei Corporation).
触媒型硬化剤としては、以下に限定されるものではないが、例えば、カチオン系熱硬化触媒、ＢＦ3－アミン錯体等が挙げられる。 Examples of the catalytic curing agent include, but are not limited to, cationic thermosetting catalysts, BF 3 -amine complexes, and the like.
成分（Ｂ）硬化剤は、固体の硬化剤を含むこと、すなわち、２５℃、１０１３ｈＰａで固体である硬化剤を含むことが、保存安定性の点で好ましい。固体の硬化剤をエポキシ樹脂組成物中に分散させておき、所定の温度、及び加熱開始後での所定時間経過後にて硬化反応が開始するメカニズムとすることで、エポキシ樹脂組成物が反応性と貯蔵安定性とを兼ね備えることができる。このような固体の硬化剤として、ジシアンジアミド、固体のイミダゾール系化合物、固体のポリアミン系化合物、及びそれらを含むマスターバッチ型潜在性硬化剤が好ましく、固体のイミダゾール系マイクロカプセル型硬化剤を含むマスターバッチ型潜在性硬化剤としてノバキュア ＨＸ－３７２１、ＨＸ－３７２２、ＨＸ－３６１３、ＨＸ－３９２１ＨＰ、ＨＸＡ９３２２ＨＰを含むことがより好ましい。
常温での保存安定性やディスペンサー等でエポキシ樹脂組成物を塗布する際の増粘制御の観点から、（Ｂ）硬化剤はマイクロカプセル型硬化剤を含むことが好ましい。マイクロカプセル型硬化剤としては、ノバキュア ＨＸ－３７２１、ＨＸ－３７２２、ＨＸ－３６１３、ＨＸ－３９２１ＨＰ、ＨＸＡ９３２２ＨＰを用いることができる。
また、架橋点を多くすることで、架橋構造を複雑化させ、硬化物の強度を向上させる観点から、成分（Ｂ）として、活性水素を４つ以上含む化合物を含むことが好ましく、さらに基材との密着性を向上させる観点で、ヘテロ原子を含み且つ活性水素を４つ以上含む化合物を含むことがより好ましい。このような化合物としては、特に限定されないが、例えば、ジシアンジアミドが挙げられる。
In terms of storage stability, the component (B) curing agent preferably contains a solid curing agent, that is, a curing agent that is solid at 25° C. and 1013 hPa. A solid curing agent is dispersed in an epoxy resin composition, and the curing reaction starts at a predetermined temperature and after a predetermined period of time after the start of heating, thereby making the epoxy resin composition less reactive. It can also have storage stability. As such a solid curing agent, dicyandiamide, a solid imidazole-based compound, a solid polyamine-based compound, and a masterbatch type latent curing agent containing these are preferable, and a masterbatch containing a solid imidazole-based microcapsule type curing agent is preferable. More preferably, Novacure HX-3721, HX-3722, HX-3613, HX-3921HP, and HXA9322HP are included as the latent curing agent.
From the viewpoint of storage stability at room temperature and control of thickening when applying the epoxy resin composition with a dispenser, the curing agent (B) preferably contains a microcapsule type curing agent. As the microcapsule type curing agent, Novacure HX-3721, HX-3722, HX-3613, HX-3921HP, and HXA9322HP can be used.
In addition, from the viewpoint of complicating the crosslinking structure and improving the strength of the cured product by increasing the number of crosslinking points, it is preferable that the component (B) contains a compound containing four or more active hydrogens, and furthermore, the base material It is more preferable to include a compound containing a hetero atom and containing four or more active hydrogens, from the viewpoint of improving the adhesion with the material. Such a compound is not particularly limited, but includes, for example, dicyandiamide.
これらの硬化剤は、１種単独で使用してもよいし、２種以上を併用してもよい。 These curing agents may be used alone or in combination of two or more.
成分（Ｂ）の含有量は、エポキシ樹脂組成物全体に対して、１質量％以上であることが好ましく、３質量％以上であることがより好ましく、５質量％以上であることがさらに好ましい。また、成分（Ｂ）の含有量は、エポキシ樹脂組成物全体に対して、４０質量％以下であることが好ましく、３５質量％以下であることがより好ましく、３０質量％以下であることがさらに好ましい。 The content of component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the entire epoxy resin composition. Further, the content of component (B) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on the entire epoxy resin composition. preferable.
＜成分（Ｃ）式（１）で示される化合物＞
本実施形態のエポキシ樹脂組成物は、下記式（１）で示される化合物（成分（Ｃ））を含む。本実施形態のエポキシ樹脂組成物は、下記式（１）で示される化合物（成分（Ｃ））を含むことで、優れた低温硬化性、低粘度化、硬化時間の短縮、十分な硬化領域の確保、が可能となる。
さらに、（Ｂ）硬化剤への配位性を高め、より硬化性を向上させる観点から、上記式（１）のＲ1がヒドロキシル基であることが好ましい。
また、ヒドロキシル基の配位性を立体障害により阻害しない観点から、上記式（１）のＲ2、Ｒ3及びＲ4が水素であることが好ましい。
<Component (C) compound represented by formula (1)>
The epoxy resin composition of this embodiment contains a compound (component (C)) represented by the following formula (1). The epoxy resin composition of this embodiment contains the compound represented by the following formula (1) (component (C)), thereby exhibiting excellent low-temperature curability, low viscosity, shortening of curing time, and sufficient hardening area. It becomes possible to secure.
Furthermore, from the viewpoint of increasing the coordination to the curing agent (B) and further improving the curability, it is preferable that R 1 in the above formula (1) is a hydroxyl group.
Further, from the viewpoint of not inhibiting the coordination of the hydroxyl group due to steric hindrance, it is preferable that R 2 , R 3 and R 4 in the above formula (1) are hydrogen.
上記式（１）で示される化合物として、特に限定されないが、例えば、３－フェノキシ－１－プロパノール、３－フェノキシ－１，２－プロパンジオール、３－フェノキシ－１，３－プロパンジオール、メフェネシン（ ３－（２－Ｍｅｔｈｙｌｐｈｅｎｏｘｙ）－１，２－ｐｒｏｐａｎｅｄｉｏｌ）、グアイフェネシン（３－（２ｍｅｔｈｏｘｙｐｈｅｎｏｘｙ）ｐｒｏｐａｎｅ－１，２－ｄｉｏｌ）、Ｂｉｓｐｈｅｎｏｌ Ａ （３－ｈｙｄｒｏｘｙｐｒｏｐｙｌ） ｇｌｙｃｉｄｙｌ ｅｔｈｅｒ、Ｂｉｓｐｈｅｎｏｌ Ａ （２，３－ｄｉｈｙｄｒｏｘｙｐｒｏｐｙｌ） ｇｌｙｃｉｄｙｌ ｅｔｈｅｒ、
下記式（１－１）で表される化合物（以下「化合物１」とも記す）、
A compound represented by the following formula (1-1) (hereinafter also referred to as "compound 1"),
成分（Ｃ）の含有量は、エポキシ樹脂組成物全体に対して、０．００００１質量％以上であることが好ましく、０．０００１質量％以上であることがより好ましく、０．００１質量％以上であることがさらに好ましい。また、成分（Ｃ）の含有量は、エポキシ樹脂組成物全体に対して、２０質量％未満であることが好ましく、１５質量％未満であることがより好ましく、１０質量％未満であることがさらに好ましく、８質量％未満であることがよりさらに好ましく、７質量％未満であることがさらにより好ましく、６質量％未満であることが極めて好ましく、５質量％未満であることがより極めて好ましく、３質量％未満であることがさらに極めて好ましく、２質量％未満であることが特に極めて好ましい。本実施形態のエポキシ樹脂組成物は、０．００００１質量％以上の成分（Ｃ）が含まれることで、増粘開始温度の低下、低粘度化、硬化時間短縮、十分な硬化領域の硬化がより一層達成される。また、保存安定性の観点で、成分（Ｃ）の含有量は、エポキシ樹脂組成物全体に対して、２０質量％未満であることが好ましい。 The content of component (C) is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and 0.001% by mass or more based on the entire epoxy resin composition. It is even more preferable that there be. Further, the content of component (C) is preferably less than 20% by mass, more preferably less than 15% by mass, and even more preferably less than 10% by mass, based on the entire epoxy resin composition. Preferably, less than 8% by weight is even more preferable, even more preferably less than 7% by weight, very preferably less than 6% by weight, even more preferably less than 5% by weight, 3 Very preferably less than % by weight, particularly very preferably less than 2% by weight. The epoxy resin composition of this embodiment contains component (C) in an amount of 0.00001% by mass or more, thereby lowering the thickening start temperature, lowering the viscosity, shortening the curing time, and further curing a sufficient hardened area. more accomplished. Further, from the viewpoint of storage stability, the content of component (C) is preferably less than 20% by mass based on the entire epoxy resin composition.
成分（Ｃ）が低粘度化、低温硬化性の改善、硬化時間の短縮、硬化領域の改善に効果を示すメカニズムとして、限定する趣旨ではないが、以下のことが考えられる。（Ａ）エポキシ樹脂同士の相互作用に対して、成分（Ｃ）の芳香族基やヒドロキシル基が作用することで、（Ａ）エポキシ樹脂同士での相互作用が解消され、エポキシ樹脂組成物全体として分子移動が容易になるため、低粘度化する。また、成分（Ｃ）のヒドロキシル基と（Ｂ）硬化剤との間での配位結合を形成することで、（Ｂ）硬化剤と（Ａ）エポキシ樹脂との相溶性が高まり、エポキシ樹脂組成物中での（Ｂ）硬化剤の拡散性が向上することで、より低温での（Ｂ）硬化剤の（Ａ）エポキシ樹脂成分中への十分な拡散と、それに伴う硬化反応を可能にする。なお、（Ｂ）硬化剤への配位性を高める観点において、成分（Ｃ）としては、末端モノヒドロキシル基構造よりも１，２－ジオール構造の方がより好ましい。硬化時間の短縮、硬化領域の改善についても、前述の成分（Ｃ）の配位後の（Ｂ）硬化剤と（Ａ）エポキシ樹脂との相溶性向上と拡散性向上が寄与している。相互作用や配位性、相溶性に対する効果は、分子構造の影響を大きく受ける。したがって、本実施形態のエポキシ樹脂組成物は、成分（Ｃ）が上記式（１）で示される化合物を含む。 Although not intended to be limiting, the following may be considered as a mechanism by which component (C) exhibits effects on lowering viscosity, improving low-temperature curability, shortening curing time, and improving cured area. (A) The aromatic group and hydroxyl group of component (C) act on the interaction between the epoxy resins, so that the interaction between the (A) epoxy resins is eliminated, and the epoxy resin composition as a whole Lower viscosity because molecules move more easily. In addition, by forming a coordination bond between the hydroxyl group of component (C) and the curing agent (B), the compatibility between the curing agent (B) and the epoxy resin (A) increases, and the epoxy resin composition By improving the diffusivity of the (B) curing agent in the material, it is possible to sufficiently diffuse the (B) curing agent into the (A) epoxy resin component and the accompanying curing reaction at lower temperatures. . In addition, from the viewpoint of improving coordination to the curing agent (B), a 1,2-diol structure is more preferable than a terminal monohydroxyl group structure as component (C). The improvement in compatibility and diffusivity between the curing agent (B) and the epoxy resin (A) after coordination of the component (C) mentioned above also contribute to the shortening of the curing time and the improvement of the curing area. The effects on interaction, coordination, and compatibility are greatly influenced by molecular structure. Therefore, in the epoxy resin composition of this embodiment, component (C) includes a compound represented by the above formula (1).
相溶性の指標として、ｓｐ値（δ）があり、化合物同士のｓｐ値差が小さい場合、良好な相溶性を示すことが知られている。成分（Ｃ）の成分（Ａ）エポキシ樹脂への優れた相溶性と、成分（Ｂ）硬化剤へ成分（Ｃ）が配位した後の成分（Ａ）への相溶性に優れることで、低粘度化、低温硬化性の改善、硬化時間の短縮、硬化領域の改善の効果をより発揮する観点から、成分（Ｃ）のｓｐ値が成分（Ａ）エポキシ樹脂に対して近しい値を有することが好ましい。以下は、ＲＯＢＥＲＴ Ｆ． ＦＥＤＯＲＳ著 ＰＯＬＹＭＥＲ ＥＮＧＩＮＥＥＲＩＮＧ ＡＮＤ ＳＣＩＥＮＣＥ， ＦＥＢＲＵＡＲＹ， １９７４， Ｖｏｌ． １４， Ｎｏ． ２に記載の値を用いて、２５℃における、各化合物のｓｐ値をＦｅｄｏｒｓの計算法（数式（ｉ））により求めたものである。
δ＝（ΣΔｅ／ΣΔｖ）1/2 ・・・・・数式（ｉ）
Δｅは置換基ごとの凝集エネルギーを表し、Δｖはモル分子容を示す。
〔成分（Ａ）〕
ビスフェノールＡ型エポキシ樹脂（ｎ＝０体）・・・・・δ＝１０．９（ｃａｌ／ｃｍ3）1/2
ビスフェノールＦ型エポキシ樹脂（ｎ＝０体）・・・・・δ＝１２．１（ｃａｌ／ｃｍ3）1/2
エポキシクレゾールノボラック ・・・・・δ＝１１．０（ｃａｌ／ｃｍ3）1/2
テトラグリシジルジアミノジフェニルメタン ・・・・δ＝１１．９（ｃａｌ／ｃｍ3）1/2
〔成分（Ｂ）〕
ジシアンジアミド ・・・・・δ＝１７．８（ｃａｌ／ｃｍ3）1/2
〔成分（Ｃ）〕
３－フェノキシ－１－プロパノール ・・・・・δ＝１２．０（ｃａｌ／ｃｍ3）1/2
３－フェノキシ－１，２－プロパンジオール ・・・・δ＝１４．３（ｃａｌ／ｃｍ3）1/2
Ｂｉｓｐｈｅｎｏｌ Ａ （３－ｈｙｄｒｏｘｙｐｒｏｐｙｌ） ｇｌｙｃｉｄｙｌ ｅｔｈｅｒ ・・・・・δ＝１１．６（ｃａｌ／ｃｍ3）1/2
Ｂｉｓｐｈｅｎｏｌ Ａ （２，３－ｄｉｈｙｄｒｏｘｙｐｒｏｐｙｌ） ｇｌｙｃｉｄｙｌ ｅｔｈｅｒ ・・・・・δ＝１２．９（ｃａｌ／ｃｍ3）1/2
化合物１ ・・・・・δ＝１２．０（ｃａｌ／ｃｍ3）1/2
化合物２ ・・・・・δ＝１２．０（ｃａｌ／ｃｍ3）1/2
化合物３ ・・・・・δ＝１２．６（ｃａｌ／ｃｍ3）1/2
〔その他成分〕
グリセロール ・・・・・δ＝２０．０（ｃａｌ／ｃｍ3）1/2
成分（Ｃ）のｓｐ値は成分（Ａ）のｓｐ値と近しいことで、低粘度化、低温硬化性の改善、硬化時間の短縮、硬化領域の改善の効果をより発揮する観点から、成分（Ａ）がｓｐ値が１０～１３（ｃａｌ／ｃｍ3）1/2のエポキシ樹脂を含む場合に、成分（Ｃ）のｓｐ値は、下限値として、７（ｃａｌ／ｃｍ3）1/2以上が好ましく、８（ｃａｌ／ｃｍ3）1/2以上がより好ましく、９（ｃａｌ／ｃｍ3）1/2以上がさらに好ましく、１０（ｃａｌ／ｃｍ3）1/2以上がよりさらに好ましく、１１（ｃａｌ／ｃｍ3）1/2以上がさらにより好ましく、上限値として、２０（ｃａｌ／ｃｍ3）1/2未満が好ましく、１８（ｃａｌ／ｃｍ3）1/2以下がより好ましく、１６（ｃａｌ／ｃｍ3）1/2以下がさらにより好ましい。
An index of compatibility is the sp value (δ), and it is known that compounds exhibit good compatibility when the difference in sp value is small. The excellent compatibility of component (C) with component (A) epoxy resin and the excellent compatibility with component (A) after component (C) coordinates with component (B) curing agent, In order to more effectively exhibit the effects of increasing viscosity, improving low-temperature curability, shortening the curing time, and improving the curing area, it is preferable that the sp value of component (C) be close to that of the component (A) epoxy resin. preferable. Below is Robert F. By FEDORS POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. The sp value of each compound at 25° C. was determined by the Fedors calculation method (formula (i)) using the values described in 2.
δ=(Σ Δ e/Σ Δ v) 1/2 ...Formula (i)
Δ e represents the cohesive energy for each substituent, and Δ v represents the molar molecular volume.
[Component (A)]
Bisphenol A type epoxy resin (n=0 body)...δ=10.9 (cal/cm 3 ) 1/2
Bisphenol F type epoxy resin (n=0 body)...δ=12.1 (cal/cm 3 ) 1/2
Epoxy cresol novolac...δ=11.0 (cal/ cm3 ) 1/2
Tetraglycidyldiaminodiphenylmethane...δ=11.9 (cal/cm 3 ) 1/2
[Component (B)]
Dicyandiamide...δ=17.8 (cal/cm 3 ) 1/2
[Component (C)]
3-phenoxy-1-propanol...δ=12.0 (cal/cm 3 ) 1/2
3-phenoxy-1,2-propanediol...δ=14.3 (cal/cm 3 ) 1/2
Bisphenol A (3-hydroxypropyl) glycidyl ether...δ=11.6 (cal/cm 3 ) 1/2
Bisphenol A (2,3-dihydroxypropyl) glycidyl ether...δ=12.9 (cal/cm 3 ) 1/2
Compound 1...δ=12.0 (cal/cm 3 ) 1/2
Compound 2...δ=12.0 (cal/cm 3 ) 1/2
Compound 3...δ=12.6 (cal/cm 3 ) 1/2
[Other ingredients]
Glycerol ・・・・・・δ=20.0 (cal/cm 3 ) 1/2
Since the sp value of component (C) is close to that of component (A), component ( When A) contains an epoxy resin with an sp value of 10 to 13 (cal/cm 3 ) 1/2 , the lower limit of the sp value of component (C) is 7 (cal/cm 3 ) 1/2 or more. is preferable, 8 (cal/cm 3 ) 1/2 or more is more preferable, 9 (cal/cm 3 ) 1/2 or more is even more preferable, 10 (cal/cm 3 ) 1/2 or more is even more preferable, 11 (cal/cm 3 ) 1/2 or more is even more preferable, the upper limit is preferably less than 20 (cal/cm 3 ) 1/2 , more preferably 18 (cal/cm 3 ) 1/2 or less, and 16 ( Cal/cm 3 ) 1/2 or less is even more preferable.
成分（Ｃ）は、その他成分との混合時に添加してもよく、混合後に系中で生成してもよく、また、その他成分（Ａ）及び（Ｂ）、後述の成分（Ｄ）及び（Ｅ）を製造する際に系中で発生させてもよい。 Component (C) may be added at the time of mixing with other components, may be generated in the system after mixing, or may be added to other components (A) and (B), components (D) and (E) described below. ) may be generated in the system during production.
＜成分（Ｄ）硬化促進剤＞
本実施形態のエポキシ樹脂組成物は、硬化反応を促進する目的で、（Ｄ）硬化促進剤（以下「成分（Ｄ）」とも記す）を含むことができる。（Ｄ）硬化促進剤としては、特に限定されないが、例えば、アミン系化合物、イミダゾール系化合物、オニウム化合物のボロン塩、リン系化合物、ルイス酸、尿素誘導体等が挙げられる。尿素誘導体としては、特に限定されないが、例えば、３，４－ジクロロフェニル－Ｎ，Ｎ－ジメチル尿素、３－（４－クロロフェニル）－１，１－ジメチル尿素等が挙げられる。これらは単独で使用してもよいし、二種以上を併用してもよい。
成分（Ｂ）硬化剤に該当するイミダゾール化合物は、他の成分（Ｂ）硬化剤を含む場合に、組み合わせによっては、成分（Ｄ）硬化促進剤に該当する。本明細書中では、以下に記載の場合にイミダゾール化合物は成分（Ｄ）硬化促進剤とする。
<Component (D) Curing accelerator>
The epoxy resin composition of this embodiment can contain (D) a curing accelerator (hereinafter also referred to as "component (D)") for the purpose of promoting the curing reaction. (D) The curing accelerator is not particularly limited, and includes, for example, amine compounds, imidazole compounds, boron salts of onium compounds, phosphorus compounds, Lewis acids, urea derivatives, and the like. Examples of the urea derivative include, but are not limited to, 3,4-dichlorophenyl-N,N-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and the like. These may be used alone or in combination of two or more.
The imidazole compound that corresponds to component (B) curing agent corresponds to component (D) curing accelerator depending on the combination when other component (B) curing agent is included. In this specification, the imidazole compound is used as component (D) curing accelerator in the following cases.
成分（Ｂ）が、グアニジン化合物、ヒドラジド系化合物、酸無水物系化合物、フェノール樹脂、ポリチオール系化合物、芳香族アミン、ベンゾオキサジン、シアネートエステルのうち少なくとも１種を含み、イミダゾール化合物を加えることで、硬化時間の短縮、硬化温度の低温化、硬化物強度の向上等の硬化性向上が発揮される場合に、イミダゾール化合物は成分（Ｄ）硬化促進剤とする。 Component (B) contains at least one of a guanidine compound, a hydrazide compound, an acid anhydride compound, a phenol resin, a polythiol compound, an aromatic amine, a benzoxazine, and a cyanate ester, and by adding an imidazole compound, An imidazole compound is used as the component (D) curing accelerator when it exhibits improvements in curability such as shortening of curing time, lowering of curing temperature, and improvement in the strength of cured products.
また、成分（Ｂ）が２種以上のイミダゾール化合物を含む場合に、硬化時間の短縮、硬化温度の低温化、硬化物強度の向上等の硬化性向上への部数当たりの寄与度が小さい方のイミダゾール化合物を成分（Ｄ）硬化促進剤とする。 In addition, when component (B) contains two or more types of imidazole compounds, the one that contributes less per unit to the improvement of curability, such as shortening the curing time, lowering the curing temperature, and improving the strength of the cured product, An imidazole compound is used as the component (D) curing accelerator.
イミダゾール化合物を成分（Ｄ）硬化促進剤とする場合の上記に記載の成分（Ｂ）硬化剤の具体的例としては、上記の［成分（Ｂ）硬化剤］の段落に記載の化合物等が使用できる。 As specific examples of the component (B) curing agent described above when an imidazole compound is used as the component (D) curing accelerator, the compounds described in the paragraph of [Component (B) curing agent] above are used. can.
組み合わせにより成分（Ｄ）硬化促進剤となるイミダゾール化合物としては、特に限定されないが、例えば、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、１－（２－シアノエチル）－２－エチル―４－メチルイミダゾール、２，４－ジアミノ－６－［２－メチルイミダゾリル‐（１）］エチル－ｓ－トリアジン、２－フェニルイミダゾリン、２，３－ジヒドロ―１Ｈ－ピロロ［１，２－ａ］ベンズイミダゾール、ノバキュア ＨＸ－３７２１、ＨＸ－３７２２、ＨＸ－３６１３、ＨＸ－３９２１ＨＰ、ＨＸＡ９３２２ＨＰ（旭化成製）、ＡＥＲハードナー Ｄ１２０７、Ｄ１３０１（旭化成製）等が挙げられる。
成分（Ｄ）の含有量はエポキシ樹脂組成物中、十分な硬化性を示す観点から、２質量％以上であることが好ましく、３質量％以上であることがより好ましく、４質量％以上であることがさらに好ましい。また、成分（Ｄ）の含有量はエポキシ樹脂組成物中、十分な保存安定性を示す観点から、２０質量％以下であることが好ましく、１７質量％以下であることがより好ましく、１４質量％以下であることがさらに好ましい。
The imidazole compound that becomes the component (D) curing accelerator in combination is not particularly limited, but includes, for example, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4 -Methylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo[1,2-a]benz Imidazole, Novacure HX-3721, HX-3722, HX-3613, HX-3921HP, HXA9322HP (manufactured by Asahi Kasei), AER Hardener D1207, D1301 (manufactured by Asahi Kasei), and the like.
The content of component (D) in the epoxy resin composition is preferably 2% by mass or more, more preferably 3% by mass or more, and 4% by mass or more from the viewpoint of exhibiting sufficient curability. It is even more preferable. Further, the content of component (D) in the epoxy resin composition is preferably 20% by mass or less, more preferably 17% by mass or less, and 14% by mass from the viewpoint of exhibiting sufficient storage stability. It is more preferable that it is the following.
＜成分（Ｅ）フィラー＞
本実施形態のエポキシ樹脂組成物は、必要に応じて（Ｅ）有機フィラー及び／又は無機フィラー（以下「成分（Ｅ）」とも記す）を含んでもよい。
<Component (E) filler>
The epoxy resin composition of this embodiment may contain (E) an organic filler and/or an inorganic filler (hereinafter also referred to as "component (E)") as necessary.
有機フィラーとしては、以下に限定されるものではないが、例えば、トリブロック共重合体のような熱可塑性樹脂及び熱可塑性エラストマー、炭素繊維、セルロース、ポリエチレン粉、並びにポリプロピレン粉等が挙げられる。これらの有機フィラーは、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the organic filler include, but are not limited to, thermoplastic resins and thermoplastic elastomers such as triblock copolymers, carbon fibers, cellulose, polyethylene powder, and polypropylene powder. These organic fillers may be used alone or in combination of two or more.
無機フィラーとしては、以下に限定されるものではないが、例えば、溶融シリカ、結晶シリカ、アルミナ、タルク、窒化ケイ素、窒化アルミ、酸化亜鉛（ＺｎＯ）、コールタール、ガラス繊維、アスベスト繊維、ほう素繊維、石英紛、鉱物性ケイ酸塩、雲母、アスベスト粉、スレート粉等が挙げられる。これらの無機フィラーは、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Inorganic fillers include, but are not limited to, fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride, zinc oxide (ZnO), coal tar, glass fiber, asbestos fiber, boron. Examples include fiber, quartz powder, mineral silicate, mica, asbestos powder, and slate powder. These inorganic fillers may be used alone or in combination of two or more.
これらの有機フィラー及び無機フィラーは、エポキシ樹脂組成物の粘弾性を変化させて、粘度、貯蔵弾性率、及びチキソトロープ性を適正化する機能があり、さらにはエポキシ樹脂組成物の硬化物の破壊靭性を向上させ、硬化収縮の低減を低減させる傾向にある。
成分（Ｅ）の含有量はエポキシ樹脂組成物中、十分なチキソトロープ性の適正化や破壊靭性の向上の観点から、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましく、２５質量％以上であることがさらに好ましい。また、成分（Ｅ）の含有量はエポキシ樹脂組成物中、粘度が十分に低く取り扱いに優れる観点から、８５質量％以下であることが好ましく、８０質量％以下であることがより好ましく、７５質量％以下であることがさらに好ましい。
These organic fillers and inorganic fillers have the function of changing the viscoelasticity of the epoxy resin composition, optimizing the viscosity, storage modulus, and thixotropy, and further improving the fracture toughness of the cured product of the epoxy resin composition. and tend to reduce curing shrinkage.
The content of component (E) in the epoxy resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of optimizing sufficient thixotropy and improving fracture toughness. , more preferably 25% by mass or more. In addition, the content of component (E) in the epoxy resin composition is preferably 85% by mass or less, more preferably 80% by mass or less, and 75% by mass or less, from the viewpoint of sufficiently low viscosity and excellent handling. % or less is more preferable.
本実施形態のエポキシ樹脂組成物には、必要に応じて、上述した成分以外に、添加剤として、希釈剤、反応性希釈剤、顔料、染料、流れ調整剤、増粘剤、強化剤、離型剤、湿潤剤、難燃剤、界面活性剤、樹脂類等を、さらに含むことができる。 In addition to the above-mentioned components, the epoxy resin composition of this embodiment may optionally contain additives such as a diluent, a reactive diluent, a pigment, a dye, a flow regulator, a thickener, a reinforcing agent, and a release agent. It may further contain molding agents, wetting agents, flame retardants, surfactants, resins, and the like.
＜エポキシ樹脂組成物の製造方法＞
本実施形態のエポキシ樹脂組成物は上記成分（Ａ）、成分（Ｂ）及び成分（Ｃ）を混合することによって得ることができる。各成分の混合方法は、特に限定されず、一般的な混合設備と加工条件が適用される。具体的には、特に限定されないが、例えば、上記成分（Ａ）～（Ｃ）と、必要に応じて上記成分（Ｄ）及び（Ｅ）並びにその他添加剤成分等とを、３本ロール等のミキシングロール、ディゾルバ、プラネタリミキサ、ニーダ、押出し機等を用いて均一になるまで充分に混合してエポキシ樹脂組成物を得る方法が挙げられる。
<Method for manufacturing epoxy resin composition>
The epoxy resin composition of this embodiment can be obtained by mixing the above component (A), component (B), and component (C). The method of mixing each component is not particularly limited, and general mixing equipment and processing conditions are applied. Specifically, although not particularly limited, for example, the above components (A) to (C) and, if necessary, the above components (D) and (E), and other additive components, etc. Examples include a method of obtaining an epoxy resin composition by sufficiently mixing until uniform using a mixing roll, a dissolver, a planetary mixer, a kneader, an extruder, or the like.
本実施形態のエポキシ樹脂組成物の製造方法において、各成分を混合する際は、成分（Ｃ）の分散性を高めることで、均一なエポキシ樹脂組成物が得られる観点と、製造途中での硬化反応を抑制することで生産性を高める観点とから、成分（Ａ）及び成分（Ｂ）の群から選ばれる少なくとも一つを有する化合物又は組成物に成分（Ｃ）を添加する工程を含むことが好ましい。 In the method for producing an epoxy resin composition of the present embodiment, when mixing each component, the dispersibility of component (C) is increased to obtain a uniform epoxy resin composition, and curing during production From the viewpoint of increasing productivity by suppressing the reaction, it may include a step of adding component (C) to a compound or composition having at least one selected from the group of component (A) and component (B). preferable.
本実施形態のエポキシ樹脂組成物の製造方法において、さらにエポキシ樹脂組成物が成分（Ｄ）を含む場合、各成分を混合する際は、成分（Ｃ）の分散性を高めることで、均一なエポキシ樹脂組成物が得られる観点と、製造途中での硬化反応を抑制することで生産性を高める観点から、成分（Ａ）、成分（Ｂ）、及び成分（Ｄ）の群から選ばれる少なくとも一つを有する化合物又は組成物に成分（Ｃ）を添加する工程を含むことが好ましい。 In the method for producing an epoxy resin composition of the present embodiment, when the epoxy resin composition further contains component (D), when mixing each component, by increasing the dispersibility of component (C), uniform epoxy resin is produced. At least one selected from the group of component (A), component (B), and component (D) from the viewpoint of obtaining a resin composition and increasing productivity by suppressing curing reaction during production. It is preferable to include a step of adding component (C) to the compound or composition having the following.
本実施形態のエポキシ樹脂組成物の製造方法において、さらにエポキシ樹脂組成物が成分（Ｅ）を含む場合、各成分を混合する際は、成分（Ｃ）の分散性を高めることで、均一なエポキシ樹脂組成物が得られる観点と、製造途中での硬化反応を抑制することで生産性を高める観点から、成分（Ａ）、成分（Ｂ）、及び成分（Ｅ）の群から選ばれる少なくとも一つを有する化合物又は組成物に成分（Ｃ）を添加する工程を含むことが好ましい。 In the method for producing an epoxy resin composition of the present embodiment, when the epoxy resin composition further contains component (E), when mixing each component, by increasing the dispersibility of component (C), uniform epoxy resin is produced. At least one selected from the group of component (A), component (B), and component (E) from the viewpoint of obtaining a resin composition and increasing productivity by suppressing curing reaction during production. It is preferable to include a step of adding component (C) to the compound or composition having the following.
次に、本発明を、実施例及び比較例によりさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。なお、以下において「部」及び「％」は、特に断りがない限り質量基準である。 Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following, "parts" and "%" are based on mass unless otherwise specified.
（エポキシ樹脂組成物の調製）
以下の表１に示す配合比率で、後述する成分（Ａ）～（Ｃ）及びその他成分を計量後、ノンバブリングニーダーでこれらの成分を２分間の撹拌及び３分間の脱泡を行い、混合し、エポキシ樹脂組成物を調製した。なお、表１における各成分の配合量は、（Ａ）成分の合計量を１００質量部としたときの質量部表示で示されている。
(Preparation of epoxy resin composition)
After weighing the components (A) to (C) and other components described below at the blending ratio shown in Table 1 below, these components were mixed using a non-bubbling kneader by stirring for 2 minutes and defoaming for 3 minutes. , an epoxy resin composition was prepared. Note that the blending amount of each component in Table 1 is expressed in parts by mass when the total amount of component (A) is 100 parts by mass.
（増粘開始温度測定）
レオメーター（ＨＡＡＫＥ ＭＡＲＳ、Ｔｈｅｒｍｏ ｓｃｉｅｎｔｉｆｉｃ製）により昇温速度５℃／分、オシレーションモード（ｆ＝１Ｈｚ）にて、エポキシ樹脂組成物を２５℃から２００℃まで昇温した際の、動的粘度η’―温度曲線を取得した。得られた動的粘度―温度曲線において、Ｔ０℃～Ｔ０＋５℃の範囲で動的粘度η‘が単調増加であり、Ｔ０℃での動的粘度η’（Ｔｏ℃）と比較してＴ０＋５℃での動的粘度η‘（Ｔ０＋５℃）が数式（１）を満たす温度Ｔ０℃を増粘開始温度とした。
η‘（Ｔ０＋５℃）－η’（Ｔ０℃）≧５００（ｍＰａ・ｓ）・・・・・・数式（１）
(Thickening start temperature measurement)
Dynamic viscosity when the epoxy resin composition was heated from 25°C to 200°C using a rheometer (HAAKE MARS, manufactured by Thermo scientific) at a heating rate of 5°C/min in oscillation mode (f = 1Hz) A η'-temperature curve was obtained. In the obtained dynamic viscosity-temperature curve, the dynamic viscosity η' increases monotonically in the range of T0°C to T0+5°C, and compared to the dynamic viscosity η' (To°C) at T0°C, it increases at T0+5°C. The temperature T0°C at which the dynamic viscosity η' (T0+5°C) satisfies the formula (1) was defined as the viscosity-increasing temperature.
η'(T0+5℃)-η'(T0℃)≧500(mPa・s)・・・Formula (1)
（エポキシ樹脂組成物の初期粘度測定）
Ｅ型粘度計（ＴＶＥ－３５Ｈ、東機産業株式会社社製）を用いて室温（２５℃）にてエポキシ樹脂組成物を調製した直後の粘度（初期粘度）を測定した。
(Initial viscosity measurement of epoxy resin composition)
The viscosity (initial viscosity) immediately after preparing the epoxy resin composition was measured at room temperature (25° C.) using an E-type viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.).
（ゲルタイム測定）
キュラストメーター（キュラストメーターＶ、テイ・エスエンジニアリング社製）を用いて、設定温度８０℃にてエポキシ樹脂組成物のゲルタイム測定を実施し、トルク－加硫時間チャートを得た。本実施形態においては、得られたチャートについて、１Ｎ・ｍとなる点と０．５Ｎ・ｍとなる点とを求め、二つの点を通る直線が加硫時間軸と交わる時間をゲルタイムと定義した。
(Gel time measurement)
The gel time of the epoxy resin composition was measured using a Curelastometer (Curelastometer V, manufactured by TS Engineering Co., Ltd.) at a set temperature of 80° C., and a torque-vulcanization time chart was obtained. In this embodiment, for the obtained chart, a point at which the pressure is 1N.m and a point at which the pressure is 0.5N.m are determined, and the time at which a straight line passing through the two points intersects with the vulcanization time axis is defined as gel time. .
（保存安定性倍率）
エポキシ樹脂組成物を調製した直後の初期粘度と、エポキシ樹脂組成物を４０℃、７日間放置後での経過時粘度とをＥ型粘度計を用いて室温（２５℃）にて測定し、下記数式（２）にて保存安定性倍率を算出した。
保存安定性倍率＝４０℃、７日放置後経過時粘度／初期粘度 ・・・・数式（２）
保存安定性倍率は、２以下が好ましく、１．５以下がより好ましく、１．２以下がさらに好ましく、１．１以下がさらにより好ましく、１が特に好ましい。
(Storage stability factor)
The initial viscosity immediately after preparing the epoxy resin composition and the elapsed viscosity after the epoxy resin composition was left at 40°C for 7 days were measured at room temperature (25°C) using an E-type viscometer. The storage stability ratio was calculated using the formula (2).
Storage stability magnification = 40℃, viscosity after 7 days of storage/initial viscosity...Equation (2)
The storage stability multiplier is preferably 2 or less, more preferably 1.5 or less, even more preferably 1.2 or less, even more preferably 1.1 or less, and particularly preferably 1.
（硬化領域）
縦：５５０ｍｍ×幅３５０ｍｍ×厚み２ｍｍのテフロン（登録商標）製の型に、エポキシ樹脂組成物を開口部まで十分に流し入れ、加熱炉にて設定温度１００℃で９０分間加熱した。加熱完了後、テフロン（登録商標）製型から取り外した硬化体の体積をＶｃ、エポキシ樹脂組成物を流し入れた体積をＶ０とし、下記数式（３）にて硬化領域を算出した。
硬化領域（％）＝１００×Ｖｃ／Ｖ０ ・・・・・・数式（３）
硬化領域の割合（％）に応じて以下の判定を下す。
The epoxy resin composition was sufficiently poured into the opening of a Teflon (registered trademark) mold having length: 550 mm x width 350 mm x thickness 2 mm, and heated in a heating furnace at a set temperature of 100° C. for 90 minutes. After completion of heating, the volume of the cured product removed from the Teflon (registered trademark) mold was set as Vc, and the volume into which the epoxy resin composition was poured was set as V0, and the cured area was calculated using the following formula (3).
Cured area (%) = 100 x Vc/V0 ... Formula (3)
The following judgment is made according to the ratio (%) of the hardened area.
以下表１に記載の成分は以下のとおりである。
〔（Ａ）エポキシ樹脂〕
成分Ａ－１：ビスフェノールＡ型エポキシ樹脂（三菱ケミカル株式会社製）（エポキシ当量 １８２ｇ／ｅｑ．）
〔（Ｂ）硬化剤〕
成分Ｂ－１：ジシアンジアミド（和光純薬工業株式会社製）
成分Ｂ－２：ノバキュアＨＸＡ９３２２ＨＰ（旭化成株式会社製）
〔（Ｃ）式（１）で示される化合物〕
成分Ｃ－１：３－フェノキシ－１，２－プロパンジオール（東京化成工業株式会社製）
成分Ｃ－２：３－フェノキシ－１－プロパノール（東京化成工業株式会社製）
〔（Ｄ）硬化促進剤〕
成分Ｄ－１：ＡＥＲハードナーＤ１３０１（旭化成株式会社製）
〔その他の成分〕
その他成分－１：グリセロール（東京化成工業株式会社製）
The components listed in Table 1 below are as follows.
[(A) Epoxy resin]
Component A-1: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) (epoxy equivalent 182 g/eq.)
[(B) Curing agent]
Component B-1: Dicyandiamide (manufactured by Wako Pure Chemical Industries, Ltd.)
Component B-2: Novacure HXA9322HP (manufactured by Asahi Kasei Corporation)
[(C) Compound represented by formula (1)]
Component C-1: 3-phenoxy-1,2-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Component C-2: 3-phenoxy-1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
[(D) Curing accelerator]
Component D-1: AER Hardener D1301 (manufactured by Asahi Kasei Corporation)
[Other ingredients]
Other ingredients-1: Glycerol (manufactured by Tokyo Chemical Industry Co., Ltd.)
［実施例１～８及び比較例１～５］
表１－１～１－４に示す割合で各成分を配合し、上記方法によりエポキシ樹脂組成物を調製した。調製したエポキシ樹脂組成物の各特性について上記方法により測定した。レオメーター測定での各エポキシ樹脂組成物の増粘開始温度測定結果、各エポキシ樹脂組成物の初期粘度測定結果を表１－１～１－４に示す。
[Examples 1 to 8 and Comparative Examples 1 to 5]
Each component was blended in the proportions shown in Tables 1-1 to 1-4, and an epoxy resin composition was prepared by the above method. Each characteristic of the prepared epoxy resin composition was measured by the above method. Tables 1-1 to 1-4 show the measurement results of the thickening start temperature of each epoxy resin composition and the initial viscosity measurement results of each epoxy resin composition by rheometer measurement.
成分（Ａ）及び（Ｂ）の配合が同じ実施例１～３と、比較例１とを対比すると、実施例１～３のエポキシ樹脂組成物は、成分（Ｃ）（成分Ｃ－１）を含まない比較例１よりも、増粘開始温度が低く、初期粘度も低く、低粘度化及び低温硬化性が向上していることがわかった。
また、成分（Ａ）、（Ｂ）及び（Ｄ）の配合が同じ実施例４と、比較例２とを対比すると、実施例４のエポキシ樹脂組成物は、成分（Ｃ）（成分Ｃ－１）を含まない比較例２よりも、増粘開始温度が低く、初期粘度も低く、低粘度化及び低温硬化性が向上していることがわかった。
また、成分（Ａ）及び（Ｂ）の配合が同じ実施例５と、比較例３とを対比すると、実施例５のエポキシ樹脂組成物は、成分（Ｃ）（成分Ｃ－１）を含まない比較例３よりも、増粘開始温度が低く、初期粘度も低く、低粘度化及び低温硬化性が向上していることがわかった。
また、成分（Ａ）及び（Ｂ）の配合が同じ実施例６～８と、比較例４とを対比すると、実施例６～８のエポキシ樹脂組成物は、成分（Ｃ）（成分Ｃ－１又は成分Ｃ－２）を含まない比較例４よりも、増粘開始温度が低く、初期粘度も低く、低粘度化及び低温硬化性が向上していることがわかった。なお、成分（Ｃ）に代えて、その他の成分として、末端にヒドロキシル基を有するが、式（１）で示される化合物に該当しない「その他成分－１：グリセロール」を用いた比較例５のエポキシ樹脂組成物は、グリセロールを含まないこと以外は同じ比較例４の初期粘度（１３Ｐａ・ｓ）と同じ初期粘度であることから、粘度低下の効果がないことがわかった。
Comparing Examples 1 to 3 with the same composition of components (A) and (B) and Comparative Example 1, the epoxy resin compositions of Examples 1 to 3 contain component (C) (component C-1). It was found that the thickening start temperature was lower, the initial viscosity was lower, and the viscosity reduction and low-temperature curability were improved than in Comparative Example 1, which did not contain it.
Further, when Comparative Example 2 is compared with Example 4, which has the same composition of components (A), (B), and (D), the epoxy resin composition of Example 4 has component (C) (component C-1). ) It was found that the thickening start temperature was lower, the initial viscosity was also lower, and the viscosity reduction and low-temperature curability were improved than in Comparative Example 2 which did not contain ).
Furthermore, when Comparative Example 3 is compared with Example 5, which has the same composition of components (A) and (B), the epoxy resin composition of Example 5 does not contain component (C) (component C-1). It was found that the thickening start temperature was lower than that of Comparative Example 3, the initial viscosity was also lower, and the viscosity reduction and low-temperature curability were improved.
Further, when Comparative Example 4 is compared with Examples 6 to 8 in which the compositions of components (A) and (B) are the same, it is found that the epoxy resin compositions of Examples 6 to 8 have the same composition as component (C) (component C-1). It was also found that the thickening start temperature was lower, the initial viscosity was lower, and the viscosity reduction and low-temperature curability were improved than in Comparative Example 4 which did not contain component C-2). In addition, instead of component (C), as another component, the epoxy of Comparative Example 5 used "Other component-1: glycerol" which has a hydroxyl group at the terminal but does not correspond to the compound represented by formula (1). Since the resin composition had the same initial viscosity as Comparative Example 4 (13 Pa·s) except that it did not contain glycerol, it was found that there was no effect of reducing the viscosity.
実施例６及び比較例４のエポキシ樹脂組成物のゲルタイム測定結果を表２に示す。比較例４のエポキシ樹脂組成物に対して成分（Ｃ）（成分Ｃ－１）を加えた実施例６のエポキシ樹脂組成物において、大幅にゲルタイム（硬化時間）が短縮されていることがわかった。 Table 2 shows the gel time measurement results of the epoxy resin compositions of Example 6 and Comparative Example 4. It was found that the gel time (curing time) was significantly shortened in the epoxy resin composition of Example 6 in which component (C) (component C-1) was added to the epoxy resin composition of Comparative Example 4. .
実施例１～３及び６～８並びに比較例５のエポキシ樹脂組成物の保存安定性倍率の測定結果を表３に示す。 Table 3 shows the measurement results of the storage stability ratio of the epoxy resin compositions of Examples 1 to 3 and 6 to 8 and Comparative Example 5.
実施例５及び６並びに比較例３及び４のエポキシ樹脂組成物の硬化領域評価結果を表４に示す。実施例５及び６のエポキシ樹脂組成物では１００％の硬化領域を示したが、成分（Ｃ）（成分Ｃ－１）を含まない比較例３及び４のエポキシ樹脂組成物では十分な硬化領域を示さなかった。 Table 4 shows the cured area evaluation results of the epoxy resin compositions of Examples 5 and 6 and Comparative Examples 3 and 4. The epoxy resin compositions of Examples 5 and 6 showed a 100% cured area, but the epoxy resin compositions of Comparative Examples 3 and 4, which did not contain component (C) (component C-1), showed a sufficient cured area. Didn't show it.
以上、本実施形態について説明してきたが、本発明はこれに限定されるものではなく、発明の趣旨を逸脱しない範囲で適宜変更可能である。 Although the present embodiment has been described above, the present invention is not limited thereto, and can be modified as appropriate without departing from the spirit of the invention.
本発明によれば、低粘度化、低温硬化性の向上、硬化時間の短縮、熱の伝わり方が不十分な場合での十分な硬化領域の確保、が可能なエポキシ樹脂組成物を提供することができる。 According to the present invention, there is provided an epoxy resin composition that can reduce viscosity, improve low-temperature curability, shorten curing time, and secure a sufficient curing area even when heat transfer is insufficient. Can be done.
Claims (9)
前記成分（Ｂ）が、アミン系硬化剤、アミド系硬化剤、潜在性硬化剤及びイミダゾール系硬化剤からなる群より選ばれる一つ以上である、
エポキシ樹脂組成物（ただし、アルキレン１，２－カーボネートを含む態様を除く）。
（Ａ）エポキシ樹脂
（Ｂ）硬化剤
（Ｃ）下記式（１）で示される化合物
The component (B) is one or more selected from the group consisting of an amine curing agent, an amide curing agent, a latent curing agent, and an imidazole curing agent.
Epoxy resin composition (excluding embodiments containing alkylene 1,2-carbonate).
(A) Epoxy resin (B) Curing agent (C) Compound represented by the following formula (1)
前記成分（Ｂ）が、アミン系硬化剤、アミド系硬化剤、潜在性硬化剤及びイミダゾール系硬化剤からなる群より選ばれる一つ以上である、
エポキシ樹脂組成物（ただし、アルキレン１，２－カーボネートを含む態様を除く）の製造方法。
（Ａ）エポキシ樹脂
（Ｂ）硬化剤
（Ｃ）下記式（１）で示される化合物
The component (B) is one or more selected from the group consisting of an amine curing agent, an amide curing agent, a latent curing agent, and an imidazole curing agent.
A method for producing an epoxy resin composition (excluding embodiments containing alkylene 1,2-carbonate).
(A) Epoxy resin (B) Curing agent (C) Compound represented by the following formula (1)
成分（Ａ）、成分（Ｂ）、及び成分（Ｄ）の群から選ばれる少なくとも一つを有する化合物又は組成物に成分（Ｃ）を添加する工程を含む、請求項７に記載のエポキシ樹脂組成物の製造方法。
（Ｄ）硬化促進剤 The epoxy resin composition further contains the following component (D),
The epoxy resin composition according to claim 7 , comprising the step of adding component (C) to a compound or composition having at least one selected from the group of component (A), component (B), and component (D). How things are manufactured.
(D) Curing accelerator
成分（Ａ）、成分（Ｂ）、及び成分（Ｅ）の群から選ばれる少なくとも一つを有する化合物又は組成物に成分（Ｃ）を添加する工程を含む、請求項７又は８に記載のエポキシ樹脂組成物の製造方法。
（Ｅ）フィラー
The epoxy resin composition further contains the following component (E),
The epoxy according to claim 7 or 8 , comprising the step of adding component (C) to a compound or composition having at least one selected from the group of component (A), component (B), and component (E). A method for producing a resin composition.
(E) Filler
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| DE4106665A1 (en) * | 1991-03-02 | 1992-09-03 | Jenoptik Jena Gmbh | Colourless, transparent epoxy resin] for high vacuum uses - comprising bisphenol=A di:glycidyl ether, 1-phenoxy:propane-2,3-diol and magnesium perchlorate |
| JP3214642B2 (en) * | 1993-08-09 | 2001-10-02 | 旭化成エポキシ株式会社 | Curable epoxy resin composition |
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