JP2019104883A - Epoxy resin, epoxy resin composition, cured product, and method for producing epoxy resin - Google Patents
Epoxy resin, epoxy resin composition, cured product, and method for producing epoxy resin Download PDFInfo
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- JP2019104883A JP2019104883A JP2017239901A JP2017239901A JP2019104883A JP 2019104883 A JP2019104883 A JP 2019104883A JP 2017239901 A JP2017239901 A JP 2017239901A JP 2017239901 A JP2017239901 A JP 2017239901A JP 2019104883 A JP2019104883 A JP 2019104883A
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- Japan
- Prior art keywords
- epoxy resin
- group
- carbon atoms
- formula
- epihalohydrin
- 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 abstract description 189
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 189
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 title abstract description 42
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 92
- 239000003054 catalyst Substances 0.000 claims description 57
- 239000011973 solid acid Substances 0.000 claims description 45
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 43
- -1 polyol compound Chemical class 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 229920005862 polyol Polymers 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000007259 addition reaction Methods 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 239000011342 resin composition Substances 0.000 claims description 7
- 238000007363 ring formation reaction Methods 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004957 naphthylene group Chemical group 0.000 claims description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 150000002367 halogens Chemical class 0.000 abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 66
- 238000006243 chemical reaction Methods 0.000 description 49
- 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 48
- 238000000034 method Methods 0.000 description 34
- 239000000047 product Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000007792 addition Methods 0.000 description 24
- 239000000126 substance Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- 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 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 230000035484 reaction time Effects 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000003444 phase transfer catalyst Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000006378 damage Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 239000002734 clay mineral Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 239000012454 non-polar solvent Substances 0.000 description 5
- 229960003742 phenol Drugs 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 239000002739 cryptand Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000003586 protic polar solvent Substances 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 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 2
- 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 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-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
- 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 2
- 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 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000000465 moulding Methods 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
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 239000010457 zeolite Substances 0.000 description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- 125000004822 1,1-dimethylpropylene group Chemical group [H]C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 125000004823 1,2-dimethylpropylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-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
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
本発明は、エポキシ樹脂、エポキシ樹脂組成物、硬化物、及びエポキシ樹脂の製造方法に関する。 The present invention relates to an epoxy resin, an epoxy resin composition, a cured product, and a method for producing an epoxy resin.
エポキシ樹脂と硬化剤とを含むエポキシ樹脂組成物の硬化物は、半導体パッケージ及び半導体チップ等の電子部材、ＬＥＤ及びカメラモジュール等の光学部材等をはじめとする、様々な用途に使用されている。
例えば、特許文献１には、アルカリ性化合物及び相間移動触媒を用い、アルコールをグリシジル化する工程を含む、繰り返し単位が１２以下であるポリエーテル基を有するエポキシ樹脂の製造方法が開示されている。
また、特許文献２には、エピハロヒドリンとアルコールとを固体酸触媒を用い反応させエピハロヒドリンエーテルを得た後、塩基を作用させることによりグリシジルエーテルを得る工程を含む、エポキシ樹脂の製造方法が開示されている。特許文献２におけるエポキシ樹脂は、繰り返し単位が４以下であるポリエーテル基を有し、特に、この文献の実施例４では、ハロゲン原子含量（塩素量）が０．０８％（８００ｐｐｍ）と記載されている。
A cured product of an epoxy resin composition containing an epoxy resin and a curing agent is used in various applications including electronic members such as semiconductor packages and semiconductor chips, and optical members such as LEDs and camera modules.
For example, Patent Document 1 discloses a method for producing an epoxy resin having a polyether group having a repeating unit of 12 or less, which comprises a step of glycidylating an alcohol using an alkaline compound and a phase transfer catalyst.
In addition, Patent Document 2 discloses a method for producing an epoxy resin, which comprises a step of obtaining glycidyl ether by reacting an epihalohydrin with an alcohol using a solid acid catalyst to obtain an epihalohydrin ether and then reacting a base. There is. The epoxy resin in Patent Document 2 has a polyether group having a repeating unit of 4 or less, and in particular, in Example 4 of this document, the halogen atom content (chlorine content) is described as 0.08% (800 ppm). ing.
近年、半導体パッケージ及び半導体チップ等の電子部材、ＬＥＤ及びカメラモジュール等の光学部材については、小型化、薄型化、軽量化の要求が強くなっている。特に携帯できる電子デバイスは上記要求を満たしながら、誤って落下した場合でも正常に作動する耐衝撃性が求められている。さらには、電子部材には耐腐食性及び電気信頼性の観点から、ハロゲン系不純物の含有量が少ないこと、光学部材には光透過性の観点から、着色が少ないことも望まれている。 In recent years, with regard to electronic members such as semiconductor packages and semiconductor chips, and optical members such as LEDs and camera modules, there has been an increasing demand for downsizing, thinning, and weight reduction. In particular, electronic devices that can be carried are required to have shock resistance that can operate properly even if they fall accidentally while satisfying the above requirements. Furthermore, from the viewpoint of corrosion resistance and electrical reliability, the electronic member is also desired to have a low content of halogen-based impurities, and to have low coloration from the viewpoint of light transparency to the optical member.
例えば、特許文献１に開示されたエポキシ樹脂は、塩素を含む副生成物が多く、当該エポキシ樹脂の製造の際に高濃度のアルカリ水溶液を使用するため、着色度合いも大きいと考えられる。
また、特許文献２には、ハロゲン原子含有不純物の少ないグリシジルエーテルの製造方法が開示されているが、このハロゲン原子含有量をさらに低減して改善する余地がある。
そのため、ハロゲン系不純物の含有量及び着色が少ないエポキシ樹脂が求められている。
For example, the epoxy resin disclosed in Patent Document 1 contains a large amount of chlorine-containing by-products, and is considered to have a high degree of coloration because a high-concentration alkaline aqueous solution is used in the production of the epoxy resin.
Moreover, although the manufacturing method of glycidyl ether with few halogen atom containing impurities is disclosed by patent document 2, there exists room for further reducing and improving this halogen atom content.
Therefore, an epoxy resin having a small content of halogen-based impurities and a small color is required.
本発明は上記事情に鑑みなされたものであり、低ハロゲン性と低着色性を有する硬化物を得ることができる、エポキシ樹脂及びエポキシ樹脂組成物を提供することを目的とする。 The present invention is made in view of the above-mentioned circumstances, and it aims at providing an epoxy resin and an epoxy resin composition which can obtain a hardened material which has low halogen nature and low coloring nature.
本発明者は鋭意検討した結果、全塩素量が特定範囲であり、特定の構造で表されるエポキシ樹脂は、低ハロゲン性と低着色性を有することを見出し、本発明を完成するに至った。 As a result of intensive investigations, the inventor of the present invention has found that the total chlorine content is within a specific range, and the epoxy resin represented by a specific structure has low halogenity and low colorability, and has completed the present invention. .
すなわち、本発明は以下のとおりである。
［１］
ＪＩＳ Ｋ７２４３−３で測定した全塩素含有量が、１〜２００ｐｐｍ以下である、下記式（１）で表されるエポキシ樹脂。
［２］
ＪＩＳ Ｋ００７１−２で測定したガードナー色数が、１．０〜３．０である、［１］に記載のエポキシ樹脂。
［３］
−Ｒ1Ｏ−で表される単位の平均付加数が、エポキシ樹脂の一分子当たり、５．０以上である、［１］又は［２］に記載のエポキシ樹脂。
［４］
前記式（１）のＲ2が、フェニレン基、ナフチレン基、ビフェニレン基、及び下記式（２）で表される構造を有する２価の芳香族基からなる群より選ばれるいずれかである、［１］〜［３］のいずれかに記載のエポキシ樹脂。
［５］
前記式（１）が、下記式（３）である、［１］〜［４］のいずれかに記載のエポキシ樹脂。
［６］
（Ａ）［１］〜［５］のいずれかに記載のエポキシ樹脂と、（Ｂ）その他のエポキシ樹脂と、（Ｃ）硬化剤と、を含み、
前記（Ａ）成分１００質量部に基づいて、前記（Ｂ）成分が１〜４００質量部であり、
前記（Ａ）成分と前記（Ｂ）成分の合計エポキシ基１当量に基づいて、前記（Ｃ）成分が０．５〜３．０当量である、樹脂組成物。
［７］
１４０℃で６０分間、さらに２２０℃で１２０分間硬化させることにより硬化物としたとき、ＪＩＳ Ｋ７２１１で測定した５０％破壊エネルギーが、４〜２０Ｊである、［６］に記載の樹脂組成物。
［８］
［６］又は［７］に記載の樹脂組成物から作製された硬化物。
［９］
下記式（４）で表されるポリオール化合物に、固体酸触媒存在下でエピハロヒドリンを付加させ、エピハロヒドリンエーテルを得る付加反応工程と、
前記エピハロヒドリンエーテルを、アルカリ性化合物存在下、閉環させ、エポキシ樹脂を得る閉環反応工程と、
を含む、［１］〜［５］のいずれかに記載のエポキシ樹脂の製造方法。
[1]
The epoxy resin represented by following formula (1) whose total chlorine content measured by JISK7243-3 is 1-200 ppm or less.
[2]
The epoxy resin as described in [1] whose Gardner color number measured by JISK0071-2 is 1.0-3.0.
[3]
The epoxy resin as described in [1] or [2] whose average addition number of the unit represented by -R < 1 > O- is 5.0 or more per one molecule of an epoxy resin.
[4]
R 2 in the formula (1) is any one selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (2) [ The epoxy resin as described in any one of 1]-[3].
[5]
The epoxy resin in any one of [1]-[4] whose said Formula (1) is following formula (3).
[6]
(A) containing the epoxy resin according to any one of [1] to [5], (B) another epoxy resin, and (C) a curing agent,
The component (B) is 1 to 400 parts by mass based on 100 parts by mass of the component (A),
The resin composition whose said (C) component is 0.5-3.0 equivalent based on the epoxy group 1 equivalent of the said (A) component and the said (B) component.
[7]
The resin composition as described in [6] whose 50% destruction energy measured by JISK7211 is 4-20 J, when setting it as a hardened | cured material by making it harden | cure by making it harden | cure at 140 degreeC for 60 minutes, and also 220 degreeC for 120 minutes.
[8]
Hardened | cured material produced from the resin composition as described in [6] or [7].
[9]
An addition reaction step of adding an epihalohydrin to a polyol compound represented by the following formula (4) in the presence of a solid acid catalyst to obtain an epihalohydrin ether;
A ring closing reaction step of ring closing the epihalohydrin ether in the presence of an alkaline compound to obtain an epoxy resin;
The manufacturing method of the epoxy resin in any one of [1]-[5] including B.
本発明によれば、低ハロゲン性と低着色性を有する硬化物を得ることができる、エポキシ樹脂及びエポキシ樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin and the epoxy resin composition which can obtain the hardened | cured material which has low halogen property and low colorability can be provided.
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。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。本発明はその趣旨の範囲内で適宜に変形して実施できる。 Hereinafter, modes for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present embodiment is an example for describing the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the spirit of the present invention.
［エポキシ樹脂］
本実施形態のエポキシ樹脂は、下記式（１）で表される。
[Epoxy resin]
The epoxy resin of the present embodiment is represented by the following formula (1).
本実施形態のエポキシ樹脂における全塩素量は、１〜２００ｐｐｍ、好ましくは１〜１５０ｐｐｍ、より好ましくは１〜１００ｐｐｍである。また、全塩素量を１〜２００ｐｐｍの範囲にすることにより、不純物が少ないために耐衝撃性が一層向上し、着色が少なくなる傾向にある。
本実施形態のエポキシ樹脂は、例えば、後述するエポキシ樹脂の製造方法によって製造することができる。また、当該製造方法においては、塩素含有副生成物を除去するための特殊な工程を実施せずとも全塩素量を１〜２００ｐｐｍの範囲に制御可能である。
The total chlorine content in the epoxy resin of the present embodiment is 1 to 200 ppm, preferably 1 to 150 ppm, more preferably 1 to 100 ppm. In addition, when the total chlorine content is in the range of 1 to 200 ppm, the impact resistance is further improved due to the small amount of impurities, and the coloring tends to be reduced.
The epoxy resin of this embodiment can be manufactured, for example, by the method of manufacturing an epoxy resin described later. Moreover, in the said manufacturing method, even if it does not implement a special process for removing a chlorine containing by-product, the total amount of chlorine can be controlled in the range of 1 to 200 ppm.
本実施形態のエポキシ樹脂におけるガードナー色相は、好ましくは１．０〜３．０、より好ましくは１．５〜３．０、さらに好ましくは１．５〜２．５である。ガードナー色相が１．０〜３．０であることによって、着色の原因となる二重結合含有副生成物が少なく、耐衝撃性が一層向上する。
ガードナー色相は、後述するエポキシ樹脂の製造方法により、１．０〜３．０の範囲に調整することができる。また、当該製造方法においては、二重結合含有副生成物を除去するための特殊な工程を実施せずともガードナー色相を１．０〜３．０の範囲に制御可能である。
The Gardner hue in the epoxy resin of this embodiment is preferably 1.0 to 3.0, more preferably 1.5 to 3.0, and still more preferably 1.5 to 2.5. When the Gardner hue is 1.0 to 3.0, the number of double bond-containing by-products that cause coloring is small, and the impact resistance is further improved.
The Gardner color can be adjusted in the range of 1.0 to 3.0 by the method for producing an epoxy resin described later. Moreover, in the said manufacturing method, Gardner hue can be controlled in the range of 1.0-3.0, without implementing the special process for removing a double bond containing by-product.
式（１）中、Ｒ1、Ｒ2における炭素数１〜１２の２価の脂肪族基は、直鎖状でもよく、分岐状でもよく、不飽和結合基を含んでいてもよい。
上記２価の脂肪族基の炭素数は、可撓性と耐熱性とのバランスの観点から、好ましくは１〜６、製造容易性の観点から、より好ましくは１〜３である。
上記２価の脂肪族基としては、例えば、メチレン基、エチレン基、ｎ−プロピレン基、イソプロピレン基、ｎ−ブチレン基、ｓｅｃ−ブチレン基、イソブチレン基、ｔｅｒｔ−ブチレン基、ｎ−ペンチレン基、１−メチルブチレン基、２−メチルブチレン基、３−メチルブチレン基、１−エチルプロピレン基、１，１−ジメチルプロピレン基、１，２−ジメチルプロピレン基、２，２−ジメチルプロピレン基等が挙げられる。これらの中でも、好ましくは、メチレン基、エチレン基、ｎ−プロピレン基、イソプロピレン基である。
In the formula (1), the divalent aliphatic group having 1 to 12 carbon atoms in R 1 and R 2 may be linear, branched or may contain an unsaturated bond group.
The carbon number of the divalent aliphatic group is preferably 1 to 6 from the viewpoint of the balance between flexibility and heat resistance, and more preferably 1 to 3 from the viewpoint of easiness of production.
As said bivalent aliphatic group, a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, sec-butylene group, isobutylene group, tert- butylene group, n-pentylene group, for example 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 1-ethylpropylene group, 1,1-dimethylpropylene group, 1,2-dimethylpropylene group, 2,2-dimethylpropylene group etc. are mentioned Be Among these, preferred are a methylene group, an ethylene group, an n-propylene group and an isopropylene group.
式（１）中、Ｒ1、Ｒ2における炭素数６〜４０の２価の芳香族基としては、例えば、フェニレン基、ナフチレン基、ビフェニレン基；フェニレン基、ナフチレン基、ビフェニレン基；ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、テトラブロモビスフェノールＡ、ビフェニル、テトラメチルビフェニル、テトラブロモビフェニル、ジフェニルエーテル、ベンゾフェノン、フェニルベンゾエート、ジフェニルスルフィド、ジフェニルスルホキシド、ジフェニルスルホン、ジフェニルジスルフィド、ナフタレン、アントラセン、ヒドロキノン、メチルヒドロキノン、ジブチルヒドロキノン、レゾルシン、メチルレゾルシン、及びカテコールからなる群より選ばれるいずれかに由来する２価の芳香族が挙げられる。 In the formula (1), examples of the divalent aromatic group having 6 to 40 carbon atoms as R 1 and R 2 include phenylene group, naphthylene group, biphenylene group; phenylene group, naphthylene group, biphenylene group; bisphenol A, Bisphenol F, bisphenol AD, tetrabromobisphenol A, biphenyl, tetramethylbiphenyl, tetrabromobiphenyl, diphenyl ether, benzophenone, phenylbenzoate, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl disulfide, naphthalene, anthracene, hydroquinone, methylhydroquinone, dibutyl Examples thereof include divalent aromatics derived from any selected from the group consisting of hydroquinone, resorcine, methylresorcine, and catechol.
式（１）のＲ1は、それぞれ、同一であってもよく、異なっていてもよい。 R 1 in the formula (1) may be identical to or different from each other.
本実施形態のエポキシ樹脂は、式（１）に包含される少なくとも１種の分子を１以上含んでいればよい。このとき、式（１）に含まれる、−Ｒ1Ｏ−で表される単位（繰り返し単位ともいう。）の平均付加数が、エポキシ樹脂の一分子当たり、好ましくは５．０以上であり、より好ましくは５．５以上であり、さらに好ましくは６．０以上である。
上記平均付加数の上限は、好ましくは１２．０以下である。
上記平均付加数が５．０以上であることにより、耐衝撃性が一層向上し、粘度を一層低くすることができハンドリング性が一層向上する傾向にある。
また、本実施形態における「平均付加数」は、エポキシ樹脂における、式（１）中のｍとｎとの和の平均値とも定義される。
The epoxy resin of the present embodiment may contain one or more of at least one molecule included in the formula (1). At this time, the average addition number of units (also referred to as repeating units) represented by -R 1 O- contained in the formula (1) is preferably 5.0 or more per one molecule of epoxy resin, More preferably, it is 5.5 or more, More preferably, it is 6.0 or more.
The upper limit of the average addition number is preferably 12.0 or less.
When the average addition number is 5.0 or more, the impact resistance is further improved, the viscosity can be further lowered, and the handling property tends to be further improved.
The “average number of additions” in the present embodiment is also defined as the average value of the sum of m and n in the formula (1) in the epoxy resin.
本実施形態のエポキシ樹脂におけるエポキシ当量は、好ましくは２００〜５００ｇ／ｅｑ．、より好ましくは２４０〜４５０ｇ／ｅｑ．、さらに好ましくは３００〜３７０ｇ／ｅｑ．である。エポキシ当量を２００〜５００ｇ／ｅｑ．の範囲にすることにより、耐衝撃性が一層向上する傾向にある。
エポキシ当量の範囲を調整する方法としては、例えば、エポキシ樹脂の製造における触媒の量を制御する方法、及び、原料であるエピハロヒドリンの量を制御する方法等が挙げられる。
エポキシ当量は、具体的には実施例に記載の方法によって測定することができる。
The epoxy equivalent of the epoxy resin of the present embodiment is preferably 200 to 500 g / eq. , More preferably 240 to 450 g / eq. , More preferably 300 to 370 g / eq. It is. Epoxy equivalent 200 to 500 g / eq. The impact resistance tends to be further improved by setting the range of
As a method of adjusting the range of epoxy equivalent, the method of controlling the quantity of the catalyst in manufacture of an epoxy resin, the method of controlling the quantity of the epihalohydrin which is a raw material, etc. are mentioned, for example.
The epoxy equivalent can be measured specifically by the method described in the examples.
式（１）中、Ｒ1が脂肪族基である場合は、Ｒ2は芳香族基であることが好ましく、Ｒ1が芳香族基である場合は、Ｒ2は脂肪族基であることが好ましい。
Ｒ2は、粘度の観点から、炭素数６〜２０の２価の芳香族基であることが好ましく、製造容易性の観点から、炭素数６〜１５の２価の芳香族基であることがより好ましい。
In formula (1), when R 1 is an aliphatic group, R 2 is preferably an aromatic group, and when R 1 is an aromatic group, R 2 is an aliphatic group preferable.
R 2 is preferably a divalent aromatic group having 6 to 20 carbon atoms from the viewpoint of viscosity, and is a divalent aromatic group having 6 to 15 carbon atoms from the viewpoint of easiness of production More preferable.
式（１）のＲ2は、耐熱性の観点から、フェニレン基、ナフチレン基、及び下記式（２）で表される構造を有する２価の芳香族基からなる群より選ばれるいずれかであることが好ましい。 R 2 in the formula (1) is any one selected from the group consisting of a phenylene group, a naphthylene group, and a divalent aromatic group having a structure represented by the following formula (2) from the viewpoint of heat resistance Is preferred.
Ｒ3及びＲ4は、入手容易性の観点から、それぞれ独立して、水素原子、塩素原子、ヒドロキシル基、メチル基、エチル基、ｔｅｒｔ−ブチル基であることが好ましい。 R 3 and R 4 are preferably each independently a hydrogen atom, a chlorine atom, a hydroxyl group, a methyl group, an ethyl group or a tert-butyl group from the viewpoint of easy availability.
式（２）で表される構造を有する２価の芳香族基としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＰ、ビスフェノールＡＦ、ビスフェノールＢ、ビスフェノールＢＰ、ビスフェノールＣ、ビスフェノールＥ、ビスフェノールＧ、ビスフェノールＭ、ビスフェノールＳ、ビスフェノールＰ、ビスフェノールＰＨ、ビスフェノールＴＭＣ、ビスフェノールＺ、オキシビフェニル、ジヒドロキシベンゾフェノン、４−ヒドロキシ安息香酸−４−ヒドロキシベンゼンエステル、ビス（４−ヒドロキシフェニル）スルフィド、４，４’−スルフィニルビスフェノール、及びビス（４−ヒドロキシフェニル）ジスルフィド等からなる群より選ばれるいずれかに由来する２価の芳香族基が挙げられる。 Examples of the divalent aromatic group having a structure represented by the formula (2) include bisphenol A, bisphenol F, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, oxybiphenyl, dihydroxy benzophenone, 4-hydroxybenzoic acid 4-hydroxybenzene ester, bis (4-hydroxyphenyl) sulfide, 4,4'-sulfinyl Divalent aromatic groups derived from any one selected from the group consisting of bisphenol and bis (4-hydroxyphenyl) disulfide and the like can be mentioned.
式（１）は、耐衝撃性の観点から、下記式（３）であることが好ましい。 Formula (1) is preferably the following formula (3) from the viewpoint of impact resistance.
式（３）中のＧ3は、吸水性及び反応速度の観点から、グリシジル基であることが好ましい。 G 3 in the formula (3) is preferably a glycidyl group from the viewpoint of water absorption and reaction rate.
式（３）のｍ及びｎは、それぞれ独立して、１〜１１の整数であることが好ましい。
また、−ＣＨ2−ＣＨ（Ｒ5）−Ｏ−で表される単位の平均付加数が、５．０以上１２．０以下であることが好ましい。平均付加数が５．０以上１２．０以下であることにより、耐衝撃性が一層向上し、粘度を一層低くすることができハンドリング性が一層向上する。
It is preferable that m and n of Formula (3) are respectively independently an integer of 1-11.
Further, -CH 2 -CH (R 5) average addition number of -O- represented by units, is preferably 5.0 to 12.0. When the average addition number is 5.0 or more and 12.0 or less, the impact resistance is further improved, the viscosity can be further lowered, and the handling property is further improved.
［エポキシ樹脂の製造方法］
本実施形態のエポキシ樹脂は、例えば、下記式（４）で表されるポリオール化合物を原料として用いることにより製造することができる。式（４）で表されるポリオール化合物で表されるポリオール化合物は、市販品として入手可能である。式（４）で表されるポリオール化合物は、式（４）に包含される少なくとも１種の化合物を１以上含む。
[Method of producing epoxy resin]
The epoxy resin of the present embodiment can be produced, for example, by using a polyol compound represented by the following formula (4) as a raw material. The polyol compound represented by the polyol compound represented by Formula (4) is commercially available. The polyol compound represented by the formula (4) contains one or more of at least one compound included in the formula (4).
式（４）における「平均付加数」は、ポリオール化合物における、式（４）中のｍとｎとの和の平均値とも定義される。
The “average number of additions” in the formula (4) is also defined as the average value of the sum of m and n in the formula (4) in the polyol compound.
本実施形態のエポキシ樹脂の製造方法としては、例えば、式（４）で表されるポリオール化合物に、固体酸触媒存在下でエピハロヒドリンを付加させ、閉環前のエポキシ樹脂前駆体（エピハロヒドリンエーテルともいう）を得る付加反応工程と、前記エピハロヒドリンエーテルを、アルカリ性化合物存在下閉環させ、エポキシ樹脂を得る閉環反応工程と、を含む。以下、当該方法について詳細に説明する。 As a method for producing the epoxy resin of the present embodiment, for example, an epoxy resin precursor (also referred to as an epihalohydrin ether) before ring closure by adding an epihalohydrin to the polyol compound represented by the formula (4) in the presence of a solid acid catalyst And a ring-closing reaction step of ring-closing the epihalohydrin ether in the presence of an alkaline compound to obtain an epoxy resin. The method will be described in detail below.
〔付加反応工程〕
上記式（４）とエピハロヒドリンの付加反応工程は、バッチ法又は流通法のいずれの方式でも実施することができる。バッチ法とは、活性水酸基化合物とエピハロヒドリンを撹拌している反応槽内に触媒を懸濁させた状態で反応させる方式である。流通法とは、容器内に触媒を充填させた固定床を循環槽に連結し、活性水酸基化合物とエピハロヒドリンを含む溶液を通液循環させて反応させる方式である。
[Addition reaction process]
The addition reaction step of the above formula (4) and epihalohydrin can be carried out by either a batch method or a flow method. The batch method is a system in which the active hydroxyl compound and the epihalohydrin are reacted in a state where the catalyst is suspended in a stirred reaction vessel. The flow method is a method in which a fixed bed in which a container is filled with a catalyst is connected to a circulation tank, and a solution containing an active hydroxyl compound and an epihalohydrin is allowed to flow and react.
エピハロヒドリンとしては、特に限定されないが、例えば、エピクロロヒドリン、エピブロモヒドリン等が挙げられる。バッチ法、流通法のいずれの場合でもエピハロヒドリンの添加量は、ポリオール化合物の活性水酸基１当量に基づいて、通常１．０〜１０．０当量、好ましくは１．２〜６．０当量、より好ましくは１．５〜３．０当量である。エピハロヒドリンの添加量が１．０当量以上であることにより、付加反応が十分進行し、ポリオール化合物の末端の少なくとも一方にエピハロヒドリンが付加したエピハロヒドリンエーテルを十分に得られる傾向にある。エピハロヒドリンエーテルを十分に得られることにより、かかるエピハロヒドリンエーテルから得られるエポキシ樹脂は、末端の少なくとも一方にエポキシ基を十分有し、硬化物としたとき架橋が密に形成され、耐衝撃性に優れる。また、エピハロヒドリンの添加量が１０当量以下であることにより、副反応を抑制でき、純度の高いエピハロヒドリンエーテルを得られる傾向にある。 The epihalohydrin is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin and the like. The amount of epihalohydrin added is usually 1.0 to 10.0 equivalents, preferably 1.2 to 6.0 equivalents, and more preferably based on one equivalent of the active hydroxyl group of the polyol compound in either the batch method or the flow method. Is 1.5 to 3.0 equivalents. When the addition amount of the epihalohydrin is 1.0 equivalent or more, the addition reaction proceeds sufficiently, and an epihalohydrin ether in which the epihalohydrin is added to at least one end of the polyol compound tends to be sufficiently obtained. By sufficiently obtaining the epihalohydrin ether, the epoxy resin obtained from such an epihalohydrin ether has an epoxy group sufficiently on at least one of the ends, and when it is a cured product, crosslinks are densely formed, and the impact resistance is excellent. Further, when the amount of the epihalohydrin added is 10 equivalents or less, side reactions can be suppressed, and a high purity epihalohydrin ether tends to be obtained.
固体酸触媒としては、特に限定されないが、例えば、粘土鉱物、シリカゲル、陽イオン交換樹脂、多孔質金属酸化物等が挙げられる。これらは、１種単独で使用してもよく、２種以上を併用してもよい。 The solid acid catalyst is not particularly limited, and examples thereof include clay mineral, silica gel, cation exchange resin, porous metal oxide and the like. These may be used alone or in combination of two or more.
粘土鉱物とは、層状ケイ酸塩鉱物を主成分とする粘土粒子の構成単位であり、層間に含まれる物質によって様々な種類に分類される。
粘土鉱物の市販品としては、ＡｌｆａＡｅｓａｒ社製 ＭｏｎｔｍｏｒｉｌｌｏｎａｉｔｅＫ−１０、黒崎白土工業株式会社製 オドソルブＲ−１等が挙げられる。
粘土鉱物の一つである酸性白土類は、酸性白土を硫酸等の鉱酸で処理することにより、活性白土、合成ゼオライト等に分類される。
酸性白土の市販品としては、黒崎白土工業株式会社製 オドアース０４、日本活性白土株式会社製 ニッカナイトＳ−２００、水澤化学工業株式会社製 ミズカエース＃２０等が挙げられる。
活性白土の市販品としては、活性白土Ｒ−１５、日本活性白土株式会社製 ニッカナイトＧＣＨ−３６、ガレオンアースＮＶ、水澤化学工業株式会社製 ガレオナイト＃３３６等が挙げられる。
合成ゼオライトの市販品としては、和光純薬工業株式会社製 合成ゼオライトＦ−９、水澤化学工業株式会社製 ミズカシーブスＹ−４２０、日揮触媒化成株式会社製 Ｈ−Ｙ、ＺＳＭ−５、ＳＡＰＯ−５等が挙げられる。
The clay mineral is a constituent unit of clay particles having a layered silicate mineral as a main component, and is classified into various types according to the substance contained in the interlayer.
Examples of commercial products of clay minerals include Montmorillonaite K-10 manufactured by Alfa Aesar, and Odosorb R-1 manufactured by Kurosaki Shirato Kogyo Co., Ltd.
Acidic white earth, which is one of clay minerals, is classified into activated white clay, synthetic zeolite and the like by treating acid white clay with a mineral acid such as sulfuric acid.
Examples of commercially available acid clay include Odo Earth 04 manufactured by Kurosaki Shirato Kogyo Co., Ltd., Nikkanite S-200 manufactured by Japan Activated White Clay Co., Ltd., Mizuka Ace # 20 manufactured by Mizusawa Chemical Industry Co., Ltd., and the like.
Examples of commercially available products of activated clay include activated clay R-15, Nippon Activated Shirato Co., Ltd. Nikkanite GCH-36, Galleon Earth NV, Mizusawa Chemical Industry Co., Ltd. Galeonite # 336 and the like.
Commercially available synthetic zeolites include synthetic zeolite F-9 manufactured by Wako Pure Chemical Industries, Ltd. Mizuka Chemical Co., Ltd. Mizuka sieves Y-420, manufactured by JGC Catalysts Chemical Corporation H-Y, ZSM-5, SAPO-5, etc. Can be mentioned.
シリカゲル系の固体酸触媒とは、シリカゲル表面にスルホン酸基等を修飾した球状触媒である。シリカゲル系固体酸触媒の市販品としては、テイカ株式会社製 テイカキュアＳＡＣ−１０等が挙げられる。 The silica gel solid acid catalyst is a spherical catalyst in which a sulfonic acid group or the like is modified on the surface of silica gel. As a commercial item of a silica gel type solid acid catalyst, Tayca Co., Ltd. Teika cure SAC-10 etc. are mentioned.
陽イオン交換樹脂とは、ポリスチレン又はアクリル樹脂表面にスルホン酸基及び／又はカルボキシル基等で修飾した球状触媒である。陽イオン交換樹脂の市販品としては、住化ケムテックス株式会社製 デュオライトＳＣ２００、ダウケミカル社製 アンバーリスト１５ＤＲＹ等が挙げられる。 The cation exchange resin is a spherical catalyst modified on the surface of polystyrene or acrylic resin with a sulfonic acid group and / or a carboxyl group. Commercially available products of the cation exchange resin include Duolite SC200 manufactured by Sumika Chemtex Co., Ltd., Amberlyst 15 DRY manufactured by Dow Chemical Co., and the like.
多孔質金属酸化物とは、チタン、亜鉛、イットリウム、ジルコニウム、ニオブ、スズ、ランタン、タンタル等の遷移金属酸化物；又は、ＳｒＴｉＯ3、ＣａＴｉＯ3等のペロブスカイト系酸化物を、鋳型法又は焼成法により多孔質化させたものである。 The porous metal oxide is a transition metal oxide such as titanium, zinc, yttrium, zirconium, niobium, tin, lanthanum, tantalum or the like; or a perovskite type oxide such as SrTiO 3 or CaTiO 3 by a template method or a firing method Are made porous.
これら固体酸触媒の中では、入手容易性の観点から、粘土鉱物、シリカゲル系固体酸触媒、陽イオン交換樹脂が好ましく、高触媒能及び低コストの観点から、粘土鉱物がより好ましい。 Among these solid acid catalysts, clay minerals, silica gel solid acid catalysts, and cation exchange resins are preferable from the viewpoint of easy availability, and clay minerals are more preferable from the viewpoint of high catalytic ability and low cost.
固体酸触媒の形態としては、粉状、グラニュール状、ビーズ状、ペレット状、チップ状のいずれであってもよく、水等に分散された懸濁状態であってもよい。 The solid acid catalyst may be in the form of powder, granules, beads, pellets, chips, or in the form of a suspension dispersed in water or the like.
固体酸触媒の添加量は、バッチ法の場合、ポリオール化合物の活性水酸基１当量に基づいて、通常１０〜９０ｇ、好ましくは２０〜８０ｇ、より好ましくは２５〜７５ｇである。固体酸触媒の添加量が１０ｇ以上であることにより、反応が十分進行し、ポリオール化合物の末端の少なくとも一方にエピハロヒドリンが付加したエピハロヒドリンエーテルを十分に得られる傾向にある。また、固体酸触媒の添加量が９０ｇ以下であることにより、エピハロヒドリンの自己重合等の副反応を抑制でき、純度の高いエピハロヒドリンエーテルを得られる傾向にある。
固体酸触媒の添加量は、流通法の場合、ポリオール化合物の活性水酸基１当量に基づいて、通常２００〜１８００ｇ、好ましくは４００〜１６００ｇ、より好ましくは５００〜１５００ｇである。固体酸触媒の添加量が２００ｇ以上であることにより、反応が十分進行し、ポリオール化合物の末端の少なくとも一方にエピハロヒドリンが付加したエピハロヒドリンエーテルを十分に得られる傾向にある。また、固体酸触媒の添加量が１８００ｇ以下であることにより、エピハロヒドリンの自己重合等の副反応を抑制でき、純度の高いエピハロヒドリンエーテルを得られる傾向にある。
エピハロヒドリンエーテルを十分に得られることにより、かかるエピハロヒドリンエーテルから得られるエポキシ樹脂は、末端の少なくとも一方にエポキシ基を十分有し、硬化物としたとき架橋が密に形成され、耐衝撃性に優れる。
The addition amount of the solid acid catalyst is usually 10 to 90 g, preferably 20 to 80 g, more preferably 25 to 75 g based on one equivalent of the active hydroxyl group of the polyol compound in the case of a batch method. When the addition amount of the solid acid catalyst is 10 g or more, the reaction proceeds sufficiently, and an epihalohydrin ether in which the epihalohydrin is added to at least one of the ends of the polyol compound tends to be sufficiently obtained. In addition, when the addition amount of the solid acid catalyst is 90 g or less, side reactions such as self polymerization of epihalohydrin can be suppressed, and a high purity epihalohydrin ether tends to be obtained.
The amount of the solid acid catalyst added is usually 200 to 1800 g, preferably 400 to 1600 g, more preferably 500 to 1500 g, in the case of the flow method, based on one equivalent of the active hydroxyl group of the polyol compound. When the addition amount of the solid acid catalyst is 200 g or more, the reaction proceeds sufficiently, and an epihalohydrin ether in which the epihalohydrin is added to at least one end of the polyol compound tends to be sufficiently obtained. Further, when the addition amount of the solid acid catalyst is not more than 1800 g, side reactions such as self polymerization of epihalohydrin can be suppressed, and a high purity epihalohydrin ether tends to be obtained.
By sufficiently obtaining the epihalohydrin ether, the epoxy resin obtained from such an epihalohydrin ether has an epoxy group sufficiently on at least one of the ends, and when it is a cured product, crosslinks are densely formed, and the impact resistance is excellent.
バッチ法、流通法のいずれの場合でも、反応温度は、通常２５〜１４０℃、好ましくは３０〜１３０℃、より好ましくは４０〜１２０℃である。反応温度が２５℃以上であることにより、反応の進行が速くなるため、エピハロヒドリンを効率よく付加できる傾向にある。また、反応温度が１４０℃以下であることにより、エピハロヒドリンの自己重合等の副反応を効率よく抑制でき、純度の高いエピハロヒドリンエーテルを得られる傾向にある。 The reaction temperature is usually 25 to 140 ° C., preferably 30 to 130 ° C., and more preferably 40 to 120 ° C. in either of the batch method and the flow method. When the reaction temperature is 25 ° C. or more, the progress of the reaction becomes fast, so that the epihalohydrin tends to be able to be added efficiently. Further, when the reaction temperature is 140 ° C. or less, side reactions such as self polymerization of epihalohydrin can be efficiently suppressed, and a high purity epihalohydrin ether tends to be obtained.
反応時間は、バッチ法の場合は、通常１〜１２時間、好ましくは２〜１０時間、より好ましくは４〜８時間である。反応時間が１時間以上であることにより、反応が十分進行し、ポリオール化合物の末端の少なくとも一方にエピハロヒドリンが付加したエピハロヒドリンエーテルを得られる傾向にある。また、反応時間が１２時間以下であることにより、エピハロヒドリンの自己重合等の副反応を抑制でき、純度の高いエピハロヒドリンエーテルを得られる傾向にある。
流通法の場合、反応速度、副反応抑制及び圧力損失による触媒劣化抑制の観点から、通液回数と、通液１回当たりの触媒及び反応液の接触時間を掛けた反応時間は、通常１〜２４時間、好ましくは２〜１８時間、より好ましくは４〜１２時間である。上記反応時間が１時間以上であることにより、反応が十分進行し、ポリオール化合物の末端の少なくとも一方にエピハロヒドリンが付加したエピハロヒドリンエーテルを得られる傾向にある。また、上記反応時間が２４時間以下であることにより、エピハロヒドリンの自己重合等の副反応及び圧力損失による反応勾配を抑制でき、純度の高いエピハロヒドリンエーテルを得られる傾向にある。
The reaction time is usually 1 to 12 hours, preferably 2 to 10 hours, more preferably 4 to 8 hours in the case of a batch method. When the reaction time is 1 hour or more, the reaction proceeds sufficiently, and it tends to be possible to obtain an epihalohydrin ether in which an epihalohydrin is added to at least one of the ends of the polyol compound. In addition, when the reaction time is 12 hours or less, side reactions such as self polymerization of epihalohydrin can be suppressed, and a high purity epihalohydrin ether tends to be obtained.
In the case of the flow method, from the viewpoint of reaction rate, suppression of side reaction and suppression of catalyst deterioration due to pressure loss, the reaction time obtained by multiplying the number of times of liquid passage and contact time of catalyst and reaction liquid per one liquid passage It is 24 hours, preferably 2 to 18 hours, more preferably 4 to 12 hours. When the reaction time is 1 hour or more, the reaction proceeds sufficiently, and it tends to be possible to obtain an epihalohydrin ether in which an epihalohydrin is added to at least one of the ends of the polyol compound. In addition, when the reaction time is 24 hours or less, side reactions such as self polymerization of epihalohydrin and reaction gradients due to pressure loss can be suppressed, and a high purity epihalohydrin ether tends to be obtained.
バッチ法、流通法のいずれの場合でも、無溶媒で反応を行ってもよく、溶媒を使用し反応を行ってもよい。溶媒としては、特に限定されないが、例えば、ヘキサン、トルエン、キシレン、酢酸エチル、クロロホルム等の無極性溶媒；アセトン、アセトニトリル、テトラヒドロフラン、メチルエチルケトン、メチルイソブチルケトン、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の極性非プロトン性溶媒；メタノール、エタノール、１−プロパノール等の極性プロトン性溶媒；水等が挙げられる。これらの溶媒は１種単独で使用してもよく、２種以上を併用してもよい。 In either of the batch method and the flow method, the reaction may be performed without a solvent, or may be performed using a solvent. The solvent is not particularly limited, but nonpolar solvents such as hexane, toluene, xylene, ethyl acetate, chloroform etc .; acetone, acetonitrile, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, dimethyl sulfoxide etc. Polar aprotic solvents; polar protic solvents such as methanol, ethanol and 1-propanol; water and the like. These solvents may be used alone or in combination of two or more.
上記溶媒の中でも、反応阻害の観点から無極性溶媒、極性プロトン性溶媒が好ましく、反応制御の観点から無極性溶媒がより好ましい。 Among the above solvents, nonpolar solvents and polar protic solvents are preferable from the viewpoint of reaction inhibition, and nonpolar solvents are more preferable from the viewpoint of reaction control.
付加反応終了後、ろ過、遠心分離、デカンテーション等によって反応液と固体酸触媒を分離することが好ましい。次いで、分離した反応液を、常圧或いは減圧下で加熱することによって、残留するエピハロヒドリンを除去し、エピハロヒドリンエーテルを回収する。 After completion of the addition reaction, the reaction solution and the solid acid catalyst are preferably separated by filtration, centrifugation, decantation or the like. Next, the separated reaction liquid is heated under normal pressure or reduced pressure to remove the remaining epihalohydrin and recover epihalohydrin ether.
分離した固体酸触媒は、洗浄、風乾、加熱等により再生させることで、再度、反応に使用することができる。 The separated solid acid catalyst can be used again for the reaction by regeneration by washing, air drying, heating or the like.
〔閉環反応工程〕
閉環反応工程は、付加反応工程により得られたエピハロヒドリンエーテルを、アルカリ性化合物存在下で閉環させることにより、エポキシ樹脂を得る工程である。
[Closing reaction step]
The ring closure reaction step is a step for obtaining an epoxy resin by ring closure of the epihalohydrin ether obtained by the addition reaction step in the presence of an alkaline compound.
アルカリ性化合物としては、特に限定されないが、例えば、水酸化ナトリウム、水酸化カリウム、水酸化バリウム、炭酸カリウム等が挙げられる。これらは、１種単独で使用してもよく、２種以上を併用してもよい。
アルカリ性化合物の状態は、特に限定されず、例えば、固体状、液状、水溶液、アルコール溶液等の状態でよい。
アルカリ性化合物の添加量は、エピハロヒドリンエーテルの活性水酸基１当量に基づいて、通常１〜１０当量、好ましくは１．２〜５．０当量、より好ましくは１．５〜３．０当量である。アルカリ性化合物の添加量が１当量以上であることにより、反応が十分に進行し、エピハロヒドリンが十分に閉環されたエポキシ樹脂を得られる傾向にある。アルカリ性化合物の添加量が１０当量以下であることにより、エピハロヒドリン及びエポキシ樹脂の重合反応を抑制でき、純度の高いエポキシ樹脂が得られる傾向にある。
The alkaline compound is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, barium hydroxide, potassium carbonate and the like. These may be used alone or in combination of two or more.
The state of the alkaline compound is not particularly limited, and may be, for example, a solid, liquid, aqueous solution, alcohol solution or the like.
The addition amount of the alkaline compound is usually 1 to 10 equivalents, preferably 1.2 to 5.0 equivalents, more preferably 1.5 to 3.0 equivalents, based on 1 equivalent of the active hydroxyl group of the epihalohydrin ether. When the addition amount of the alkaline compound is 1 equivalent or more, the reaction proceeds sufficiently, and it tends to be possible to obtain an epoxy resin in which the epihalohydrin is sufficiently closed. When the addition amount of the alkaline compound is 10 equivalents or less, the polymerization reaction of the epihalohydrin and the epoxy resin can be suppressed, and an epoxy resin with high purity tends to be obtained.
閉環反応工程では、反応を促進させる観点から、相間移動触媒を用いることが好ましい。特に、上記したアルカリ性化合物と相間移動触媒とを併用することがより好ましい。 In the cyclization reaction step, a phase transfer catalyst is preferably used from the viewpoint of promoting the reaction. In particular, it is more preferable to use the above-mentioned alkaline compound and the phase transfer catalyst in combination.
相間移動触媒としては、特に限定されないが、例えば、テトラメチルアンモニウムクロリド、テトラメチルアンモニウムブロミド、テトラプロピルアンモニウムクロリド、テトラプロピルアンモニウムブロミド、テトラブチルアンモニウムクロリド、テトラブチルアンモニウムブロミド、テトラブチルアンモニウムヨージド、ベンジルトリメチルアンモニウムクロリド、ベンジルトリメチルアンモニウムブロミド、ベンジルトリエチルアンモニウムクロリド、ベンジルトリエチルアンモニウムブロミド、フェニルトリメチルアンモニウムクロリド等の四級アンモニウム塩類；テトラメチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド等の四級アンモニウム水酸化物類；１５−クラウン−５、１８−クラウン−６、ジベンゾ−１８−クラウン−６、ジシクロヘキシル−１８−クラウン−６、ジアザ−１８−クラウン−６等のクラウンエーテル類；［２．１．１］−クリプタンド、［２．２．１］−クリプタンド、［２．２．２］クリプタンド、［２．２．２］−デシルクリプタンド、［２．２．２］−ベンゾクリプタンド等のクリプタンド類等が挙げられる。これらは、１種単独で使用してもよく、２種以上を併用してもよい。
相間移動触媒の状態は、特に限定されず、例えば、固体状、液状、水溶液、アルコール溶液等の状態でよい。
The phase transfer catalyst is not particularly limited. For example, tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetrapropyl ammonium chloride, tetrapropyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, benzyl Quaternary ammonium salts such as trimethyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl triethyl ammonium chloride, benzyl triethyl ammonium bromide, phenyltrimethyl ammonium chloride and the like; tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide and the like; Grade ammonium hydroxides; Crown ethers such as 5-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, diaza-18-crown-6, etc. [2.1.1] -cryptand And cryptands such as [2.2.1] -cryptand, [2.2.2] cryptand, [2.2.2] -decyl cryptand, [2.2.2] -benzocryptand and the like. Be These may be used alone or in combination of two or more.
The state of the phase transfer catalyst is not particularly limited, and may be, for example, a solid, liquid, aqueous solution, alcohol solution or the like.
相間移動触媒の添加量は、エピハロヒドリンエーテルの活性水酸基１モルに基づいて、通常０．００５〜１モル、好ましくは０．０１〜０．１モルである。相間移動触媒の添加量が０．００５モル以上であることにより、反応が十分に進行し、エピハロヒドリンが十分に閉環されたエポキシ樹脂を得られる傾向にある。また、相間移動触媒の添加量が１モル以下であることにより、エポキシ樹脂組成物から相間移動触媒を、水洗等により十分除去できる傾向にある。 The amount of phase transfer catalyst added is usually 0.005 to 1 mol, preferably 0.01 to 0.1 mol, based on 1 mol of the active hydroxyl group of the epihalohydrin ether. When the addition amount of the phase transfer catalyst is 0.005 mol or more, the reaction proceeds sufficiently, and the epihalohydrin tends to be able to obtain an epoxy resin sufficiently closed. In addition, when the addition amount of the phase transfer catalyst is 1 mole or less, the phase transfer catalyst tends to be sufficiently removed from the epoxy resin composition by water washing or the like.
反応温度は、通常２５〜１００℃、好ましくは３０〜８０℃である。反応温度が２５℃以上であることにより、反応の進行が速くなるため、エピハロヒドリンエーテルを効率よく閉環できる傾向にある。また、反応温度が１００℃以下であることにより、エピハロヒドリンエーテル同士の高分子化反応を抑制でき、エピハロヒドリンエーテルを効率よく閉環できる傾向にある。 The reaction temperature is generally 25 to 100 ° C., preferably 30 to 80 ° C. When the reaction temperature is 25 ° C. or more, the progress of the reaction becomes fast, and thus the epihalohydrin ether tends to be able to be ring-closed efficiently. In addition, when the reaction temperature is 100 ° C. or less, the polymerization reaction of the epihalohydrin ethers can be suppressed, and the epihalohydrin ether tends to be able to be ring-closed efficiently.
反応時間は、通常０．５〜１２時間、好ましくは１〜８時間、より好ましくは２〜６時間である。反応時間が０．５時間以上であることにより、反応が十分進行し、エピハロヒドリンエーテルを効率よく閉環できる傾向にある。また、反応時間が１２時間以下であることにより、エピハロヒドリンエーテル同士の高分子化反応を抑制でき、エピハロヒドリンエーテルを効率よく閉環できる傾向にある。 The reaction time is usually 0.5 to 12 hours, preferably 1 to 8 hours, more preferably 2 to 6 hours. When the reaction time is 0.5 hours or more, the reaction proceeds sufficiently, and the epihalohydrin ether tends to be able to be closed efficiently. In addition, when the reaction time is 12 hours or less, the polymerization reaction of the epihalohydrin ethers can be suppressed, and the epihalohydrin ether tends to be able to be ring-closed efficiently.
閉環反応工程は、無溶媒で反応を行ってもよく、溶媒を使用して反応を行ってもよい。溶媒としては、特に限定されないが、例えば、ヘキサン、トルエン、キシレン、酢酸エチル、クロロホルム等の無極性溶媒；アセトン、アセトニトリル、テトラヒドロフラン、メチルエチルケトン、メチルイソブチルケトン、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の極性非プロトン性溶媒；メタノール、エタノール、１−プロパノール等の極性プロトン性溶媒；水等が挙げられる。これらの溶媒は１種単独で使用してもよく、２種以上を併用してもよい。 In the cyclization reaction step, the reaction may be carried out without a solvent, or the reaction may be carried out using a solvent. The solvent is not particularly limited, but nonpolar solvents such as hexane, toluene, xylene, ethyl acetate, chloroform etc .; acetone, acetonitrile, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, dimethyl sulfoxide etc. Polar aprotic solvents; polar protic solvents such as methanol, ethanol and 1-propanol; water and the like. These solvents may be used alone or in combination of two or more.
上記溶媒の中でも、反応の進行が阻害されることを防ぐ観点から、無極性溶媒、極性プロトン性溶媒が好ましく、反応制御と回収容易性の観点から、トルエン、メチルエチルケトン、メチルイソブチルケトンがより好ましい。 Among the above solvents, nonpolar solvents and polar protic solvents are preferred from the viewpoint of preventing the progress of the reaction from being inhibited, and toluene, methyl ethyl ketone and methyl isobutyl ketone are more preferred from the viewpoint of reaction control and recovery ease.
生成塩、残留するアルカリ性化合物及び相間移動触媒等は、閉環反応終了後、例えば、水洗等によって、反応液から除去することが好ましい。次いで、例えば、反応液を常圧或いは減圧下で加熱することによって、溶媒を反応液から除去し、エポキシ樹脂を回収することができる。 It is preferable to remove the formed salt, the remaining alkaline compound, the phase transfer catalyst and the like from the reaction solution by, for example, water washing after completion of the ring closure reaction. Then, the solvent can be removed from the reaction solution, for example, by heating the reaction solution under normal pressure or reduced pressure, and the epoxy resin can be recovered.
［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）本実施形態のエポキシ樹脂（本明細書中、単「（Ａ）成分」ともいう）を含むものであれば特に制限されないが、（Ａ）本実施形態のエポキシ樹脂と、（Ｂ）その他のエポキシ樹脂（本明細書中、単に「（Ｂ）成分」ともいう）と、（Ｃ）硬化剤（本明細書中、単に「（Ｃ）成分」ともいう）と、を含み、前記（Ａ）成分１００質量部に基づいて、前記（Ｂ）成分が１〜４００質量部であり、前記（Ａ）成分と前記（Ｂ）成分の合計エポキシ基１当量に基づいて、前記（Ｃ）成分が０．５〜３．０当量であることが好ましい。各成分について、以下で詳述する。
[Epoxy resin composition]
The epoxy resin composition of the present embodiment is not particularly limited as long as it contains (A) the epoxy resin of the present embodiment (also referred to as a single “(A) component” in the present specification). The epoxy resin of the embodiment, (B) another epoxy resin (also referred to simply as “component (B)” herein), and (C) a curing agent (only “component (C)” herein) And the component (B) is 1 to 400 parts by mass based on 100 parts by mass of the component (A), and the total epoxy group 1 of the component (A) and the component (B) It is preferable that the said (C) component is 0.5-3.0 equivalent based on an equivalent. Each component is described in detail below.
〔（Ｂ）その他のエポキシ樹脂〕
（Ｂ）その他のエポキシ樹脂とは、上記の（Ａ）成分以外のエポキシ樹脂である。（Ｂ）成分としては、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、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等が挙げられる。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。
[(B) Other epoxy resin]
(B) Other epoxy resins are epoxy resins other than the above-mentioned (A) ingredient. As the component (B), for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, tetrabromobisphenol A epoxy resin, biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, tetrabromobiphenyl Type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenyl benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene Type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin And bifunctional epoxy resins such as resorcinol type epoxy resin, methyl resorcinol type epoxy resin, catechol type epoxy resin, N, N-diglycidyl aniline type epoxy resin; N, N-diglycidyl aminobenzene type epoxy resin, o- Trifunctional epoxy resins such as (N, N-diglycidylamino) toluene type epoxy resin, triazine type epoxy resin; tetrafunctional epoxy resins such as tetraglycidyl diaminodiphenylmethane type epoxy resin, diaminobenzene type epoxy resin; phenol Novolak type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, naphthol aralkyl type epoxy resin, brominated phenol no Polyfunctional epoxy resins of the rack-type epoxy resin or the like; and alicyclic epoxy resins and the like. Furthermore, epoxy resin etc. which modified these with isocyanate etc. can be used together.
本実施形態のエポキシ樹脂組成物中の（Ａ）成分１００質量部に基づいて、（Ｂ）成分は１〜４００質量部であり、好ましくは２０〜３００部である。（Ｂ）成分が１質量部以上であることにより、ミクロ相分離が起こり、十分な耐衝撃性を有したまま、良好な強度を有する硬化物を得られる傾向にある。また、（Ｂ）成分が４００質量部以下であることにより、十分な強度を有したまま、良好な耐衝撃性を有する硬化物を得られる傾向にある。 Based on 100 parts by mass of the component (A) in the epoxy resin composition of the present embodiment, the amount of the component (B) is 1 to 400 parts by mass, preferably 20 to 300 parts. When the component (B) is 1 part by mass or more, microphase separation occurs, and a cured product having good strength tends to be obtained while having sufficient impact resistance. In addition, when the component (B) is 400 parts by mass or less, a cured product having good impact resistance tends to be obtained while having sufficient strength.
［（Ｃ）硬化剤］
（Ｃ）硬化剤としては、特に制限されないが、例えば、酸無水物系硬化剤、アミン系硬化剤、フェノール系硬化剤、潜在性硬化剤、触媒型硬化剤等が挙げられる。
[(C) curing agent]
The curing agent (C) is not particularly limited, and examples thereof include acid anhydride curing agents, amine curing agents, phenol curing agents, latent curing agents, and catalyst curing agents.
酸無水物系硬化剤としては、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。 As the acid anhydride curing agent, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, Methyl hexahydrophthalic anhydride etc. are mentioned.
アミン系硬化剤としては、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、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、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等が挙げられる。
Examples of the amine curing agent include aliphatic amines and aromatic amines.
Examples of aliphatic amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane And bis (4-aminocyclohexyl) methane, norbornene diamine, 1,2-diaminocyclohexane and the like.
Examples of the aromatic amine include diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylene bis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate and the like.
フェノール系硬化剤としては、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。 As a phenol type curing agent, for example, phenol novolak resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol resin, biphenyl modified phenol aralkyl resin, dicyclopentadiene modified phenol resin, aminotriazine modified resin Phenol resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, allyl acrylic phenol resin and the like can be mentioned.
潜在性硬化剤としては、例えば、イミダゾール化合物、ジシアンジアミド及びその誘導体、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硬化剤、包摂化合物と錯形成してなる硬化剤、多孔質体に吸着させてなる硬化剤等が挙げられる。潜在性硬化剤としては、具体的には、旭化成株式会社製 ノバキュア ＨＸ−３７２１、ＨＸ−３７２２、ＨＸ−３６１３、ＨＸ−３９２１ＨＰ、ＨＸＡ４９２２ＨＰ、ＨＸＡ５９４５ＨＰ；味の素ファインテクノ株式会社製 アミキュア ＰＮ−２３Ｊ、ＰＮ−４０Ｊ、ＭＹ−２４；富士化成工業株式会社製 フジキュアー ＦＸＲ−１０２０、ＦＸＲ−１０３０；等が挙げられる。 Examples of latent curing agents include imidazole compounds, dicyandiamide and derivatives thereof, amine-epoxy adducts, amine-urea adducts, curing agents formed by coating these, curing agents formed by complexing with inclusion compounds, The curing agent etc. which make it adsorb | suck to a porous body are mentioned. As the latent curing agent, specifically, Novacuer HX-3721, HX-3722, HX-3613, HX-3921HP, HXA4922HP, HXA5945HP manufactured by Asahi Kasei Co., Ltd .; 40J, MY-24; Fujicure FXR-1020 manufactured by Fuji Kasei Kogyo Co., Ltd., FXR-1030, and the like.
触媒型硬化剤としては、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。 As a catalyst type curing agent, a cationic thermosetting catalyst, BF 3 -amine complex, etc. are mentioned, for example.
これらの硬化剤は、１種単独で使用してもよく、２種以上を併用してもよい。
上記硬化剤の中でも、可撓性及び接着性の観点から、アミン系硬化剤が好ましい。また、耐熱性及び低吸水性の観点から、フェノール系硬化剤が好ましい。
These curing agents may be used alone or in combination of two or more.
Among the above-mentioned curing agents, amine-based curing agents are preferable from the viewpoint of flexibility and adhesiveness. In addition, from the viewpoint of heat resistance and low water absorption, a phenolic curing agent is preferable.
本実施形態のエポキシ樹脂組成物中の前記（Ａ）成分と（Ｂ）成分の合計エポキシ基１当量に基づいて、（Ｃ）成分は、０．５〜３．０当量であり、好ましくは０．８〜２．０当量である。（Ｃ）成分が０．５当量以上であることにより、耐衝撃を発現するために十分な度合いの架橋密度を有する硬化物を得られる傾向にある。（Ｃ）成分が３．０当量以下であることにより、硬化物の物性に左右されることなく、十分な耐衝撃性を有する硬化物を得られる傾向にある。 Component (C) is 0.5 to 3.0 equivalents, preferably 0, based on one equivalent of the total epoxy group of the components (A) and (B) in the epoxy resin composition of the present embodiment. .8 to 2.0 equivalents. When the amount of the component (C) is 0.5 equivalent or more, a cured product having a sufficient degree of crosslinking density to develop impact resistance tends to be obtained. When the amount of the component (C) is 3.0 equivalents or less, a cured product having sufficient impact resistance tends to be obtained regardless of the physical properties of the cured product.
また、本実施形態のエポキシ樹脂組成物は、硬化促進剤を更に含有してもよい。硬化促進剤としては、特に限定されないが、例えば、２−メチルイミダゾール、２−エチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール系硬化促進剤；２−（ジメチルアミノメチル）フェノール、１，５−ジアザビシクロ［４．３．０］ノナ−５−エン、１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン等の３級アミン系硬化促進剤；トリフェニルホスフィン等のリン系硬化促進剤；有機酸金属塩；ルイス酸；アミン錯塩等が挙げられる。これらは上述した硬化剤と併用することにより硬化反応を促進させることができる。硬化促進剤は、上述した硬化剤の種類に応じて、適切な種類を選択することができる。 The epoxy resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include imidazole-based curing accelerators such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) phenol, 1, Tertiary amine curing accelerators such as 5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] undec-7-ene; phosphorus systems such as triphenylphosphine Curing accelerators; organic acid metal salts; Lewis acids; amine complex salts and the like. The curing reaction can be accelerated by using these in combination with the above-mentioned curing agent. An appropriate type of curing accelerator can be selected according to the type of curing agent described above.
本実施形態のエポキシ樹脂組成物において、硬化促進剤の含有量は、本実施形態の効果が得られる範囲であれば特に限定されない。硬化促進剤の含有量は、通常、エポキシ樹脂の総量１００質量部に基づいて０．１〜５．０質量部であることが好ましい。硬化促進剤の含有量が０．１〜５．０質量部であることにより、硬化反応が十分に促進され、一層良好な硬化物性が得られる傾向にある。 In the epoxy resin composition of the present embodiment, the content of the curing accelerator is not particularly limited as long as the effects of the present embodiment can be obtained. The content of the curing accelerator is usually preferably 0.1 to 5.0 parts by mass based on 100 parts by mass of the total amount of epoxy resin. When the content of the curing accelerator is 0.1 to 5.0 parts by mass, the curing reaction is sufficiently accelerated, and it is likely that better cured physical properties can be obtained.
本実施形態のエポキシ樹脂組成物は、必要に応じて無機充填剤を更に含有してもよい。無機充填剤としては、特に限定されないが、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、窒化アルミ等が挙げられる。 The epoxy resin composition of the present embodiment may further contain an inorganic filler, if necessary. The inorganic filler is not particularly limited, and examples thereof include fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride and the like.
本実施形態のエポキシ樹脂組成物における無機充填剤の含有量は、本実施形態の効果が得られる範囲であれば特に限定されない。通常、本実施形態のエポキシ樹脂組成物の９０質量％以下であることが好ましい。無機充填剤の含有量を９０質量％以下とすることにより、エポキシ樹脂組成物の粘度が十分低く、取扱性に優れる傾向にある。 The content of the inorganic filler in the epoxy resin composition of the present embodiment is not particularly limited as long as the effects of the present embodiment can be obtained. Usually, it is preferable that it is 90 mass% or less of the epoxy resin composition of this embodiment. By setting the content of the inorganic filler to 90% by mass or less, the viscosity of the epoxy resin composition is sufficiently low, and the handling property tends to be excellent.
本実施形態のエポキシ樹脂組成物は、必要に応じて、難燃剤、シランカップリング剤、離型剤、顔料等の他の配合剤を更に含有してもよい。これらは、本実施形態の効果が得られる範囲であれば、適宜好適なものを選択することができる。例えば、難燃剤としては、特に限定されないが、例えば、ハロゲン化物、リン原子含有化合物、窒素原子含有化合物、無機系難燃化合物等が挙げられる。 The epoxy resin composition of the present embodiment may further contain other compounding agents such as a flame retardant, a silane coupling agent, a mold release agent, and a pigment, as necessary. As long as the effects of the present embodiment can be obtained, suitable ones can be appropriately selected. For example, the flame retardant is not particularly limited, and examples thereof include halides, phosphorus atom-containing compounds, nitrogen atom-containing compounds, inorganic flame retardant compounds and the like.
本実施形態のエポキシ樹脂組成物における、１４０℃で６０分間、さらに２２０℃で１２０分間硬化させて得られる硬化物の５０％破壊エネルギーは、好ましくは４〜２０Ｊであり、より好ましくは５〜１５Ｊであり、さらに好ましくは５〜１０Ｊである。５０％破壊エネルギーが４Ｊ以上であることにより、十分な耐衝撃性を得ることができ、衝撃等により接着面からの剥離及びクラックが発生しにくい傾向にある。５０％破壊エネルギーが２０Ｊ以下であることにより、落下等により発生する衝撃エネルギーが被着体や他の接着部位へ伝搬しにくくなるため、被着体の破壊や他の接着部位の剥離を抑制できる傾向にある。 The 50% breaking energy of the cured product obtained by curing at 140 ° C. for 60 minutes and further at 220 ° C. for 120 minutes in the epoxy resin composition of the present embodiment is preferably 4 to 20 J, more preferably 5 to 15 J More preferably, it is 5 to 10 J. When the 50% breaking energy is 4 J or more, sufficient impact resistance can be obtained, and peeling and cracking from the adhesive surface tend to be less likely to occur due to impact or the like. When the 50% destruction energy is 20 J or less, the impact energy generated due to the drop or the like is less likely to propagate to the adherend or other adhesion site, so the destruction of the adherend or the peeling off of other adhesion sites can be suppressed. There is a tendency.
本実施形態の硬化物は、本実施形態の樹脂組成物から作製され、本実施形態のエポキシ樹脂組成物を硬化してなる硬化物である。
本実施形態の硬化物は、上記のエポキシ樹脂組成物を、例えば、従来公知の方法等により熱硬化させることで得られる。具体的には、以下の方法により本実施形態の硬化物を得ることができる。
まず、本実施形態のエポキシ樹脂と、硬化剤と、更に必要に応じて硬化促進剤、無機充填剤、及び／又は配合剤等とを、押出機、ニーダ、ロール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。その後、エポキシ樹脂組成物を注型あるいはトランスファー成形機、コンプレッション成形機、射出成形機等を用いて成形し、６０〜２５０℃程度で１分〜１０時間程度の条件で更に加熱することにより、硬化物を得ることができる。
The cured product of the present embodiment is a cured product produced from the resin composition of the present embodiment and cured by curing the epoxy resin composition of the present embodiment.
The cured product of the present embodiment can be obtained by, for example, thermally curing the above-mentioned epoxy resin composition by a conventionally known method or the like. Specifically, the cured product of the present embodiment can be obtained by the following method.
First, until the epoxy resin of the present embodiment, a curing agent, and, if necessary, a curing accelerator, an inorganic filler, and / or a compounding agent, etc. are uniformed using an extruder, a kneader, a roll, etc. The mixture is thoroughly mixed to obtain an epoxy resin composition. Thereafter, the epoxy resin composition is molded using a casting or transfer molding machine, a compression molding machine, an injection molding machine or the like, and is further heated at about 60 to 250 ° C. under conditions of about 1 minute to 10 hours. You can get things.
また、本実施形態の硬化物は、以下の方法によりを得ることもできる。
まず、本実施形態のエポキシ樹脂組成物を、トルエン、キシレン、アセトン、メチルエチルケトン、メチルイソブチルケトン等の溶剤に溶解させ、溶液を得る。得られた溶液を、ガラス繊維、カーボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙等の基材に含浸させ、加熱乾燥してプリプレグを得る。次に、得られたプリプレグを熱プレス成形することにより、硬化物を得ることもできる。
Moreover, the hardened | cured material of this embodiment can also be obtained by the following method.
First, the epoxy resin composition of the present embodiment is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone and methyl isobutyl ketone to obtain a solution. The obtained solution is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and the like, and dried by heating to obtain a prepreg. Next, a cured product can be obtained by subjecting the obtained prepreg to hot press molding.
本実施形態のエポキシ樹脂組成物は、耐衝撃性に優れ、さらには透明性も有している。そのため、本実施形態のエポキシ樹脂組成物は、半導体パッケージや半導体チップ等の電子部材、及びＬＥＤやカメラモジュール等の光学部材における封止材、接着剤として好適に用いることができる。 The epoxy resin composition of the present embodiment is excellent in impact resistance and further has transparency. Therefore, the epoxy resin composition of the present embodiment can be suitably used as a sealing material or an adhesive in electronic members such as semiconductor packages and semiconductor chips, and optical members such as LEDs and camera modules.
本実施形態のエポキシ樹脂組成物、及びその硬化物からなる成形体は、エポキシ樹脂が材料として用いられる種々の用途に使用できる。用途としては、特に限定されないが、ＬＥＤやカメラモジュール等の光学部材封止材が好ましい。また、用途としては、アンダーフィルやモールディング等の半導体封止材、異方性導電フィルム（ＡＣＦともいう）等の導電性接着剤、ソルダーレジストやカバーレイフィルム等のプリント配線基板等にも好適に用いられる。 The epoxy resin composition of the present embodiment and the molded product made of the cured product thereof can be used in various applications where an epoxy resin is used as a material. Although it does not specifically limit as a use, Optical member sealing materials, such as LED and a camera module, are preferable. In addition, as applications, semiconductor encapsulation materials such as underfill and molding, conductive adhesives such as anisotropic conductive film (also referred to as ACF), printed wiring boards such as solder resist and cover lay film, etc. Used.
次に、本発明を、実施例及び比較例により更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 more specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto. In the following, "parts" and "%" are based on mass unless otherwise noted.
各物性の測定方法は以下のとおりとした。 The measuring method of each physical property was as follows.
（１）エポキシ当量
後述するエポキシ樹脂を対象とし、ＪＩＳ Ｋ７２３６に準拠して、エポキシ当量を測定した。
(1) Epoxy equivalent The epoxy equivalent was measured based on JISK7236 for the epoxy resin mentioned later.
（２）全塩素量
後述するエポキシ樹脂を対象とし、ＪＩＳ Ｋ７２４３−３に準拠して、全塩素量を測定した。
(2) Total chlorine content The total chlorine content was measured based on JISK7243-3 for the epoxy resin mentioned later.
（３）ガードナー色数
後述するエポキシ樹脂を対象とし、ＪＩＳ Ｋ００７１−２に準拠して、ガードナー色数を測定した。
(3) Gardner color number Gardner color number was measured based on JISK0071-2 for the epoxy resin mentioned later.
（４）５０％破壊エネルギー
後述する硬化物を対象とし、ＪＩＳ Ｋ７２１１に準拠して、５０％破壊エネルギーを測定した。
(4) 50% destruction energy 50% destruction energy was measured based on JISK7211 for the hardened | cured material mentioned later.
［実施例１］
（付加反応工程）
温度計、滴下ロート、冷却管、及び撹拌機を備えたガラス製のジャケット式反応器に、ビスフェノールＡのエチレンオキシド６モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−６０」；水酸基価：２２８ｍｇＫＯＨ／ｇ １００ｇ、固体酸触媒；日本活性白土株式会社製 商品名「ニッカナイトＧＣＨ−３６」 １０ｇ、トルエン８０ｇを混合した。反応器内に窒素を導入しながら、８０℃で撹拌し懸濁させた。そして、エピクロロヒドリン５６ｇを２時間かけて滴下した。滴下後、さらに４時間反応させた後、混合物を冷却しデカンテーションにより反応液と固体酸触媒を分離した。反応液をメンブレンフィルターで加圧ろ過し、得られたろ液から、過剰のエピクロロヒドリンを減圧下で蒸留して除去し、エピハロヒドリンエーテルを得た。
（閉環反応工程）
得られたエピハロヒドリンエーテル１００ｇをトルエン１００ｇに溶解し、エピハロヒドリンエーテルの活性水酸基１当量に基づいて、１．５当量の５０質量％水酸化ナトリウム水溶液を加え、さらにエピハロヒドリンエーテルの活性水酸基１当量に基づいて、０．０１当量の５０質量％テトラメチルアンモニウムクロリド水溶液を加え、８０℃で２時間反応させた。反応終了後、反応生成物の水洗を繰り返して、反応生成物から、副生した塩化ナトリウムを除去した。また、反応生成物から、メチルイソブチルケトンを減圧下で蒸留して除去し、エポキシ樹脂Ａ−１を得た。
Example 1
(Addition reaction process)
In a glass jacketed reactor equipped with a thermometer, a dropping funnel, a condenser and a stirrer, ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name "New pole BPE-60"; hydroxyl group Value: 228 mg KOH / g 100 g, solid acid catalyst; 10 g of Nikkanite GCH-36 (trade name) manufactured by Nippon Activated Shirato Co., and 80 g of toluene were mixed. The mixture was stirred and suspended at 80 ° C. while introducing nitrogen into the reactor. Then, 56 g of epichlorohydrin was dropped over 2 hours. After dropping, the mixture was allowed to react for 4 hours, then the mixture was cooled, and the reaction solution and the solid acid catalyst were separated by decantation. The reaction solution was pressure-filtered with a membrane filter, and excess epichlorohydrin was removed by distillation under reduced pressure from the obtained filtrate to obtain epihalohydrin ether.
(Closing reaction process)
100 g of the obtained epihalohydrin ether is dissolved in 100 g of toluene, and 1.5 equivalents of 50% by mass aqueous sodium hydroxide solution is added based on 1 equivalent of active hydroxyl group of epihalohydrin ether, and further based on 1 equivalent of active hydroxyl group of epihalohydrin ether Then, 0.01 equivalent of 50% by mass of tetramethylammonium chloride aqueous solution was added and reacted at 80 ° C. for 2 hours. After completion of the reaction, the reaction product was repeatedly washed with water to remove by-produced sodium chloride from the reaction product. Further, methyl isobutyl ketone was removed by distillation under reduced pressure from the reaction product to obtain epoxy resin A-1.
［実施例２］
固体酸触媒の量を３１ｇに変更したこと以外は、実施例１と同様に行い、エポキシ樹脂Ａ−２を得た。
Example 2
An epoxy resin A-2 was obtained in the same manner as in Example 1 except that the amount of the solid acid catalyst was changed to 31 g.
［実施例３］
固体酸触媒の量を２０ｇに変更し、エピクロロヒドリンの量を１１３ｇに変更したこと以外は、実施例１と同様に行い、エポキシ樹脂Ａ−３を得た。
[Example 3]
An epoxy resin A-3 was obtained in the same manner as in Example 1 except that the amount of the solid acid catalyst was changed to 20 g and the amount of epichlorohydrin was changed to 113 g.
［実施例４］
エピクロロヒドリンの量を７５ｇに変更したこと以外は、実施例３と同様に行い、エポキシ樹脂Ａ−４を得た。
Example 4
An epoxy resin A-4 was obtained in the same manner as in Example 3 except that the amount of epichlorohydrin was changed to 75 g.
［実施例５］
固体酸触媒の種類を日本活性白土株式会社製；商品名「ニッカナイトＳ−２００」に変更したこと以外は、実施例４と同様に行い、エポキシ樹脂Ａ−５を得た。
[Example 5]
An epoxy resin A-5 was obtained in the same manner as in Example 4 except that the type of solid acid catalyst was changed to Nippon Activated Shirato Co., Ltd .; trade name "Nikkanite S-200".
［実施例６］
固体酸触媒の種類を日揮触媒化成株式会社製；商品名「ＺＳＭ−５」に変更したこと以外は、実施例４と同様に行い、エポキシ樹脂Ａ−６を得た。
[Example 6]
An epoxy resin A-6 was obtained in the same manner as in Example 4 except that the type of solid acid catalyst was changed to JGC Catalyst Chemical Co., Ltd .; trade name "ZSM-5".
［実施例７］
固体酸触媒の種類をテイカ株式会社製 商品名「テイカキュアＳＡＣ−１０」に変更し、固体酸触媒の量を２４ｇに変更し、エピクロロヒドリンの量を７１ｇに変更したこと以外は、実施例１と同様に行い、エポキシ樹脂Ａ−７を得た。
[Example 7]
Example except changing the kind of solid acid catalyst into the brand name "Taikacure SAC-10" made by Tayca Co., Ltd., changing the amount of solid acid catalyst to 24 g and changing the amount of epichlorohydrin to 71 g It carried out like 1 and obtained epoxy resin A-7.
［実施例８］
（付加反応工程）
温度計及び撹拌機を備えたガラス製のジャケット式反応器に、ビスフェノールＡのエチレンオキシド６モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−６０」；水酸基価：２２８ｍｇＫＯＨ／ｇ １００ｇ、エピクロロヒドリン１１３ｇ、トルエン８０ｇを混合した。反応器内に窒素を導入しながら、８０℃で撹拌し懸濁させた。固体酸触媒；日本活性白土株式会社製 商品名「ニッカナイトＧＣＨ−３６」 ４６２ｇを充填したステンレス製の固定床の入側及び出側を反応器に連結した後、ポンプで反応液を８時間循環させた。１サイクルあたりの反応液の固定床滞留時間は約２分であり、サイクル回数は約２００回であった。反応終了後、反応液から過剰のエピクロロヒドリンを減圧下で蒸留して除去し、エピハロヒドリンエーテルを得た。
（閉環反応工程）
得られたエピハロヒドリンエーテル１００ｇをトルエン１００ｇに溶解し、エピハロヒドリンエーテルの活性水酸基１当量に基づいて、１．５当量の５０質量％水酸化ナトリウム水溶液を加え、さらにエピハロヒドリンエーテルの活性水酸基１当量に基づいて、０．０１当量の５０質量％テトラメチルアンモニウムクロリド水溶液を加え、８０℃で２時間反応させた。反応終了後、反応生成物の水洗を繰り返して、反応生成物から、副生した塩化ナトリウムを除去した。また、反応生成物から、メチルイソブチルケトンを減圧下で蒸留して除去し、エポキシ樹脂Ａ−８を得た。
[Example 8]
(Addition reaction process)
In a glass jacketed reactor equipped with a thermometer and a stirrer, ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name "New pole BPE-60"; hydroxyl value: 228 mg KOH / g 100 g, 113 g of epichlorohydrin and 80 g of toluene were mixed. The mixture was stirred and suspended at 80 ° C. while introducing nitrogen into the reactor. Solid acid catalyst; Nippon Activated Shirato Co., Ltd. product name "Nikkanite GCH-36" Trade name: "Nickanite GCH-36" After connecting the inlet side and outlet side of the fixed bed made of stainless steel to the reactor, the reaction liquid is circulated by pump for 8 hours I did. The fixed bed residence time of the reaction solution per cycle was about 2 minutes, and the number of cycles was about 200 times. After completion of the reaction, excess epichlorohydrin was removed by distillation under reduced pressure from the reaction solution to obtain epihalohydrin ether.
(Closing reaction process)
100 g of the obtained epihalohydrin ether is dissolved in 100 g of toluene, and 1.5 equivalents of 50% by mass aqueous sodium hydroxide solution is added based on 1 equivalent of active hydroxyl group of epihalohydrin ether, and further based on 1 equivalent of active hydroxyl group of epihalohydrin ether Then, 0.01 equivalent of 50% by mass of tetramethylammonium chloride aqueous solution was added and reacted at 80 ° C. for 2 hours. After completion of the reaction, the reaction product was repeatedly washed with water to remove by-produced sodium chloride from the reaction product. Further, methyl isobutyl ketone was removed by distillation under reduced pressure from the reaction product to obtain epoxy resin A-8.
［実施例９］
ビスフェノールＡのエチレンオキシド６モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−６０」；水酸基価：２２８ｍｇＫＯＨ／ｇからビスフェノールＡのエチレンオキシド１０モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−１００」；水酸基価：１６７ｍｇＫＯＨ／ｇに変更し、固体酸触媒の量を１５ｇに変更し、エピクロロヒドリンの量を５６ｇに変更し、溶媒をメチルエチルケトンに変更し、反応時間を８時間に変更した以外は、実施例１と同様に行い、エポキシ樹脂Ａ−９を得た。
[Example 9]
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to 10 mol adduct of bisphenol A ethylene oxide; manufactured by Sanyo Chemical Industries Ltd. trade name “ Hydroxyl value: changed to 167 mg KOH / g, the amount of solid acid catalyst was changed to 15 g, the amount of epichlorohydrin was changed to 56 g, the solvent was changed to methyl ethyl ketone, the reaction time was changed An epoxy resin A-9 was obtained in the same manner as in Example 1 except that the time was changed to 8 hours.
［実施例１０］
固体酸触媒の種類をテイカ株式会社製 商品名「テイカキュアＳＡＣ−１０」に変更し、固体酸触媒の量を２２ｇに変更し、エピクロロヒドリンの量を８３ｇに変更し、反応時間を７時間に変更したこと以外は、実施例９と同様に行い、エポキシ樹脂Ａ−１０を得た。
[Example 10]
The type of solid acid catalyst was changed to Taika Co., Ltd. under the trade name "Taikacure SAC-10", the amount of solid acid catalyst was changed to 22 g, the amount of epichlorohydrin was changed to 83 g, and the reaction time was 7 hours The epoxy resin A-10 was obtained in the same manner as in Example 9 except for changing to.
［実施例１１］
ビスフェノールＡのエチレンオキシド６モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−６０」；水酸基価：２２８ｍｇＫＯＨ／ｇからビスフェノールＡのプロピレンオキシド５モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰ−５Ｐ」；水酸基価：２１１ｍｇＫＯＨ／ｇに変更し、固体酸触媒の量を１９ｇに変更し、エピクロロヒドリンの量を５３ｇに変更したこと以外は、実施例１と同様に行い、エポキシ樹脂Ａ−１１を得た。
[Example 11]
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to propylene oxide 5 mol adduct of bisphenol A; trade name made by Sanyo Chemical Industries, Ltd. "Neupol BP-5P"; hydroxyl value: changed to 211 mg KOH / g, changed amount of solid acid catalyst to 19 g, changed amount of epichlorohydrin to 53 g as in Example 1 To obtain an epoxy resin A-11.
［実施例１２］
エピクロロヒドリンの量を７１ｇに変更したこと以外は、実施例１１と同様に行い、エポキシ樹脂Ａ−１２を得た。
[Example 12]
An epoxy resin A-12 was obtained in the same manner as in Example 11 except that the amount of epichlorohydrin was changed to 71 g.
［実施例１３］
固体酸触媒の量を２９ｇに変更したこと以外は、実施例１２と同様に行い、エポキシ樹脂Ａ−１３を得た。
[Example 13]
An epoxy resin A-13 was obtained in the same manner as in Example 12 except that the amount of the solid acid catalyst was changed to 29 g.
［実施例１４］
固体酸触媒の種類を日揮触媒化成株式会社製 商品名「ＺＳＭ−５」に変更したこと以外は、実施例１２と同様に行い、エポキシ樹脂Ａ−１４を得た。
Example 14
An epoxy resin A-14 was obtained in the same manner as in Example 12 except that the type of solid acid catalyst was changed to a product name "ZSM-5" manufactured by JGC Co., Ltd.
［実施例１５］
固体酸触媒の種類をダウケミカル社製 商品名「アンバーリスト１５ＤＲＹ」に変更したこと以外は、実施例１２と同様に行い、エポキシ樹脂Ａ−１５を得た。
[Example 15]
An epoxy resin A-15 was obtained in the same manner as in Example 12 except that the type of solid acid catalyst was changed to Dow Chemical Co., Ltd. trade name "Amberlyst 15 DRY".
［実施例１６］
固体酸触媒の種類をテイカ株式会社製 商品名「テイカキュアＳＡＣ−１０」に変更したこと以外は、実施例１２と同様に行い、エポキシ樹脂Ａ−１６を得た。
[Example 16]
An epoxy resin A-16 was obtained in the same manner as in Example 12 except that the type of the solid acid catalyst was changed to Taika Co., Ltd. trade name "Taikacure SAC-10".
［実施例１７］
ビスフェノールＡのエチレンオキシド６モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−６０」；水酸基価：２２８ｍｇＫＯＨ／ｇからビスフェノールＡのプロピレンオキシド５モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰ−５Ｐ」；水酸基価：２１１ｍｇＫＯＨ／ｇに変更し、固体酸触媒の量を４６２ｇに変更し、エピクロロヒドリンの量を１０７ｇに変更したこと以外は、実施例１と同様に行い、エポキシ樹脂Ａ−１７を得た。
[Example 17]
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to propylene oxide 5 mol adduct of bisphenol A; trade name made by Sanyo Chemical Industries, Ltd. "Neupol BP-5P"; hydroxyl value: changed to 211 mg KOH / g, changed amount of solid acid catalyst to 462 g, changed amount of epichlorohydrin to 107 g, as in Example 1 The epoxy resin A-17 was obtained.
［実施例１８］
ビスフェノールＡのエチレンオキシド６モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−６０」；水酸基価：２２８ｍｇＫＯＨ／ｇからビスフェノールＡのエチレンオキシド４モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−４０」；水酸基価：２７６ｍｇＫＯＨ／ｇに変更し、固体酸触媒の量を１９ｇに変更し、エピクロロヒドリンの量を７２ｇに変更し、反応時間を５時間に変更したこと以外は、実施例１と同様に行い、エポキシ樹脂Ａ−１８を得た。
[Example 18]
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to ethylene oxide 4 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries Ltd. trade name “ Newpole BPE-40 "; hydroxyl value: changed to 276 mg KOH / g, changed amount of solid acid catalyst to 19 g, changed amount of epichlorohydrin to 72 g, and changed reaction time to 5 hours Were carried out in the same manner as in Example 1 to obtain an epoxy resin A-18.
［実施例１９］
エピクロロヒドリンの量を４５ｇに変更したこと以外は、実施例１と同様に行い、エポキシ樹脂Ａ−１９を得た。
[Example 19]
An epoxy resin A-19 was obtained in the same manner as in Example 1 except that the amount of epichlorohydrin was changed to 45 g.
［実施例２０］
固体酸触媒の量を８ｇに変更したこと以外は、実施例４と同様に行い、エポキシ樹脂Ａ−２０を得た。
[Example 20]
An epoxy resin A-20 was obtained in the same manner as in Example 4 except that the amount of the solid acid catalyst was changed to 8 g.
［実施例２１］
固体酸触媒の量を３３ｇに変更したこと以外は、実施例４と同様に行い、エポキシ樹脂Ａ−２１を得た。
[Example 21]
An epoxy resin A-21 was obtained in the same manner as in Example 4 except that the amount of the solid acid catalyst was changed to 33 g.
［実施例２２］
ビスフェノールＡのエチレンオキシド４モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−４０」；水酸基価：２７６ｍｇＫＯＨ／ｇからビスフェノールＡのプロピレンオキシド３モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰ−３Ｐ」；水酸基価：２８０ｍｇＫＯＨ／ｇに変更し、固体酸触媒の量を２５ｇに変更し、エピクロロヒドリンの量を９２ｇに変更したこと以外は、実施例１８と同様に行い、エポキシ樹脂Ａ−２２を得た。
Example 22
Ethylene oxide 4 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-40”; hydroxyl value: 276 mg KOH / g to propylene oxide 3 mol adduct of bisphenol A; trade name manufactured by Sanyo Chemical Industries, Ltd. "Neupol BP-3P"; hydroxyl value: changed to 280 mg KOH / g, the amount of solid acid catalyst was changed to 25 g, and the amount of epichlorohydrin was changed to 92 g as in Example 18 The epoxy resin A-22 was obtained.
［比較例１］
エピクロロヒドリンの量を２２５ｇに変更したこと以外は、実施例３と同様に行い、エポキシ樹脂Ａ−２３を得た。
Comparative Example 1
An epoxy resin A-23 was obtained in the same manner as in Example 3 except that the amount of epichlorohydrin was changed to 225 g.
［比較例２］
（付加反応工程）
温度計、滴下ロート、冷却管、及び撹拌機を備えたガラス製のジャケット式反応器に、ビスフェノールＡのエチレンオキシド６モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−６０」；水酸基価：２２８ｍｇＫＯＨ／ｇ １００ｇ、エピクロロヒドリン１８８ｇ、及び５０質量％テトラメチルアンモニウムクロリド水溶液４ｇを混合し、減圧下に加熱して６０℃で還流を行った。そして、５０質量％水酸化ナトリウム水溶液１６２ｇを２時間かけて滴下した。滴下の際、水をエピクロロヒドリンとの共沸混合物として連続的に除去するとともに、凝縮したエピクロロヒドリン層のみを連続的に反応器に戻した。滴下後、さらに２時間反応させた後、混合物を冷却し、水洗を繰り返して副生した塩化ナトリウムを除去した。過剰のエピクロロヒドリンを減圧下で蒸留して除去し、エピハロヒドリンエーテルを得た。
（閉環反応工程）
得られたエピハロヒドリンエーテル１００ｇをトルエン１００ｇに溶解し、エピハロヒドリンエーテルの活性水酸基１当量に基づいて、１．５当量の５０質量％水酸化ナトリウム水溶液を加え、さらにエピハロヒドリンエーテルの活性水酸基１当量に基づいて、０．０１当量の５０質量％テトラメチルアンモニウムクロリド水溶液を加え、８０℃で２時間反応させた。反応終了後、反応生成物の水洗を繰り返して、反応生成物から、副生した塩化ナトリウムを除去した。また、反応生成物から、メチルイソブチルケトンを減圧下で蒸留して除去し、エポキシ樹脂Ａ−２４を得た。
Comparative Example 2
(Addition reaction process)
In a glass jacketed reactor equipped with a thermometer, a dropping funnel, a condenser and a stirrer, ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name "New pole BPE-60"; hydroxyl group 100 mg of epichlorohydrin and 4 g of 50% by mass aqueous tetramethylammonium chloride solution were mixed, heated under reduced pressure, and refluxed at 60.degree. And 162 g of 50 mass% sodium hydroxide aqueous solution was dripped over 2 hours. During the addition, water was continuously removed as an azeotropic mixture with epichlorohydrin, and only the condensed epichlorohydrin layer was continuously returned to the reactor. After dropping, the mixture was allowed to react for another 2 hours, and then the mixture was cooled and washed with water repeatedly to remove by-produced sodium chloride. The excess epichlorohydrin was distilled off under reduced pressure to give epihalohydrin ether.
(Closing reaction process)
100 g of the obtained epihalohydrin ether is dissolved in 100 g of toluene, and 1.5 equivalents of 50% by mass aqueous sodium hydroxide solution is added based on 1 equivalent of active hydroxyl group of epihalohydrin ether, and further based on 1 equivalent of active hydroxyl group of epihalohydrin ether Then, 0.01 equivalent of 50% by mass of tetramethylammonium chloride aqueous solution was added and reacted at 80 ° C. for 2 hours. After completion of the reaction, the reaction product was repeatedly washed with water to remove by-produced sodium chloride from the reaction product. Further, methyl isobutyl ketone was removed by distillation under reduced pressure from the reaction product to obtain epoxy resin A-24.
［比較例３］
ビスフェノールＡのエチレンオキシド１０モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−１００」、水酸基価：１６７ｍｇＫＯＨ／ｇからビスフェノールＡのエチレンオキシド１８モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−１８０」；水酸基価：１１０ｍｇＫＯＨ／ｇに変更し、固体酸触媒の量を１０ｇに変更し、エピクロロヒドリンの量を３６ｇに変更し、反応時間を１０時間に変更したこと以外は、実施例９と同様に行い、エポキシ樹脂Ａ−２５を得た。
Comparative Example 3
Ethylene oxide 10 molar adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-100”, hydroxyl value: 167 mg KOH / g to ethylene oxide 18 molar adduct of bisphenol A; manufactured by Sanyo Chemical Industries Ltd. trade name “ Newpole BPE-180 "; hydroxyl value: changed to 110 mg KOH / g, changed amount of solid acid catalyst to 10 g, changed amount of epichlorohydrin to 36 g, and changed reaction time to 10 hours Were carried out in the same manner as in Example 9 to obtain an epoxy resin A-25.
［比較例４］
ビスフェノールＡのエチレンオキシド６モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−６０」；水酸基価：２２８ｍｇＫＯＨ／ｇからビスフェノールＡのプロピレンオキシド５モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰ−５Ｐ」；水酸基価：２１１ｍｇＫＯＨ／ｇに変更し、エピクロロヒドリンの量を１７２ｇに変更し、５０質量％水酸化ナトリウム水溶液の量を１４８ｇに変更したこと以外は、比較例２と同様に行い、エポキシ樹脂Ａ−２６を得た。
Comparative Example 4
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to propylene oxide 5 mol adduct of bisphenol A; trade name made by Sanyo Chemical Industries, Ltd. “New pole BP-5P”; hydroxyl value: changed to 211 mg KOH / g, changed amount of epichlorohydrin to 172 g, changed amount of 50% by mass aqueous sodium hydroxide solution to 148 g, Comparative Example It carried out similarly to 2, and obtained epoxy resin A-26.
［比較例５］
（付加反応工程）
温度計及び撹拌機を備えたガラス製のジャケット式反応器に、ビスフェノールＡのプロピレンオキシド５モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰ−５Ｐ」；水酸基価：２１１ｍｇＫＯＨ／ｇ １００ｇ、エピクロロヒドリン１７２ｇ、フレーク状水酸化ナトリウム５２ｇ、及び５０質量％テトラメチルアンモニウムクロリド水溶液４ｇを混合し、常圧下に加熱して６０℃で８時間反応させた。反応終了後、混合物を冷却し、水洗を繰り返して副生した塩化ナトリウムを除去した。過剰のエピクロロヒドリンを減圧下で蒸留して除去し、エピハロヒドリンエーテルを得た。
（閉環反応工程）
得られたエピハロヒドリンエーテル１００ｇをトルエン１００ｇに溶解し、エピハロヒドリンエーテルの活性水酸基１当量に基づいて、１．５当量の５０質量％水酸化ナトリウム水溶液を加え、さらにエピハロヒドリンエーテルの活性水酸基１当量に基づいて、０．０１当量の５０質量％テトラメチルアンモニウムクロリド水溶液を加え、８０℃で２時間反応させた。反応終了後、反応生成物の水洗を繰り返して、反応生成物から、副生した塩化ナトリウムを除去した。また、反応生成物から、メチルイソブチルケトンを減圧下で蒸留して除去し、エポキシ樹脂Ａ−２７を得た。
Comparative Example 5
(Addition reaction process)
In a glass jacket-type reactor equipped with a thermometer and a stirrer, 5 mol of propylene oxide adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd .; trade name "New Pole BP-5P"; hydroxyl value: 211 mg KOH / g 100 g A mixture of 172 g of epichlorohydrin, 52 g of flaky sodium hydroxide and 4 g of 50% by mass aqueous solution of tetramethylammonium chloride was heated under normal pressure and reacted at 60 ° C. for 8 hours. After completion of the reaction, the mixture was cooled and repeatedly washed with water to remove by-produced sodium chloride. The excess epichlorohydrin was distilled off under reduced pressure to give epihalohydrin ether.
(Closing reaction process)
100 g of the obtained epihalohydrin ether is dissolved in 100 g of toluene, and 1.5 equivalents of 50% by mass aqueous sodium hydroxide solution is added based on 1 equivalent of active hydroxyl group of epihalohydrin ether, and further based on 1 equivalent of active hydroxyl group of epihalohydrin ether Then, 0.01 equivalent of 50% by mass of tetramethylammonium chloride aqueous solution was added and reacted at 80 ° C. for 2 hours. After completion of the reaction, the reaction product was repeatedly washed with water to remove by-produced sodium chloride from the reaction product. Further, methyl isobutyl ketone was removed by distillation under reduced pressure from the reaction product to obtain an epoxy resin A-27.
［比較例６］
ビスフェノールＡのエチレンオキシド６モル付加物；三洋化成工業株式会社製 商品名「ニューポール ＢＰＥ−６０」；水酸基価：２２８ｍｇＫＯＨ／ｇからビスフェノールＡ；水酸基価：４８９ｍｇＫＯＨ／ｇに変更し、固体酸触媒の量を４４ｇに変更し、エピクロロヒドリンの量を１６２ｇに変更し、反応時間を４時間に変更したこと以外は、実施例１と同様に行い、エポキシ樹脂Ａ−２８を得た。
Comparative Example 6
Ethylene oxide 6 mole adduct of bisphenol A; Sanyo Chemical Industries, Ltd. trade name "New pole BPE-60"; hydroxyl value: changed from 228 mg KOH / g to bisphenol A; hydroxyl value: 489 mg KOH / g, amount of solid acid catalyst Was changed to 44 g, the amount of epichlorohydrin was changed to 162 g, and the reaction time was changed to 4 hours, in the same manner as in Example 1, to obtain an epoxy resin A-28.
［比較例７］
ビスフェノールＡ；水酸基価：４８９ｍｇＫＯＨ／ｇからビスフェノールＦ；水酸基価：５５８ｍｇＫＯＨ／ｇに変更し、固体酸触媒の量を５０ｇに変更し、エピクロロヒドリンの量を１８５ｇに変更したこと以外は、比較例６と同様に行い、エポキシ樹脂Ａ−２９を得た。
Comparative Example 7
Bisphenol A; hydroxyl value: 489 mg KOH / g to bisphenol F; hydroxyl value: 558 mg KOH / g, the amount of solid acid catalyst was changed to 50 g, and the amount of epichlorohydrin was changed to 185 g It carried out similarly to Example 6, and obtained epoxy resin A-29.
実施例１〜２２で得られたエポキシ樹脂Ａ−１〜Ａ−２２、及び比較例１〜７で得られたエポキシ樹脂Ａ−２３〜Ａ−２９のエポキシ当量、全塩素量及びガードナー色数を測定した。この結果を表１〜３に示す。 The epoxy equivalent weight, total chlorine content and Gardner color number of the epoxy resins A-1 to A-22 obtained in Examples 1 to 22 and the epoxy resins A-23 to A-29 obtained in Comparative Examples 1 to 7 It was measured. The results are shown in Tables 1 to 3.
［実施例２３〜５３、参考例１〜７］
表４〜７に示すとおり、実施例１〜２２及び比較例１〜７で得られた（Ａ）エポキシ樹脂；Ａ−１〜Ａ２９、及び（Ｂ）その他のエポキシ樹脂；株式会社ダイセル社製 商品名「ＣＥＬ２０２１Ｐ」、ＤＩＣ株式会社製 商品名「ＥＸＡ８５０ＣＲＰ」、又はＤＩＣ株式会社製 商品名「ＥＸＡ８３０ＣＲＰ」に、エポキシ基１当量に基づいて（Ｃ）酸無水物；日立化成株式会社製 商品名「ＨＮ−５５００」分子量１６８を０．９６当量の割合で添加し、さらに（Ａ）成分と（Ｂ）成分の合計１００重量部に基づいて、（Ｄ）硬化促進剤；２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺともいう）を１重量部添加し、エポキシ樹脂組成物を得た。
得られたエポキシ樹脂組成物を、１００ｍｍ×１００ｍｍ×２ｍｍのフッ素樹脂板の型に流し込み、オーブンにて１４０℃、６０分及び２２０℃、１２０分の条件で硬化させてエポキシ樹脂硬化物を得た。得られた硬化物の５０％破壊エネルギーを、デュポン衝撃試験機Ｈ５０を使用して測定した。
[Examples 23 to 53, Reference Examples 1 to 7]
As shown in Tables 4 to 7, (A) epoxy resin obtained in Examples 1 to 22 and Comparative Examples 1 to 7; A-1 to A 29 and (B) other epoxy resins; Name "CEL 2021 P", product name "EXA850 CRP" manufactured by DIC Corporation or product name "EXA 830 CRP" manufactured by DIC Corporation (C) acid anhydride based on 1 equivalent of epoxy group; product name "HN" manufactured by Hitachi Chemical Co., Ltd. -5500 "molecular weight 168 is added in a proportion of 0.96 equivalents, and (D) a curing accelerator based on a total of 100 parts by weight of the (A) component and the (B) component; 2-ethyl-4-methylimidazole One part by weight of (also referred to as 2E4MZ) was added to obtain an epoxy resin composition.
The obtained epoxy resin composition was poured into a 100 mm × 100 mm × 2 mm fluorine resin plate mold and cured in an oven at 140 ° C., 60 minutes and 220 ° C., 120 minutes to obtain a cured epoxy resin product. . The 50% breaking energy of the obtained cured product was measured using a Dupont impact tester H50.
実施例２３〜５３及び参考例１〜７の評価結果を、表４〜７に示す。なお、表６及び７中、実施例４７及び参考例３の５０％破壊エネルギーにおける「−」は、測定試料が柔軟であるが強度がなく、破壊されずに千切れたため、数値化できなかったことを示す。 The evaluation results of Examples 23 to 53 and Reference Examples 1 to 7 are shown in Tables 4 to 7. In Tables 6 and 7, "-" at 50% breaking energy in Example 47 and Reference Example 3 could not be quantified because the measurement sample was flexible but lacked strength and was broken without breaking. Indicates that.
実施例１〜２２の樹脂、すなわち、エポキシ樹脂：Ａ−１〜Ａ−２２は、いずれも、全塩素量が２００ｐｐｍ以下、ガードナー色数が３以下であった。
比較例１〜７の樹脂、すなわち、エポキシ樹脂：Ａ−２３〜Ａ−２９のうち、比較例１〜５の樹脂、すなわち、エポキシ樹脂：Ａ−２３〜２７はいずれも、全塩素量が２００ｐｐｍ以上、ガードナー色数が３．５以上であった。
比較例１〜７の樹脂、すなわち、エポキシ樹脂：Ａ−２３〜Ａ−２９のうち、比較例６〜７の樹脂、すなわち、エポキシ樹脂：Ａ−２８〜Ａ−２９はいずれも、全塩素量が２００ｐｐｍ以上、ガードナー色数が３以下であった。
The resins of Examples 1 to 22, that is, epoxy resins: A-1 to A-22, all had a total chlorine content of 200 ppm or less and a Gardner color number of 3 or less.
Among the resins of Comparative Examples 1 to 7, that is, the epoxy resins: A-23 to A-29, the resins of Comparative Examples 1 to 5, that is, the epoxy resins: A-23 to 27 all have a total chlorine content of 200 ppm. As mentioned above, the Gardner color number was 3.5 or more.
Resins of Comparative Examples 1 to 7, that is, among epoxy resins: A-23 to A-29, resins of Comparative Examples 6 to 7, that is, all of epoxy resins: A-28 to A-29, the total chlorine amount Was 200 ppm or more, and the Gardner color number was 3 or less.
エポキシ樹脂：Ａ−１〜Ａ−１７を用いた実施例２３〜４６は、いずれも、５０％破壊エネルギーの値が４Ｊ以上であった。
エポキシ樹脂組成物中の（Ａ）成分１００質量部に基づいて、（Ｂ）成分が２０重量部以下である実施例４７は、柔軟であるが強度がなく、脆い硬化物であった。
エポキシ樹脂組成物中の（Ａ）成分１００質量部に基づいて、（Ｂ）成分が３００重量部以上である実施例４８は、５０％破壊エネルギーが４Ｊ未満であった。
上記式（１）中の（ｍ＋ｎ）が５未満である実施例４９、５３及び参考例６〜７は、いずれも５０％破壊エネルギーが４Ｊ未満であった。
ポリオール化合物の活性水酸基１当量に基づいて、エピクロロヒドリンの添加量が、１．５当量以下である実施例５０、ポリオール化合物の活性水酸基１当量に基づいて、エピクロロヒドリンの添加量が、３当量以上である参考例１は、いずれも５０％破壊エネルギーが４Ｊ未満であった。
ポリオール化合物の活性水酸基１当量に基づいて、固体酸触媒の添加量が、２５ｇ未満である実施例５１、ポリオール化合物の活性水酸基１当量に基づいて、固体酸触媒の添加量が、７５ｇを越える実施例５２は、いずれも５０％破壊エネルギーが４Ｊ未満であった。
（Ａ）成分の全塩素量が２００ｐｐｍ以上であり、ガードナー色数が３．５以上である、参考例２及び４〜５は、いずれも５０％破壊エネルギーが４Ｊ未満であった。
上記式（１）中の（ｍ＋ｎ）が１０を越える参考例３は、柔軟であるが強度がなく、脆い硬化物であった。
Epoxy resins: Examples 23 to 46 using A-1 to A-17 all had a 50% breaking energy value of 4 J or more.
Example 47 in which the component (B) was at most 20 parts by weight based on 100 parts by mass of the component (A) in the epoxy resin composition was a soft but brittle but brittle cured product.
Example 48 in which the component (B) was at least 300 parts by weight based on 100 parts by weight of the component (A) in the epoxy resin composition had a 50% breaking energy of less than 4 J.
In Examples 49 and 53 and Reference Examples 6 to 7 in which (m + n) in the above formula (1) is less than 5, the 50% destruction energy was less than 4 J in all cases.
The amount of epichlorohydrin added is 1.5 equivalents or less based on one equivalent of the active hydroxyl group of the polyol compound, Example 50 the amount of epichlorohydrin added based on one equivalent of the active hydroxyl group of the polyol compound The 50% destruction energy was less than 4 J in all of Reference Example 1 of 3 equivalents or more.
Example 51 in which the amount of solid acid catalyst added is less than 25 g based on one equivalent of the active hydroxyl group of the polyol compound, the amount of solid acid catalyst added exceeds 75 g based on one equivalent of the active hydroxyl group of the polyol compound In each of Example 52, 50% destruction energy was less than 4 J.
The 50% destruction energy was less than 4 J in all of Reference Examples 2 and 4-5 in which the total chlorine content of the component (A) is 200 ppm or more and the Gardner color number is 3.5 or more.
The reference example 3 in which (m + n) in the above formula (1) exceeds 10 is a soft but weak strength and a brittle cured product.
上記結果から、低ハロゲン性、低着色性を充足している実施例の中でも、実施例２３〜４６は、さらに耐衝撃性を充足している。参考例６及び７は低着色性を充足しているものの、低ハロゲン性及び耐衝撃性を充足しない。参考例１〜５は低ハロゲン性、低着色性、耐衝撃性のいずれも充足しない。 From the above results, among the examples satisfying the low halogen property and the low coloring property, Examples 23 to 46 further satisfy the impact resistance. Although the reference examples 6 and 7 satisfy the low colorability, they do not satisfy the low halogen and impact resistance. The reference examples 1 to 5 do not satisfy any of the low halogen property, the low coloring property, and the impact resistance.
本発明によれば、低塩素性と低着色性を有し、硬化物、さらには、耐衝撃性に優れた硬化物を得ることができる、エポキシ樹脂及びエポキシ樹脂組成物を提供することができ、特に、耐衝撃性を必要とする半導体パッケージや半導体チップ等の電子部材、及びＬＥＤやカメラモジュール等の光学部材における封止材、接着剤として有用であることから、産業上の有用性は高い。 According to the present invention, it is possible to provide an epoxy resin and an epoxy resin composition having low chlorination and low colorability and capable of obtaining a cured product, and further a cured product having excellent impact resistance. Particularly, it is useful as an encapsulating material and adhesive agent in electronic components such as semiconductor packages and semiconductor chips which require impact resistance, and optical components such as LEDs and camera modules, so that the utility in industry is high. .
Claims (9)
前記（Ａ）成分１００質量部に基づいて、前記（Ｂ）成分が１〜４００質量部であり、
前記（Ａ）成分と前記（Ｂ）成分の合計エポキシ基１当量に基づいて、前記（Ｃ）成分が０．５〜３．０当量である、樹脂組成物。 (A) containing the epoxy resin according to any one of claims 1 to 5, (B) another epoxy resin, and (C) a curing agent,
The component (B) is 1 to 400 parts by mass based on 100 parts by mass of the component (A),
The resin composition whose said (C) component is 0.5-3.0 equivalent based on the epoxy group 1 equivalent of the said (A) component and the said (B) component.
前記エピハロヒドリンエーテルを、アルカリ性化合物存在下、閉環させ、エポキシ樹脂を得る閉環反応工程と、
を含む、請求項１〜５のいずれか一項に記載のエポキシ樹脂の製造方法。
A ring closing reaction step of ring closing the epihalohydrin ether in the presence of an alkaline compound to obtain an epoxy resin;
The manufacturing method of the epoxy resin as described in any one of Claims 1-5.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61278525A (en) * | 1985-05-28 | 1986-12-09 | ザ ダウ ケミカル カンパニ− | Production of epoxy resin |
| JPH01108217A (en) * | 1987-10-21 | 1989-04-25 | Mitsui Petrochem Ind Ltd | Purification of epoxy resin |
| JPH05331155A (en) * | 1992-06-01 | 1993-12-14 | Sanyo Chem Ind Ltd | Production of glycidyl ether |
| JP2004099744A (en) * | 2002-09-10 | 2004-04-02 | Mitsui Chemicals Inc | Method for purifying epoxy resin |
| JP2005314512A (en) * | 2004-04-28 | 2005-11-10 | Japan Epoxy Resin Kk | Liquid epoxy resin and method for producing the same, epoxy resin composition and its cured product |
| JP2005343990A (en) * | 2004-06-02 | 2005-12-15 | Dainippon Ink & Chem Inc | Epoxy resin composition, cured product thereof, method for producing epoxy resin and epoxy resin |
| JP2009203425A (en) * | 2008-02-29 | 2009-09-10 | Sanyo Chem Ind Ltd | Method for producing glycidyl ether |
| JP2010095727A (en) * | 2009-12-21 | 2010-04-30 | Japan Epoxy Resin Kk | Curable epoxy resin composition and cured product |
| JP2010168548A (en) * | 2008-12-26 | 2010-08-05 | Sanyo Chem Ind Ltd | Multifunctional epoxy resin and method for producing the same |
| JP2011207932A (en) * | 2010-03-29 | 2011-10-20 | Mitsubishi Chemicals Corp | Epoxy resin and epoxy resin composition |
| JP2012132028A (en) * | 2012-04-09 | 2012-07-12 | Mitsubishi Chemicals Corp | Epoxy resin composition for optical element sealing material |
| JP2013095916A (en) * | 2011-11-07 | 2013-05-20 | Asahi Kasei E-Materials Corp | Production method of epoxy resin and epoxy resin obtained by the production method |
| JP2013100384A (en) * | 2011-11-07 | 2013-05-23 | Asahi Kasei E-Materials Corp | Method for producing epoxy resin and epoxy resin obtained using the same |
| JP2013100385A (en) * | 2011-11-07 | 2013-05-23 | Asahi Kasei E-Materials Corp | Method for producing epoxy resin and epoxy resin obtained using the same |
| JP2015117333A (en) * | 2013-12-19 | 2015-06-25 | 旭化成イーマテリアルズ株式会社 | Masterbatch type latent epoxy resin hardening agent composition and epoxy resin composition using the same |
| JP2016084295A (en) * | 2014-10-23 | 2016-05-19 | 旭化成イーマテリアルズ株式会社 | Polyhydroxy compound and producing method thereof |
| WO2018021495A1 (en) * | 2016-07-29 | 2018-02-01 | 日本合成化学工業株式会社 | Resin composition, use thereof, and method for producing resin composition |
-
2017
- 2017-12-14 JP JP2017239901A patent/JP2019104883A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61278525A (en) * | 1985-05-28 | 1986-12-09 | ザ ダウ ケミカル カンパニ− | Production of epoxy resin |
| JPH01108217A (en) * | 1987-10-21 | 1989-04-25 | Mitsui Petrochem Ind Ltd | Purification of epoxy resin |
| JPH05331155A (en) * | 1992-06-01 | 1993-12-14 | Sanyo Chem Ind Ltd | Production of glycidyl ether |
| JP2004099744A (en) * | 2002-09-10 | 2004-04-02 | Mitsui Chemicals Inc | Method for purifying epoxy resin |
| JP2005314512A (en) * | 2004-04-28 | 2005-11-10 | Japan Epoxy Resin Kk | Liquid epoxy resin and method for producing the same, epoxy resin composition and its cured product |
| JP2005343990A (en) * | 2004-06-02 | 2005-12-15 | Dainippon Ink & Chem Inc | Epoxy resin composition, cured product thereof, method for producing epoxy resin and epoxy resin |
| JP2009203425A (en) * | 2008-02-29 | 2009-09-10 | Sanyo Chem Ind Ltd | Method for producing glycidyl ether |
| JP2010168548A (en) * | 2008-12-26 | 2010-08-05 | Sanyo Chem Ind Ltd | Multifunctional epoxy resin and method for producing the same |
| JP2010095727A (en) * | 2009-12-21 | 2010-04-30 | Japan Epoxy Resin Kk | Curable epoxy resin composition and cured product |
| JP2011207932A (en) * | 2010-03-29 | 2011-10-20 | Mitsubishi Chemicals Corp | Epoxy resin and epoxy resin composition |
| JP2013095916A (en) * | 2011-11-07 | 2013-05-20 | Asahi Kasei E-Materials Corp | Production method of epoxy resin and epoxy resin obtained by the production method |
| JP2013100384A (en) * | 2011-11-07 | 2013-05-23 | Asahi Kasei E-Materials Corp | Method for producing epoxy resin and epoxy resin obtained using the same |
| JP2013100385A (en) * | 2011-11-07 | 2013-05-23 | Asahi Kasei E-Materials Corp | Method for producing epoxy resin and epoxy resin obtained using the same |
| JP2012132028A (en) * | 2012-04-09 | 2012-07-12 | Mitsubishi Chemicals Corp | Epoxy resin composition for optical element sealing material |
| JP2015117333A (en) * | 2013-12-19 | 2015-06-25 | 旭化成イーマテリアルズ株式会社 | Masterbatch type latent epoxy resin hardening agent composition and epoxy resin composition using the same |
| JP2016084295A (en) * | 2014-10-23 | 2016-05-19 | 旭化成イーマテリアルズ株式会社 | Polyhydroxy compound and producing method thereof |
| WO2018021495A1 (en) * | 2016-07-29 | 2018-02-01 | 日本合成化学工業株式会社 | Resin composition, use thereof, and method for producing resin composition |
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