JP2023033883A - Epoxy resin, its composition and cured product - Google Patents
Epoxy resin, its composition and cured product Download PDFInfo
- Publication number
- JP2023033883A JP2023033883A JP2021139814A JP2021139814A JP2023033883A JP 2023033883 A JP2023033883 A JP 2023033883A JP 2021139814 A JP2021139814 A JP 2021139814A JP 2021139814 A JP2021139814 A JP 2021139814A JP 2023033883 A JP2023033883 A JP 2023033883A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- epoxy
- resin composition
- cured product
- resin
- 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.)
- Pending
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 103
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 103
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- 238000005227 gel permeation chromatography Methods 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 abstract description 18
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 239000011342 resin composition Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000012774 insulation material Substances 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 26
- 239000011347 resin Substances 0.000 description 26
- 238000001723 curing Methods 0.000 description 23
- 150000002989 phenols Chemical class 0.000 description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 18
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 229920003986 novolac Polymers 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- JFDZBHWFFUWGJE-KWCOIAHCSA-N benzonitrile Chemical group N#[11C]C1=CC=CC=C1 JFDZBHWFFUWGJE-KWCOIAHCSA-N 0.000 description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 9
- 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 9
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- -1 t-butyl pyrogallol Chemical compound 0.000 description 5
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229940079877 pyrogallol Drugs 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- IXCOKTMGCRJMDR-UHFFFAOYSA-N 9h-fluorene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 IXCOKTMGCRJMDR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 2
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 2
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 2
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 2
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- XOOMNEFVDUTJPP-UHFFFAOYSA-N naphthalene-1,3-diol Chemical compound C1=CC=CC2=CC(O)=CC(O)=C21 XOOMNEFVDUTJPP-UHFFFAOYSA-N 0.000 description 2
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 2
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 2
- OENHRRVNRZBNNS-UHFFFAOYSA-N naphthalene-1,8-diol Chemical compound C1=CC(O)=C2C(O)=CC=CC2=C1 OENHRRVNRZBNNS-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide 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
- 230000009257 reactivity Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-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
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- MIQRQLRZDQTHGM-UHFFFAOYSA-N 2,4-dibromobenzonitrile Chemical compound BrC1=CC=C(C#N)C(Br)=C1 MIQRQLRZDQTHGM-UHFFFAOYSA-N 0.000 description 1
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 description 1
- ATOKQLGYVAAFEC-UHFFFAOYSA-N 2,5-dibromobenzonitrile Chemical compound BrC1=CC=C(Br)C(C#N)=C1 ATOKQLGYVAAFEC-UHFFFAOYSA-N 0.000 description 1
- LNGWRTKJZCBXGT-UHFFFAOYSA-N 2,5-dichlorobenzonitrile Chemical compound ClC1=CC=C(Cl)C(C#N)=C1 LNGWRTKJZCBXGT-UHFFFAOYSA-N 0.000 description 1
- KBLLYABRMLFXFZ-UHFFFAOYSA-N 2,6-dibromobenzonitrile Chemical compound BrC1=CC=CC(Br)=C1C#N KBLLYABRMLFXFZ-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- QUJGDNCWTBTBQD-UHFFFAOYSA-N 3,5-dibromobenzonitrile Chemical compound BrC1=CC(Br)=CC(C#N)=C1 QUJGDNCWTBTBQD-UHFFFAOYSA-N 0.000 description 1
- AERZMMNNWVZSNB-UHFFFAOYSA-N 3-dodec-1-ynyloxolane-2,5-dione Chemical compound CCCCCCCCCCC#CC1CC(=O)OC1=O AERZMMNNWVZSNB-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- XSTITJMSUGCZDH-UHFFFAOYSA-N 4-(4-hydroxy-2,6-dimethylphenyl)-3,5-dimethylphenol Chemical group CC1=CC(O)=CC(C)=C1C1=C(C)C=C(O)C=C1C XSTITJMSUGCZDH-UHFFFAOYSA-N 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
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Images
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- Epoxy Resins (AREA)
Abstract
Description
本発明は、エポキシ樹脂、エポキシ樹脂組成物、及びエポキシ樹脂硬化物に関し、詳しくは、半導体封止、積層板、放熱基板等の電気・電子部品用絶縁材料に有用な常温で固形としての取扱性、成形時の低粘度性、溶剤溶解性に優れたエポキシ樹脂、エポキシ樹脂組成物、及びそれらを硬化させて得られる耐熱性、熱分解安定性、熱伝導性、優れるエポキシ樹脂硬化物に関する。 TECHNICAL FIELD The present invention relates to epoxy resins, epoxy resin compositions, and cured epoxy resins. More specifically, the present invention relates to an epoxy resin, an epoxy resin composition, and a cured epoxy resin, which are useful as insulating materials for electric and electronic parts such as semiconductor encapsulation, laminates, and heat dissipation substrates, and have good handleability as solids at room temperature. , epoxy resins and epoxy resin compositions having low viscosity during molding and excellent solvent solubility, and epoxy resin cured products having excellent heat resistance, thermal decomposition stability, and thermal conductivity obtained by curing them.
エポキシ樹脂は工業的に幅広い用途で使用されてきているが、その要求性能は近年ますます高度化している。電子回路の高密度化、高周波化が進む電気・電子分野、パワーエレクトロニクス分野においては、電子回路からの発熱が大きくなっていることから、絶縁部に用いられるエポキシ樹脂組成物の放熱性が問題となっている。この放熱性については、従来はフィラーの熱伝導性で賄っていたが、更なる高集積化に向けて、マトリクスであるエポキシ樹脂自体の熱伝導性の向上が求められるようになってきた。 Epoxy resins have been used in a wide range of industrial applications, and their required performance has become increasingly sophisticated in recent years. In the electric/electronics field and the power electronics field, where electronic circuits are increasing in density and frequency, heat generation from electronic circuits is increasing. It's becoming Conventionally, this heat dissipation has been covered by the thermal conductivity of the filler, but in order to achieve higher integration, it has become necessary to improve the thermal conductivity of the matrix epoxy resin itself.
高熱伝導性に優れたエポキシ樹脂組成物としては、メソゲン構造を有するエポキシ樹脂を用いたものが知られており、例えば、特許文献1には、ビフェノール型エポキシ樹脂と多価フェノール樹脂硬化剤を必須成分としたエポキシ樹脂組成物が示され、高温下での安定性と強度に優れ、接着、注型、封止、成型、積層等の広い分野で使用できることが開示されている。また、特許文献2には、屈曲鎖で連結された二つのメソゲン構造を分子内に有するエポキシ化合物の開示がある。さらに、特許文献3には、メソゲン基を有するエポキシ化合物を含む樹脂組成物の開示がある。 As an epoxy resin composition excellent in high thermal conductivity, one using an epoxy resin having a mesogenic structure is known. It discloses an epoxy resin composition as a component, which is excellent in stability and strength at high temperatures and can be used in a wide range of fields such as adhesion, casting, sealing, molding and lamination. Further, Patent Document 2 discloses an epoxy compound having two mesogenic structures linked by a bent chain in its molecule. Furthermore, Patent Document 3 discloses a resin composition containing an epoxy compound having a mesogenic group.
しかし、このようなメソゲン構造を有するエポキシ樹脂は融点が高く、混合処理を行う場合、高融点成分が溶解し難く溶け残りを生じるため、硬化性や耐熱性が低下する問題があった。また、このようなエポキシ樹脂を硬化剤と均一に混合するには、高温が必要であった。高温では、エポキシ樹脂の硬化反応が急速に進みゲル化時間が短くなるため、混合処理は厳しく制限され取り扱いが難しいという問題があった。そして、その欠点を補うために溶解性の良いの第3成分を添加すると、樹脂の融点が低下して均一混合しやすくなるが、その硬化物は熱伝導率が低下するという問題を生じた。 However, such an epoxy resin having a mesogenic structure has a high melting point, and when a mixing treatment is performed, the high melting point component is difficult to dissolve and remains undissolved, resulting in a problem of reduced curability and heat resistance. Also, a high temperature was required to uniformly mix such an epoxy resin with a curing agent. At high temperatures, the curing reaction of the epoxy resin proceeds rapidly and the gelling time is shortened. When a third component with good solubility is added to make up for the drawback, the melting point of the resin is lowered and uniform mixing becomes easier, but the cured product has a problem of reduced thermal conductivity.
溶融混合処理が可能な高熱伝導樹脂として、特許文献4においてヒドロキノンと4,4’-ジヒドロキシビフェニルの混合物をエポキシ化したエポキシ樹脂が開示されており、特許文献5においては、4,4’-ジヒドロキシジフェニルメタンと4,4’-ジヒドロキシビフェニルの混合物をエポキシ化したエポキシ樹脂が開示されている。しかしながら、これらの樹脂は溶剤溶解性に乏しく、適用用途が限定されていた。特許文献6において、ジフェニルエーテル構造を有するエポキシ樹脂の組成物が開示されているが、硬化剤が限定されており、フェノールノボラック等の汎用の硬化剤では熱伝導率および耐熱性が不十分であった。 As a high thermal conductive resin that can be melt-mixed, Patent Document 4 discloses an epoxy resin obtained by epoxidizing a mixture of hydroquinone and 4,4'-dihydroxybiphenyl, and Patent Document 5 discloses 4,4'-dihydroxy Epoxy resins are disclosed which are epoxidized mixtures of diphenylmethane and 4,4'-dihydroxybiphenyl. However, these resins are poorly soluble in solvents and have limited applications. Patent Document 6 discloses an epoxy resin composition having a diphenyl ether structure, but the curing agent is limited, and general-purpose curing agents such as phenol novolak are insufficient in thermal conductivity and heat resistance. .
従って、本発明の目的は、上記問題を解消し、信頼性に優れた半導体封止、積層板、放熱基板等の電気・電子部品用絶縁材料に有用な常温で固形としての取扱性に優れ、かつ成形時の低粘度性、溶剤溶解性に優れたエポキシ樹脂、及びこれを用いたエポキシ樹脂組成物、並びにそれから得られる高熱伝導性に優れた硬化物を提供することである。 Accordingly, an object of the present invention is to solve the above problems, and to provide excellent handleability as a solid at normal temperature, which is useful as an insulating material for electric and electronic parts such as highly reliable semiconductor encapsulation, laminates, and heat dissipation substrates. An object of the present invention is to provide an epoxy resin having low viscosity during molding and excellent solvent solubility, an epoxy resin composition using the same, and a cured product obtained therefrom having excellent high thermal conductivity.
本発明者らは、鋭意検討により、ベンゾニトリル構造を有する特定のエポキシ樹脂が上記の課題を解決することが期待されること、そしてその硬化物が熱伝導性、耐熱性に効果を発現することを見出した。 Through intensive studies, the present inventors have found that a specific epoxy resin having a benzonitrile structure is expected to solve the above problems, and that the cured product exhibits effects in terms of thermal conductivity and heat resistance. I found
すなわち、本発明は、下記一般式(1)で表されるエポキシ樹脂であって、エポキシ当量が230~350g/eq、軟化点が130℃以下であることを特徴とするエポキシ樹脂である。
上記一般式(1)において、ゲルパーミエーションクロマトグラフィーで測定した面積%(GPC面積%)で、n=0である成分が40%以下であることが好ましい。 In the above general formula (1), it is preferable that the area % (GPC area %) measured by gel permeation chromatography, where n=0, is 40% or less.
さらに、本発明は上記のエポキシ樹脂、及び硬化剤を必須成分とすることを特徴とするエポキシ樹脂組成物であり、また、このエポキシ樹脂硬化物を硬化させたことを特徴とするエポキシ樹脂硬化物である。 Further, the present invention relates to an epoxy resin composition characterized by comprising the above epoxy resin and a curing agent as essential components, and an epoxy resin cured product characterized by curing the epoxy resin cured product. is.
本発明のエポキシ樹脂は、100℃以下での溶融混練性が良好であり、溶剤溶解性に優れるので、積層、成形、注型、接着等の用途に使用されるエポキシ樹脂組成物及びその硬化物に適する。そして、この硬化物は耐熱性、熱分解安定性、熱伝導性にも優れたものとなるので、電気・電子部品類の封止、回路基板材料等に好適である。 The epoxy resin of the present invention has good melt-kneadability at 100° C. or less and excellent solvent solubility. Suitable for The cured product has excellent heat resistance, thermal decomposition stability, and thermal conductivity, and is therefore suitable for sealing electric/electronic parts, circuit board materials, and the like.
以下、本発明を詳細に説明する。 The present invention will be described in detail below.
まず、本発明は、一般式(1)で表されるエポキシ樹脂であって、エポキシ当量が230~350g/eq、軟化点が130℃以下であることを特徴とするエポキシ樹脂である。
nは繰り返し数(数平均)であり、0~15の数を示す。好ましくは、nの値が異なる成分の混合物である。また、ゲルパーミエーションクロマトグラフィーで測定した面積%(GPC面積%)で、n=0のものは40%以下が好ましい。より好ましくは、30%以下である。n=0のものが40%より多く含まれている場合、結晶性が強く、融点が130℃以上となり、溶剤溶解性も低下する傾向がある。また、nが15よりも大きいものは、反応性が低く、硬化時に未反応となる成分が生じると耐熱性が低下する。 n is the number of repetitions (number average) and represents a number from 0 to 15; Preferred are mixtures of components with different values of n. In addition, the area % (GPC area %) measured by gel permeation chromatography, where n=0, is preferably 40% or less. More preferably, it is 30% or less. If the n=0 content is more than 40%, the crystallinity is strong, the melting point is 130° C. or higher, and the solvent solubility tends to decrease. On the other hand, when n is larger than 15, the reactivity is low, and if unreacted components are generated during curing, the heat resistance is lowered.
本発明のエポキシ樹脂の軟化点は、130℃以下の範囲である。130℃よりも高いと溶融混練性が低下し、結晶性を有する場合はさらに溶剤溶解性も低下する。なお、封止材用途など、べたつきによるブロッキングが防止されることが好ましい用途・分野においては、軟化点が低すぎないことがよく、その場合の好ましい軟化点は50~120℃、より好ましくは60~110℃である。 The softening point of the epoxy resin of the present invention is in the range of 130° C. or lower. If the temperature is higher than 130°C, the melt-kneadability is lowered, and if it has crystallinity, the solvent solubility is also lowered. In applications and fields where it is preferable to prevent blocking due to stickiness, such as sealing material applications, the softening point should not be too low. ~110°C.
本発明のエポキシ樹脂のエポキシ当量は、230~350の範囲である。この範囲より大きいと反応性が低く、硬化時に未反応となる成分が生じ、耐熱性、信頼性が低下する。この範囲より小さいとベンゾニトリル構造を含まない二官能エポキシ樹脂成分が多くなることを示し、二官能の結晶性エポキシ樹脂が多い場合は溶剤溶解性、溶融混練性が低下し、二官能の液状エポキシ樹脂が多い場合は硬化物の耐熱性、熱伝導率が低下する。 The epoxy equivalent weight of the epoxy resin of the present invention is in the range of 230-350. If it exceeds this range, the reactivity is low, and unreacted components are produced during curing, resulting in deterioration of heat resistance and reliability. If it is less than this range, it indicates that the bifunctional epoxy resin component that does not contain a benzonitrile structure increases. When the amount of resin is large, the heat resistance and thermal conductivity of the cured product are lowered.
本発明のエポキシ樹脂の製法は、特に限定されるものではないが、下記式(2)のベンゾニトリル構造を持つフェノール性化合物とエピクロルヒドリンを反応させることにより製造することができる。この反応は、通常のエポキシ化反応と同様に行うことができる。
式(2)で表されるフェノール性化合物は、水酸基当量(g/eq)が、好ましくは1150~250、より好ましくは180~230である。また、融点が、好ましくは140℃~300℃、より好ましくは150℃~280℃である。
The method for producing the epoxy resin of the present invention is not particularly limited, but it can be produced by reacting a phenolic compound having a benzonitrile structure of the following formula (2) with epichlorohydrin. This reaction can be carried out in the same manner as a normal epoxidation reaction.
The phenolic compound represented by formula (2) has a hydroxyl equivalent (g/eq) of preferably 1150-250, more preferably 180-230. Also, the melting point is preferably 140°C to 300°C, more preferably 150°C to 280°C.
ここで、この式(2)で表されるフェノール性化合物については、限定されないが、例えば、2,4-ジクロロベンゾニトリル、2,5-ジクロロベンゾニトリル、2,6-ジクロロベンゾニトリル、3,5-ジクロロベンゾニトリル、2,4-ジブロモベンゾニトリル、2,5-ジブロモベンゾニトリル、2,6-ジブロモベンゾニトリル、3,5-ジブロモベンゾニトリルなどのベンゾニトリル化合物に対して、4,4’-ジヒドロキシビフェニル、4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシジフェニルスルフィド、4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジヒドロキシベンゾフェノン、ビスフェノールA、ビスフェノールF等の、上記X基を持つジヒドロキシ化合物を塩基性触媒の存在下に反応させる方法により得ることができる。 Here, the phenolic compound represented by formula (2) is not limited, but examples include 2,4-dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,6-dichlorobenzonitrile, 3, For benzonitrile compounds such as 5-dichlorobenzonitrile, 2,4-dibromobenzonitrile, 2,5-dibromobenzonitrile, 2,6-dibromobenzonitrile, 3,5-dibromobenzonitrile, 4,4' -dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, bisphenol A, bisphenol F, etc. It can be obtained by a method of reacting a dihydroxy compound possessed in the presence of a basic catalyst.
式(2)のフェノール性化合物とエピクロルヒドリンとの反応は、例えば、フェノール性化合物を過剰のエピクロルヒドリンに溶解した後、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物の存在下に、50~150℃、好ましくは、60~100℃の範囲で1~10時間反応させる方法が挙げられる。この際の、アルカリ金属水酸化物の使用量は、ジヒドロキシ体中の水酸基1モルに対して、0.8~2.0モル、好ましくは、0.9~1.5モルの範囲である。エピクロルヒドリンは、フェノール性化合物中の水酸基に対して過剰量が用いられ、通常は、フェノール性化合物中の水酸基1モルに対して、1.5から15モルである。反応終了後、過剰のエピクロルヒドリンを留去し、残留物をトルエン、メチルイソブチルケトン等の溶剤に溶解し、濾過し、水洗して無機塩を除去し、次いで溶剤を留去することにより目的のエポキシ樹脂を得ることができる。 The reaction between the phenolic compound of formula (2) and epichlorohydrin can be carried out, for example, by dissolving the phenolic compound in an excess of epichlorohydrin and then reacting it in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. A method of reacting at 150° C., preferably at 60 to 100° C. for 1 to 10 hours can be mentioned. At this time, the amount of alkali metal hydroxide to be used is in the range of 0.8 to 2.0 mol, preferably 0.9 to 1.5 mol, per 1 mol of hydroxyl group in the dihydroxy compound. Epichlorohydrin is used in an excess amount relative to the hydroxyl groups in the phenolic compound, usually 1.5 to 15 mol per 1 mol of hydroxyl groups in the phenolic compound. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and the solvent is distilled off to obtain the desired epoxy. resin can be obtained.
本発明のエポキシ樹脂は、ベンゾニトリル構造を持つフェノール性化合物とベンゾニトリル構造を持たない他のフェノール性化合物と混合させたものを用いて合成することもできる。この場合のベンゾニトリル構造を持つフェノール性化合物の混合比率は50wt%以上である。また、他のフェノール性化合物には特に制約はなく、一分子中に水酸基を2個以上有するものの中から選択される。 The epoxy resin of the present invention can also be synthesized using a mixture of a phenolic compound having a benzonitrile structure and another phenolic compound having no benzonitrile structure. In this case, the mixing ratio of the phenolic compound having a benzonitrile structure is 50 wt % or more. Also, other phenolic compounds are not particularly limited, and are selected from those having two or more hydroxyl groups in one molecule.
このベンゾニトリル構造を持つエポキシ樹脂の純度、特に加水分解性塩素量は、適用する電子部品の信頼性向上の観点より少ない方がよい。特に限定するものではないが、好ましくは1000ppm以下、さらに好ましくは500ppm以下である。なお、本発明でいう加水分解性塩素とは、以下の方法により測定された値をいう。すなわち、試料0.5gをジオキサン30mlに溶解後、1N-KOH、10mlを加え30分間煮沸還流した後、室温まで冷却し、さらに80%アセトン水100mlを加え、0.002N-AgNO3水溶液で電位差滴定を行い得られる値である。 The purity of the epoxy resin having a benzonitrile structure, particularly the amount of hydrolyzable chlorine, should be less from the viewpoint of improving the reliability of electronic components to which it is applied. Although not particularly limited, it is preferably 1000 ppm or less, more preferably 500 ppm or less. In addition, the hydrolyzable chlorine referred to in the present invention refers to the value measured by the following method. That is, after dissolving 0.5 g of the sample in 30 ml of dioxane, 10 ml of 1N-KOH was added and the mixture was boiled and refluxed for 30 minutes, cooled to room temperature, further 100 ml of 80% acetone water was added, and a potential difference was obtained with an aqueous 0.002N- AgNO3 solution. It is a value obtained by titration.
本発明のエポキシ樹脂組成物には、必須成分として使用される式(1)のベンゾニトリル構造を持つエポキシ樹脂以外に、エポキシ樹脂成分として分子中にエポキシ基を2個以上有する他のエポキシ樹脂を併用してもよい。例を挙げれば、ビスフェノールA、ビスフェノールF、3,3',5,5'-テトラメチル-4,4'-ジヒドロキシジフェニルメタン、4,4'-ジヒドロキシジフェニルスルホン、4,4'-ジヒドロキシジフェニルスルフィド、4,4'-ジヒドロキシジフェニルケトン、フルオレンビスフェノール、4,4'-ビフェノール、3,3',5,5'-テトラメチル-4,4'-ジヒドロキシビフェニル、2,2'-ビフェノール、レゾルシン、カテコール、t-ブチルカテコール、t-ブチルハイドロキノン、1,2-ジヒドロキシナフタレン、1,3-ジヒドロキシナフタレン、1,4-ジヒドロキシナフタレン、1,5-ジヒドロキシナフタレン、1,6-ジヒドロキシナフタレン、1,7-ジヒドロキシナフタレン、1,8-ジヒドロキシナフタレン、2,3-ジヒドロキシナフタレン、2,4-ジヒドロキシナフタレン、2,5-ジヒドロキシナフタレン、2,6-ジヒドロキシナフタレン、2,7-ジヒドロキシナフタレン、2,8-ジヒドロキシナフタレン、上記ジヒドロキシナフタレンのアリル化物又はポリアリル化物、アリル化ビスフェノールA、アリル化ビスフェノールF、アリル化フェノールノボラック等の2価のフェノール類、あるいは、フェノールノボラック、ビスフェノールAノボラック、o-クレゾールノボラック、m-クレゾールノボラック、p-クレゾールノボラック、キシレノールノボラック、ポリ-p-ヒドロキシスチレン、トリス-(4-ヒドロキシフェニル)メタン、1,1,2,2-テトラキス(4-ヒドロキシフェニル)エタン、フルオログリシノール、ピロガロール、t-ブチルピロガロール、アリル化ピロガロール、ポリアリル化ピロガロール、1,2,4-ベンゼントリオール、2,3,4-トリヒドロキシベンゾフェノン、フェノールアラルキル樹脂、ナフトールアラルキル樹脂、ジシクロペンタジエン系樹脂等の3価以上のフェノール類、または、テトラブロモビスフェノールA等のハロゲン化ビスフェノール類から誘導されるグリシジルエーテル化物等がある。これらのエポキシ樹脂は、1種または2種以上を混合して用いることができる。 In the epoxy resin composition of the present invention, in addition to the epoxy resin having a benzonitrile structure of formula (1) used as an essential component, other epoxy resins having two or more epoxy groups in the molecule are added as epoxy resin components. They may be used together. Examples include bisphenol A, bisphenol F, 3,3′,5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, fluorene bisphenol, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,2'-biphenol, resorcin, catechol , t-butyl catechol, t-butyl hydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7- Dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxy Naphthalene, allylated or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, dihydric phenols such as allylated phenol novolak, or phenol novolak, bisphenol A novolak, o-cresol novolak, m- cresol novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxystyrene, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, fluoroglycinol, pyrogallol , t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene-based resin, etc. There are glycidyl etherified products derived from the above phenols or halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins can be used singly or in combination of two or more.
本発明のエポキシ樹脂組成物に用いる式(1)のベンゾニトリル構造を持つエポキシ樹脂の配合割合は、全エポキシ樹脂の50wt%以上であり、好ましくは70wt%以上、より好ましくは90wt%以上である。さらには、二官能性エポキシ樹脂の合計量が90wt%以上、好ましくは95wt%以上であることが望ましい。これより少ないと硬化物とした際の熱伝導率等の物性向上効果が小さくなるおそれがある。これは、ベンゾニトリル構造を持つエポキシ樹脂の含有率が高く、かつ二官能性エポキシ樹脂の含有率が高いものほど、成形物としての配向度が高くなるためである。 The proportion of the epoxy resin having a benzonitrile structure of formula (1) used in the epoxy resin composition of the present invention is 50 wt% or more, preferably 70 wt% or more, and more preferably 90 wt% or more of the total epoxy resin. . Furthermore, it is desirable that the total amount of the bifunctional epoxy resin is 90 wt % or more, preferably 95 wt % or more. If the amount is less than this, there is a possibility that the effect of improving physical properties such as thermal conductivity in the cured product may be reduced. This is because the higher the content of the epoxy resin having a benzonitrile structure and the higher the content of the bifunctional epoxy resin, the higher the degree of orientation of the molded product.
本発明のエポキシ樹脂組成物に用いる硬化剤としては、一般にエポキシ樹脂の硬化剤として知られているものはすべて使用でき、ジシアンジアミド、酸無水物類、多価フェノール類、芳香族及び脂肪族アミン類等がある。これらの中でも、半導体封止材等の高い電気絶縁性が要求される分野においては、多価フェノール類を硬化剤として用いることが好ましい。以下に、硬化剤の具体例を示す。 As the curing agent used in the epoxy resin composition of the present invention, all those generally known as curing agents for epoxy resins can be used, including dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. etc. Among these, polyhydric phenols are preferably used as a curing agent in fields such as semiconductor encapsulants that require high electrical insulation. Specific examples of the curing agent are shown below.
多価フェノール類としては、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S、フルオレンビスフェノール、4,4’-ビフェノール、2,2’-ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の2価のフェノール類、あるいは、トリス-(4-ヒドロキシフェニル)メタン、1,1,2,2-テトラキス(4-ヒドロキシフェニル)エタン、フェノールノボラック、o-クレゾールノボラック、ナフトールノボラック、ポリビニルフェノール等に代表される3価以上のフェノール類がある。更には、フェノール類、ナフトール類、ビスフェノールA、ビスフェノールF、ビスフェノールS、フルオレンビスフェノール、4,4’-ビフェノール、2,2’-ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の2価のフェノール類と、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、p-ヒドロキシベンズアルデヒド、p-キシリレングリコール等の縮合剤により合成される多価フェノール性化合物等がある。 Examples of polyhydric phenols include dihydric phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalene diol, or , tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. There are phenols. Furthermore, dihydric phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthalenediol, There are polyhydric phenolic compounds synthesized with condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde and p-xylylene glycol.
酸無水物硬化剤としては、例えば、無水フタル酸、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、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、メチル無水ハイミック酸、無水ドデシニルコハク酸、無水ナジック酸、無水トリメリット酸等がある。 Examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl himic anhydride, dodecynylsuccinic anhydride, nadic anhydride, and trimellitic anhydride.
アミン系硬化剤としては、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルプロパン、4,4’-ジアミノジフェニルスルホン、m-フェニレンジアミン、p-キシリレンジアミン等の芳香族アミン類、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン等の脂肪族アミン類がある。 Amine curing agents include aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine and p-xylylenediamine; There are aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine.
上記エポキシ樹脂組成物には、これら硬化剤の1種又は2種以上を混合して用いることができる。 One or a mixture of two or more of these curing agents can be used in the epoxy resin composition.
エポキシ樹脂と硬化剤の配合比率は、エポキシ基と硬化剤中の官能基が当量比で0.8~1.5の範囲であることが好ましい。この範囲外では硬化後も未反応のエポキシ基、又は硬化剤中の官能基が残留し、封止機能に関しての信頼性が低下する場合がある。 The mixing ratio of the epoxy resin and the curing agent is preferably in the range of 0.8 to 1.5 in terms of the equivalent ratio of the epoxy groups to the functional groups in the curing agent. Outside this range, unreacted epoxy groups or functional groups in the curing agent remain even after curing, which may reduce the reliability of the sealing function.
本発明のエポキシ樹脂組成物中には、ポリエステル、ポリアミド、ポリイミド、ポリエーテル、ポリウレタン、石油樹脂、インデン樹脂、インデン・クマロン樹脂、フェノキシ樹脂等のオリゴマー又は高分子化合物を他の改質剤等として適宜配合してもよい。添加量は、通常、樹脂成分の合計100重量部に対して、1~30重量部の範囲である。 In the epoxy resin composition of the present invention, oligomers or polymer compounds such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-cumarone resin, phenoxy resin, etc. may be used as other modifiers. It may be blended as appropriate. The amount added is usually in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the total resin components.
本発明のエポキシ樹脂組成物には、無機充填剤、顔料、難然剤、揺変性付与剤、カップリング剤、流動性向上剤等の添加剤を配合できる。無機充填剤としては、例えば、球状あるいは、破砕状の溶融シリカ、結晶シリカ等のシリカ粉末、アルミナ粉末、ガラス粉末、又はマイカ、タルク、炭酸カルシウム、アルミナ、水和アルミナ等が挙げられ、半導体封止材に用いる場合の好ましい配合量は70重量%以上であり、更に好ましくは80重量%以上である。 Additives such as inorganic fillers, pigments, flame retardants, thixotropic agents, coupling agents, fluidity improvers and the like can be added to the epoxy resin composition of the present invention. Examples of inorganic fillers include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, and hydrated alumina. When used as a sealing material, the blending amount is preferably 70% by weight or more, more preferably 80% by weight or more.
顔料としては、有機系又は無機系の体質顔料、鱗片状顔料等がある。揺変性付与剤としては、シリコン系、ヒマシ油系、脂肪族アマイドワックス、酸化ポリエチレンワックス、有機ベントナイト系等を挙げることができる。 Pigments include organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite-based agents.
本発明のエポキシ樹脂組成物には必要に応じて硬化促進剤を用いることができる。例を挙げれば、アミン類、イミダゾール類、有機ホスフィン類、ルイス酸等があり、具体的には、1,8-ジアザビシクロ(5,4,0)ウンデセン-7、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノールなどの三級アミン、2-メチルイミダゾール、2-フェニルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニル-4-メチルイミダゾール、2-へプタデシルイミダゾールなどのイミダゾール類、トリブチルホスフィン、メチルジフェニルホスフイン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィンなどの有機ホスフィン類、テトラフェニルホスホニウム・テトラフェニルボレート、テトラフェニルホスホニウム・エチルトリフェニルボレート、テトラブチルホスホニウム・テトラブチルボレートなどのテトラ置換ホスホニウム・テトラ置換ボレート、2-エチル-4-メチルイミダゾール・テトラフェニルボレート、N-メチルモルホリン・テトラフェニルボレートなどのテトラフェニルボロン塩などがある。添加量としては、通常、樹脂成分の合計100重量部に対して、0.01から5重量部の範囲である。 A curing accelerator can be used in the epoxy resin composition of the present invention, if necessary. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc. Specific examples include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, tri Tertiary amines such as ethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2- imidazoles such as heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; tetraphenylphosphonium/tetraphenylborate; tetraphenylphosphonium/ethyltriphenylborate; Tetra-substituted phosphonium/tetra-substituted borate such as butylphosphonium/tetrabutylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole/tetraphenylborate, and N-methylmorpholine/tetraphenylborate. The amount added is usually in the range of 0.01 to 5 parts by weight per 100 parts by weight of the total resin components.
更に必要に応じて、本発明のエポキシ樹脂組成物には、カルナバワックス、OPワックス等の離型剤、γ-グリシドキシプロピルトリメトキシシラン等のカップリング剤、カーボンブラック等の着色剤、三酸化アンチモン等の難燃剤、シリコンオイル等の低応力化剤、ステアリン酸カルシウム等の滑剤等を使用できる。 Furthermore, if necessary, the epoxy resin composition of the present invention may contain a releasing agent such as carnauba wax or OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a coloring agent such as carbon black, Flame retardants such as antimony oxide, stress reducing agents such as silicone oil, and lubricants such as calcium stearate can be used.
本発明のエポキシ樹脂組成物は、有機溶剤を溶解させたワニス状態とした後に、ガラスクロス、アラミド不織布、液晶ポリマー等のポリエステル不織布等の繊維状物に含浸させた後に溶剤除去を行い、プリプレグとすることができる。また、場合により銅箔、ステンレス箔、ポリイミドフィルム、ポリエステルフィルム等のシート状物上に塗布することにより積層物とすることができる。 The epoxy resin composition of the present invention is made into a varnish state by dissolving an organic solvent, impregnated with a fibrous material such as a glass cloth, an aramid nonwoven fabric, a polyester nonwoven fabric such as a liquid crystal polymer, etc., and then the solvent is removed to form a prepreg. can do. In some cases, a laminate can be obtained by coating a sheet-like material such as a copper foil, a stainless steel foil, a polyimide film, a polyester film, or the like.
本発明のエポキシ樹脂組成物を加熱硬化させれば、本発明の樹脂硬化物とすることができる。この硬化物は、エポキシ樹脂組成物を注型、圧縮成形、トランスファー成形等の方法により、成形加工して得ることができる。この際の温度は通常、120~220℃の範囲である。 The resin cured product of the present invention can be obtained by heat-curing the epoxy resin composition of the present invention. This cured product can be obtained by molding the epoxy resin composition by a method such as casting, compression molding, or transfer molding. The temperature at this time is usually in the range of 120 to 220°C.
以下、実施例及び比較例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。特に断りがない限り、「部」は重量部を表し、「%」は重量%を表す。また、測定方法はそれぞれ以下の方法により測定した。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to these. Unless otherwise specified, "parts" represent parts by weight and "%" represents weight percent. Moreover, the measurement method was each measured by the following methods.
1)エポキシ当量
電位差滴定装置を用い、溶媒としてメチルエチルケトンを使用し、臭素化テトラエチルアンモニウム酢酸溶液を加え、電位差滴定装置にて0.1mol/L過塩素酸-酢酸溶液を用いて測定した。
1) Epoxy equivalent Using a potentiometric titrator, using methyl ethyl ketone as a solvent, adding a tetraethylammonium bromide acetic acid solution, and measuring using a 0.1 mol/L perchloric acid-acetic acid solution with a potentiometric titrator.
2)OH当量
電位差滴定装置を用い、1,4-ジオキサンを溶媒に用い、1.5mol/L塩化アセチルでアセチル化を行い、過剰の塩化アセチルを水で分解して0.5mol/L-水酸化カリウムを使用して滴定した。
2) OH equivalent Using a potentiometric titrator, 1,4-dioxane is used as a solvent, acetylation is performed with 1.5 mol/L acetyl chloride, and excess acetyl chloride is decomposed with water to 0.5 mol/L-water. It was titrated using potassium oxide.
3)融点
示差走査熱量分析装置(エスアイアイ・ナノテクノロジー株式会社製 EXSTAR6000 DSC/6200)により、昇温速度5℃/分の条件で、DSCピーク温度を求めた。すなわち、このDSCピーク温度を樹脂の融点とした。
3) Melting point A DSC peak temperature was obtained with a differential scanning calorimeter (EXSTAR6000 DSC/6200, manufactured by SII Nanotechnology Co., Ltd.) under the condition of a heating rate of 5°C/min. That is, this DSC peak temperature was taken as the melting point of the resin.
4)溶融粘度
BROOKFIELD製、CAP2000H型回転粘度計を用いて、150℃にて測定した。
4) Melt viscosity Measured at 150°C using a CAP2000H rotational viscometer manufactured by BROOKFIELD.
5)軟化点
JIS-K-2207に従い環球法にて測定した。
5) Softening point Measured by the ring and ball method according to JIS-K-2207.
6)GPC測定
本体(東ソー株式会社製、HLC-8220GPC)にカラム(東ソー株式会社製、TSKgelG4000HXL、TSKgelG3000HXL、TSKgelG2000HXL)を直列に備えたものを使用し、カラム温度は40℃にした。また、溶離液にはテトラヒドロフラン(THF)を使用し、1mL/分の流速とし、検出器は示差屈折率検出器を使用した。測定試料はサンプル0.1gを10mLのTHFに溶解し、マイクロフィルターで濾過したものを50μL使用した。データ処理は、東ソー株式会社製GPC-8020モデルIIバージョン6.00を使用した。
6) GPC Measurement A column (TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL, manufactured by Tosoh Corporation) in series with a main body (HLC-8220GPC manufactured by Tosoh Corporation) was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as an eluent at a flow rate of 1 mL/min, and a differential refractive index detector was used as a detector. As a measurement sample, 0.1 g of the sample was dissolved in 10 mL of THF and filtered through a microfilter, and 50 μL of the solution was used. For data processing, GPC-8020 model II version 6.00 manufactured by Tosoh Corporation was used.
7)ガラス転移点(Tg)
熱機械測定装置(エスアイアイ・ナノテクノロジー株式会社製 EXSTAR6000TMA/6100)により、昇温速度10℃/分の条件でTgを求めた。
7) Glass transition point (Tg)
Tg was determined at a temperature increase rate of 10° C./min using a thermomechanical measurement device (EXSTAR6000TMA/6100 manufactured by SII Nanotechnology Co., Ltd.).
8)5%重量減少温度(Td5)、残炭率
熱重量/示差熱分析装置(エスアイアイ・ナノテクノロジー製 EXSTAR6000TG/DTA6200、)を用いて、窒素雰囲気下、昇温速度10℃/分の条件において、5%重量減少温度(Td5)を測定した。また、700℃における重量減少を測定し、残炭率として算出した。
8) 5% weight loss temperature (Td5), residual carbon ratio Using a thermogravimetric/differential thermal analyzer (EXSTAR6000TG/DTA6200, manufactured by SII Nanotechnology), under a nitrogen atmosphere, at a heating rate of 10°C/min. , the 5% weight loss temperature (Td5) was measured. Also, the weight loss at 700° C. was measured and calculated as the residual charcoal rate.
9)熱伝導率
熱伝導率は、NETZSCH製LFA447型熱伝導率計を用いて非定常熱線法により測定した。
9) Thermal conductivity Thermal conductivity was measured by the unsteady hot wire method using a NETZSCH LFA447 thermal conductivity meter.
10)溶融混練性
100℃における溶融混練性を確認。〇は混練可能、△は混練困難、×は未溶融成分あり、である。
10) Melt-kneadability Melt-kneadability at 100°C was confirmed. ○ indicates that kneading is possible, Δ indicates that kneading is difficult, and x indicates that unmelted components are present.
11)溶剤溶解性
サンプル瓶に樹脂組成物2g、メチルエチルケトン2gを秤量し、加熱溶解させた後、恒温槽内にて徐々に温度を低下させ、樹脂が析出した槽内の温度を測定した。
析出温度が25℃以下を○、26℃以上60℃未満を△、60℃以上を×とした。
11) Solvent Solubility After weighing 2 g of the resin composition and 2 g of methyl ethyl ketone into a sample bottle and heating and dissolving them, the temperature was gradually lowered in a constant temperature bath, and the temperature in the bath where the resin was deposited was measured.
A deposition temperature of 25° C. or less was evaluated as ◯, a deposition temperature of 26° C. or more and less than 60° C. was evaluated as Δ, and a deposition temperature of 60° C. or more was evaluated as X.
実施例1
2Lの4口セパラブルフラスコに4,4’-ジヒドロキシビフェニル54.6g、4,4’-ジヒドロキシジフェニルエーテル29.6gをN-メチル-2-ピロリドン250gに溶解した後、炭酸カリウム24.1gを加え、窒素気流下、攪拌しながら120℃に昇温した。その後、2,6-ジクロロベンゾニトリル25.2gを加え、145℃に昇温し6時間反応させた。反応液に酢酸20.9gを加えて中和した後、減圧下、N-メチル-2-ピロリドンを留去した。反応液にメチルイソブチルケトン250mLを加えて生成物を溶解した後、水洗により生成塩を除去した。その後、メチルイソブチルケトンを減圧蒸留により除いて、ヒドロキシ樹脂84gを得た。得られたヒドロキシ樹脂の水酸基当量は195g/eq.、融点は235℃、Mnは500であった。
次に、得られたヒドロキシ樹脂84gに、エピクロルヒドリン800g、ジエチレングリコールジメチルエーテル160gを仕込み、減圧下(約130Torr)、65℃にて48%水酸化ナトリウム水溶液37.5gを3時間かけて滴下した。この間、生成する水はエピクロルヒドリンとの共沸により系外に除き、留出したエピクロルヒドリンは系内に戻した。滴下終了後、さらに1時間反応を継続し脱水した。その後、エピクロルヒドリンを減圧留去し、メチルイソブチルケトンを加えた後、水洗により塩を除いた後、濾過、水洗を行い、メチルイソブチルケトンを減圧留去し、常温固形のエポキシ樹脂105gを得た(エポキシ樹脂A)。得られたエポキシ樹脂Aの軟化点は113℃、エポキシ当量は251g/eq.、溶融粘度は0.06Pa・s、GPCにて測定したn=0体は30%、Mnは460であった。
Example 1
After dissolving 54.6 g of 4,4'-dihydroxybiphenyl and 29.6 g of 4,4'-dihydroxydiphenyl ether in 250 g of N-methyl-2-pyrrolidone in a 2 L four-necked separable flask, 24.1 g of potassium carbonate was added. The temperature was raised to 120° C. under a nitrogen stream while stirring. After that, 25.2 g of 2,6-dichlorobenzonitrile was added, the temperature was raised to 145° C., and reaction was carried out for 6 hours. After neutralizing the reaction mixture by adding 20.9 g of acetic acid, N-methyl-2-pyrrolidone was distilled off under reduced pressure. After adding 250 mL of methyl isobutyl ketone to the reaction solution to dissolve the product, the resulting salt was removed by washing with water. Thereafter, methyl isobutyl ketone was removed by distillation under reduced pressure to obtain 84 g of hydroxy resin. The hydroxyl equivalent of the obtained hydroxy resin was 195 g/eq. , a melting point of 235° C. and an Mn of 500.
Next, 800 g of epichlorohydrin and 160 g of diethylene glycol dimethyl ether were added to 84 g of the obtained hydroxy resin, and 37.5 g of a 48% sodium hydroxide aqueous solution was added dropwise at 65° C. under reduced pressure (about 130 Torr) over 3 hours. During this time, the generated water was removed from the system by azeotroping with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropwise addition was completed, the reaction was continued for 1 hour to remove water. Thereafter, epichlorohydrin was distilled off under reduced pressure, methyl isobutyl ketone was added, and after removing the salt by washing with water, filtration and washing were carried out, methyl isobutyl ketone was distilled off under reduced pressure, and 105 g of epoxy resin solid at room temperature was obtained ( Epoxy resin A). The obtained epoxy resin A had a softening point of 113° C. and an epoxy equivalent of 251 g/eq. , the melt viscosity was 0.06 Pa·s, the n = 0 body measured by GPC was 30%, and the Mn was 460.
実施例2
4,4’-ジヒドロキシビフェニルの使用量を40.9g、4,4’-ジヒドロキシジフェニルエーテルの使用量を44.4gとした他は、実施例1と同様にして反応を行い、エポキシ樹脂112gを得た(エポキシ樹脂B)。得られたエポキシ樹脂Bの軟化点は104℃、エポキシ当量は241g/eq.、溶融粘度は0.04Pa・s、GPCにて測定したn=0体は23%、Mnは590であった。なお、中間体のヒドロキシ樹脂の水酸基当量は、184g/eq.、融点は221℃、Mnは670であった。
Example 2
The reaction was carried out in the same manner as in Example 1 except that the amount of 4,4'-dihydroxybiphenyl used was changed to 40.9 g and the amount of 4,4'-dihydroxydiphenyl ether used was changed to 44.4 g to obtain 112 g of an epoxy resin. (epoxy resin B). The obtained epoxy resin B had a softening point of 104° C. and an epoxy equivalent of 241 g/eq. , the melt viscosity was 0.04 Pa·s, the n = 0 body measured by GPC was 23%, and the Mn was 590. Incidentally, the hydroxyl equivalent of the intermediate hydroxy resin was 184 g/eq. , a melting point of 221° C. and an Mn of 670.
実施例3
4,4’-ジヒドロキシビフェニルの使用量を54.5g、4,4’-ジヒドロキシジフェニルエーテルの代わりにジヒドロキシジフェニルメタン(4,4’-ジヒドロキシジフェニルメタン:36.2%、2,4’-ジヒドロキシジフェニルメタン:46.6%、2,2’―ジヒドロキシジフェニルメタン:17.2% )を29.0g使用した他は、実施例1と同様にして反応を行い、エポキシ樹脂96gを得た。(エポキシ樹脂C)。得られたエポキシ樹脂Cの軟化点は120℃、エポキシ当量は264g/eq.、溶融粘度は0.06Pa・s、GPCにて測定したn=0体は28%、Mnは480であった。なお、中間体のヒドロキシ樹脂の水酸基当量は、193g/eq.、融点は276℃、Mnは540であった。
Example 3
The amount of 4,4'-dihydroxybiphenyl used was 54.5 g, and instead of 4,4'-dihydroxydiphenyl ether, dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane: 36.2%, 2,4'-dihydroxydiphenylmethane: 46 6%, 2,2'-dihydroxydiphenylmethane: 17.2%) was used, but the reaction was carried out in the same manner as in Example 1 to obtain 96 g of an epoxy resin. (epoxy resin C). The obtained epoxy resin C had a softening point of 120° C. and an epoxy equivalent of 264 g/eq. , the melt viscosity was 0.06 Pa·s, the n = 0 body measured by GPC was 28%, and the Mn was 480. Incidentally, the hydroxyl group equivalent of the intermediate hydroxy resin was 193 g/eq. , a melting point of 276° C. and an Mn of 540.
実施例4
4,4’-ジヒドロキシビフェニルの使用量を40.9g、4,4’-ジヒドロキシジフェニルエーテルの代わりにジヒドロキシジフェニルメタン(4,4’-ジヒドロキシジフェニルメタン:36.2%、2,4’-ジヒドロキシジフェニルメタン:46.6%、2,2’―ジヒドロキシジフェニルメタン:17.2% )を43.6gとした他は、実施例1と同様にして反応を行い、エポキシ樹脂98gを得た。(エポキシ樹脂D)。得られたエポキシ樹脂Dの軟化点は109℃、エポキシ当量は250g/eq.、溶融粘度は0.05Pa・s、GPCにて測定したn=0体は29%、Mnは630であった。なお、中間体のヒドロキシ樹脂の水酸基当量は、205g/eq.、融点は255℃、Mnは540であった。
Example 4
The amount of 4,4'-dihydroxybiphenyl used was 40.9 g, and instead of 4,4'-dihydroxydiphenyl ether, dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane: 36.2%, 2,4'-dihydroxydiphenylmethane: 46 .6%, 2,2'-dihydroxydiphenylmethane: 17.2%) was changed to 43.6 g, but the reaction was carried out in the same manner as in Example 1 to obtain 98 g of an epoxy resin. (epoxy resin D). The obtained epoxy resin D had a softening point of 109° C. and an epoxy equivalent of 250 g/eq. , the melt viscosity was 0.05 Pa·s, the n = 0 body measured by GPC was 29%, and the Mn was 630. Incidentally, the hydroxyl group equivalent of the intermediate hydroxy resin was 205 g/eq. , a melting point of 255° C. and an Mn of 540.
実施例5
4,4’-ジヒドロキシビフェニルを使用せず、4,4’-ジヒドロキシジフェニルエーテルの使用量を88.8gとした以外は実施例1と同様にして反応を行い、エポキシ樹脂107gを得た。(エポキシ樹脂E)。得られたエポキシ樹脂Eの軟化点は50℃、エポキシ当量は258g/eq.、溶融粘度は0.03Pa・s、GPCにて測定したn=0体は28%、Mnは540であった。なお、中間体のヒドロキシ樹脂の水酸基当量は、202g/eq.、融点は157℃、Mnは600であった。
Example 5
The reaction was carried out in the same manner as in Example 1 except that 4,4'-dihydroxybiphenyl was not used and the amount of 4,4'-dihydroxydiphenyl ether used was changed to 88.8 g to obtain 107 g of an epoxy resin. (epoxy resin E). The obtained epoxy resin E had a softening point of 50° C. and an epoxy equivalent of 258 g/eq. , the melt viscosity was 0.03 Pa·s, the n = 0 body measured by GPC was 28%, and the Mn was 540. Incidentally, the hydroxyl group equivalent of the intermediate hydroxy resin was 202 g/eq. , a melting point of 157° C. and an Mn of 600.
比較例1
4,4’-ジヒドロキシビフェニルの使用量を81.8gとし、4,4’-ジヒドロキシジフェニルエーテルを使用せず、N-メチル-2-ピロリドンの使用量を500gとした以外は実施例1と同様にして反応を行い、エポキシ樹脂78gを得た。(エポキシ樹脂F)。得られたエポキシ樹脂Fは結晶性を有し、その融点は139℃、エポキシ当量は226g/eq.、溶融粘度は0.10Pa・s、GPCにて測定したn=0体は34%、Mnは400であった。なお、中間体のヒドロキシ樹脂の水酸基当量は、220g/eq.、融点は272℃、Mnは500であった。
Comparative example 1
Example 1 was repeated except that the amount of 4,4'-dihydroxybiphenyl used was 81.8 g, 4,4'-dihydroxydiphenyl ether was not used, and N-methyl-2-pyrrolidone was used in an amount of 500 g. 78 g of epoxy resin was obtained. (epoxy resin F). The obtained epoxy resin F has crystallinity, has a melting point of 139° C. and an epoxy equivalent of 226 g/eq. , the melt viscosity was 0.10 Pa·s, the n = 0 body measured by GPC was 34%, and the Mn was 400. Incidentally, the hydroxyl group equivalent of the intermediate hydroxy resin was 220 g/eq. , a melting point of 272° C. and an Mn of 500.
実施例6~10および比較例2~4
エポキシ樹脂成分として、実施例1で得たエポキシ樹脂A、実施例2で得たエポキシ樹脂B、実施例3で得たエポキシ樹脂C、実施例4で得たエポキシ樹脂D、実施例5で得たエポキシ樹脂E、比較例1で得たエポキシ樹脂F、エポキシ樹脂G(4,4’-ジヒドロキシジフェニルエーテル型エポキシ樹脂、エポキシ当量163g/eq.;YSLV-80XY、日鉄ケミカル&マテリアル製)およびエポキシ樹脂H(ビフェニル型エポキシ樹脂、エポキシ当量195g/eq.;YX-4000H、三菱ケミカル製)を用い、硬化剤として、フェノールノボラック樹脂(OH当量105、軟化点83℃、;BRG-557、アイカ工業製)を用い、硬化促進剤としてトリフェニルホスフィンを用い、表1に示す配合でエポキシ樹脂組成物を得た。エポキシ樹脂組成物の溶融混練性と溶剤溶解性の結果を表1に示す。表中の数値は配合における重量部を示す。
このエポキシ樹脂組成物を用いて175℃にて成形し、175℃にて5時間ポストキュアを行い、硬化物試験片を得た後、Tg、Td5、残炭率、熱伝導率の各種物性測定に供した。
Examples 6-10 and Comparative Examples 2-4
As epoxy resin components, epoxy resin A obtained in Example 1, epoxy resin B obtained in Example 2, epoxy resin C obtained in Example 3, epoxy resin D obtained in Example 4, and epoxy resin D obtained in Example 5 were used. Epoxy resin E obtained in Comparative Example 1, epoxy resin F obtained in Comparative Example 1, epoxy resin G (4,4'-dihydroxydiphenyl ether type epoxy resin, epoxy equivalent 163 g / eq.; YSLV-80XY, manufactured by Nippon Steel Chemical & Material) and epoxy Using resin H (biphenyl type epoxy resin, epoxy equivalent 195 g / eq.; YX-4000H, manufactured by Mitsubishi Chemical), as a curing agent, phenol novolak resin (OH equivalent 105, softening point 83 ° C.; BRG-557, Aica Kogyo (manufactured) and triphenylphosphine as a curing accelerator to obtain an epoxy resin composition with the formulation shown in Table 1. Table 1 shows the melt kneadability and solvent solubility of the epoxy resin composition. Numerical values in the table indicate parts by weight in the formulation.
This epoxy resin composition was molded at 175° C. and post-cured at 175° C. for 5 hours to obtain a cured product test piece. served to
これらの結果から明らかなとおり、実施例で得られるエポキシ樹脂は溶融混練性、溶剤溶解性に優れ、その硬化物は熱安定性、熱伝導率が良好であることからパワーデバイス、および車載用途に適する。
As is clear from these results, the epoxy resins obtained in the examples have excellent melt-kneadability and solvent solubility, and the cured products thereof have good thermal stability and thermal conductivity. Suitable.
Claims (4)
A cured epoxy resin obtained by curing the epoxy resin composition according to claim 3 .
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