JPH0350229A - Epoxy resin and its production - Google Patents
Epoxy resin and its productionInfo
- Publication number
- JPH0350229A JPH0350229A JP18377489A JP18377489A JPH0350229A JP H0350229 A JPH0350229 A JP H0350229A JP 18377489 A JP18377489 A JP 18377489A JP 18377489 A JP18377489 A JP 18377489A JP H0350229 A JPH0350229 A JP H0350229A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- epoxy resin
- phenol
- tables
- polyhydric phenol
- 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
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 63
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- -1 hydroxy aromatic aldehyde Chemical class 0.000 claims description 10
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 abstract description 14
- 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 abstract description 10
- 238000007259 addition reaction Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000007363 ring formation reaction Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000003377 acid catalyst Substances 0.000 abstract description 4
- 150000001299 aldehydes Chemical class 0.000 abstract description 4
- 235000013824 polyphenols Nutrition 0.000 abstract 3
- 150000008442 polyphenolic compounds Chemical class 0.000 abstract 2
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 14
- 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 14
- 238000000034 method Methods 0.000 description 14
- 150000002989 phenols Chemical class 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 11
- 241000238557 Decapoda Species 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000003944 halohydrins Chemical class 0.000 description 9
- 229930185605 Bisphenol Natural products 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 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
- 238000004898 kneading Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- VZQSBJKDSWXLKX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C=C(O)C=CC=2)=C1 VZQSBJKDSWXLKX-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 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 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 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
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 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
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XVBLEUZLLURXTF-UHFFFAOYSA-N 2,4-dimethylbenzene-1,3-diamine Chemical group CC1=CC=C(N)C(C)=C1N XVBLEUZLLURXTF-UHFFFAOYSA-N 0.000 description 1
- PAPPEKHULAQSEJ-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)propanenitrile Chemical compound N#CC(C)C1=NC=CN1 PAPPEKHULAQSEJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RJGXLSPAKXWJGN-UHFFFAOYSA-N 2-bromo-4-(3-bromo-4-hydroxyphenyl)phenol Chemical group C1=C(Br)C(O)=CC=C1C1=CC=C(O)C(Br)=C1 RJGXLSPAKXWJGN-UHFFFAOYSA-N 0.000 description 1
- BWBGEYQWIHXDKY-UHFFFAOYSA-N 3-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC(O)=C1 BWBGEYQWIHXDKY-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- QNZWAJZEJAOVPN-UHFFFAOYSA-N 4-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC(Cl)=CC=C1C=O QNZWAJZEJAOVPN-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- HNJXPTMEWIVQQM-UHFFFAOYSA-M triethyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC HNJXPTMEWIVQQM-UHFFFAOYSA-M 0.000 description 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（、）発明の目的
（産業上の利用分野）
本発明は多価エポキシ樹脂及びその製造法に関するもの
である０本発明のエポキシ樹脂は、耐熱性、機械的強度
及び耐水性に富む硬化物を与えることができるので、注
型材、繊維補強用樹脂フェン、粉体塗料、電気機器封止
材用等のエポキシ樹脂として優れたものである。Detailed Description of the Invention (,) Object of the Invention (Industrial Application Field) The present invention relates to a polyvalent epoxy resin and a method for producing the same.The epoxy resin of the present invention has excellent heat resistance, mechanical strength and Since it can provide a cured product with high water resistance, it is an excellent epoxy resin for casting materials, fiber reinforcing resin fenestrations, powder coatings, electrical equipment sealants, etc.
（従来技術）
エポキシ樹脂は優れ九耐熱性、機械強度、電気特性を有
することから塗料、電気絶縁材、注凰材、構造材等の分
野で広く用いられている。(Prior Art) Epoxy resins have excellent heat resistance, mechanical strength, and electrical properties, and are therefore widely used in fields such as paints, electrical insulation materials, potting materials, and structural materials.
これらのエポキシ樹脂には、一般にビスフェノール人と
エピクロルヒドリンから製造される１分子中に約２個の
エポキシ基を有するビスフェノール人のジグリシジルエ
ーテルが広く使用されている。As these epoxy resins, bisphenol diglycidyl ether having about two epoxy groups in one molecule, which is generally produced from bisphenol and epichlorohydrin, is widely used.
近年、小型電気製品、ＬＳＩ、ＩＣ，宇宙航空機器の発
達に伴ない、よｐ耐熱性、機械強度の高い硬化物を与え
るエポキシ樹脂が要求され、１分子中に３個以上のエポ
キシ基を有する、いわゆる多官能エポキシ樹脂が用いら
れるようになりてきた。In recent years, with the development of small electrical appliances, LSI, IC, and aerospace equipment, epoxy resins that provide cured products with high heat resistance and mechanical strength are required, and epoxy resins that have three or more epoxy groups in one molecule are required. , so-called polyfunctional epoxy resins have come to be used.
多官能エポキシ樹脂を用いると、硬化反応後の架橋密度
が高くなるために機械的特性、電気特性が向上する。When a polyfunctional epoxy resin is used, the crosslinking density after the curing reaction becomes high, so that mechanical properties and electrical properties are improved.
かかる多官能のエポキシ樹脂としては、フェノールノダ
ラック樹脂のポリエポキシド（たとえば油化シェルニー
キシ株式会社商品名エピコート１５４）、Ｏ−クレゾー
ルノＮラック樹脂のポリエポキシド（たとえば日本化薬
株式会社商品名ＥＯＣＮ １０４ Ｓ ）等が実用化さ
れ、耐熱性や高強度の必要な絶縁塗料、半導体封止材料
、ＦＲＴＰ構造材、プリント配線基板等の分野において
使用されている。しかし、これらのエポキシ樹脂の硬化
物も、耐熱温度がせいぜい２００℃程度であシ、よシ耐
熱性の高い硬化物を与えるエポキシ樹脂の出現が望まれ
ている。Such polyfunctional epoxy resins include polyepoxides of phenol nodalac resins (e.g., Yuka Shell Nixi Co., Ltd., trade name Epicote 154), O-cresol no-Nlac resin polyepoxides (for example, Nippon Kayaku Co., Ltd., trade name EOCN 104 S). etc. have been put into practical use and are used in fields such as insulating paints that require heat resistance and high strength, semiconductor sealing materials, FRTP structural materials, and printed wiring boards. However, even the cured products of these epoxy resins have a heat resistance temperature of about 200° C. at most, and there is a desire for the emergence of epoxy resins that can provide cured products with even higher heat resistance.
また、多官能エポキシ樹脂として、ジアミノノフェニル
メタンのテトラニブキシド、テトラフェノールエタンの
テトラグリシツルエーテル等も知られている。しかし、
これらのエポキシ樹脂は。Further, as polyfunctional epoxy resins, tetraniboxide of diaminonophenylmethane, tetraglycityl ether of tetraphenol ethane, etc. are also known. but,
These epoxy resins.
耐熱温度がせいぜい２００℃を若干超える程度の硬化物
しか与えることができず、また高温時の耐水性に劣るの
で、たとえばプレッシャー・クツカーテストに合格しな
い。また、分子内にアミノ基を有するニーキシ樹脂は保
存性が悪（、ｆル化しやすく、かつ吸水性が高い欠点を
有する。It can only provide a cured product with a heat resistance temperature of slightly over 200°C at most, and it has poor water resistance at high temperatures, so it does not pass, for example, the pressure Kutsuker test. In addition, Nixy resin having an amino group in its molecule has the disadvantages of poor storage stability (easily oxidation) and high water absorption.
（発明の課題）
本発明は、耐熱性が２００℃以上であり、機械的強度の
優れた硬化物を与える多官能エポキシ樹脂及びその製造
法を提供しようとするものである。(Problem of the Invention) The present invention provides a polyfunctional epoxy resin that provides a cured product with heat resistance of 200° C. or higher and excellent mechanical strength, and a method for producing the same.
（ｂ）発明の構成
（課題の解決手段）
本発明者等は、前記の課題を解決するために種種研究を
重ねた結果、ビスフェノール類若しくはジＬドロキシビ
フェノール類と、とドロキシ芳香族アルデヒド類との縮
合で得られた多価フェ／−ル化合物に、エビハロヒドリ
ンをアルカリ金属水酸化物の存在下で反応させて得られ
たエポキシ樹脂によって、その目的を達成することがで
き九のである。(b) Structure of the invention (means for solving the problem) As a result of repeated research in order to solve the above problems, the present inventors have discovered that bisphenols or di-L-droxybiphenols, and droxyaromatic aldehydes This objective can be achieved by using an epoxy resin obtained by reacting a polyhydric fer/fer compound obtained by condensation with shrimp halohydrin in the presence of an alkali metal hydroxide.
すなわち、
本発明のエポキシ樹脂は、
一般式
炭素数１〜９のアルキレン基、又は直接結合を示し、Ｗ
は炭素数１〜９のアルキル基又は／Ｓログン原子を示し
、各ビは互いに同一であっても異なりていてもよく、ｐ
及びｑはそれぞれ０、ｌ又は２を示す、）
で茨わされるフェノール類の少なくとも１種と、一般式
（式中 Ｒ２は水素原子、メトキシ基、炭素数１〜９の
アルキル基、ハロダン原子、又はニトロ基を示す。）
で表わされるヒドロキシ芳香族アルデヒド類との縮合物
である多価フェノール類をエビハロヒドリンと反応させ
てなるエポキシ樹脂である。That is, the epoxy resin of the present invention has a general formula of an alkylene group having 1 to 9 carbon atoms or a direct bond, and W
represents an alkyl group having 1 to 9 carbon atoms or a /S logon atom, each Bi may be the same or different from each other, and p
and q represent 0, l or 2, respectively) and a general formula (wherein R2 is a hydrogen atom, a methoxy group, an alkyl group having 1 to 9 carbon atoms, a halodane atom) This is an epoxy resin made by reacting a polyhydric phenol, which is a condensation product with a hydroxy aromatic aldehyde (or a nitro group), with shrimp halohydrin.
また、本発明のエポキシ樹脂の製造法は、一般式
炭素数１〜９のフルキレン基、又は直接結合を示し Ｈ
／は炭素数１〜９のアルキル基又はハロゲン原子を示し
、各Ｗは互いに同一であっても異なりていてもよく、ｐ
及びｑはそれぞれＯｌｌ又は２を示す。）
で表わされるフェノール類の少なくとも１種と、一般式
（式中、Ｒ２は水素原子、メトキシ基、炭素数１〜９の
アルキル基、ハロゲン原子、又はニトロ基を示す、）
で表わされるヒドロキシ芳香族アルデヒド類の少なくと
も１種とを縮合反応させて多価フェノール類とし、得ら
れた多価フェノール類とエビハロヒドリンとをアルカリ
金属水酸化物の存在下で反応させることを特徴とする方
法である。In addition, the method for producing an epoxy resin of the present invention has a general formula of a fullylene group having 1 to 9 carbon atoms, or a direct bond.
/ represents an alkyl group having 1 to 9 carbon atoms or a halogen atom, each W may be the same or different from each other, and p
and q represent Oll or 2, respectively. ) and a hydroxy aromatic represented by the general formula (wherein R2 represents a hydrogen atom, a methoxy group, an alkyl group having 1 to 9 carbon atoms, a halogen atom, or a nitro group) This method is characterized by carrying out a condensation reaction with at least one kind of group aldehydes to obtain polyhydric phenols, and reacting the obtained polyhydric phenols with shrimp halohydrin in the presence of an alkali metal hydroxide.
本発明における前記−数式囚で表わされる７エ／ −ル
類ｔｉ、 詳しくはビスフェノール、ジヒドロキシビフ
ェニル及びそれらの特定の誘導体類であるが、そのビス
フェノール類としては、たとえば４．４′−ジヒドロキ
シ？）フェニルメタン、４．４’−２ヒドロキシジフ工
ニルグロノダン％Ｌ２’−ジヒドロキシジフェニルブタ
ン、４．４’−ジヒドロキシジフェニルブタ／、４．４
’−ジヒドロキシジフェニルペンタン、４ｍ４’−ジヒ
ドロキシジフェニルエーテル、４．４’−＆ヒドロキシ
ノフェニルケトン、 ４．４’−ジヒドロキジノフェニ
ルスルフィド、 ４．４’−ジヒドロキシジフェニルス
ルホンがあげられる。In the present invention, the 7-ethyl compounds represented by the above formula are specifically bisphenol, dihydroxybiphenyl, and specific derivatives thereof, and the bisphenols include, for example, 4,4'-dihydroxy? ) Phenylmethane, 4.4'-2hydroxydiphenylgronodan% L2'-dihydroxydiphenylbutane, 4.4'-dihydroxydiphenylbutane/, 4.4
Examples include '-dihydroxydiphenylpentane, 4m4'-dihydroxydiphenyl ether, 4,4'-&hydroxynophenyl ketone, 4,4'-dihydroxydiphenyl sulfide, and 4,4'-dihydroxydiphenyl sulfone.
また、炭素数１〜９のアルキル置換基を有するビス７８
ノール類としては、たとえば２，２′−ジメチル−４，
４′−ジヒドロキシジフェニルメタン、３．３’ −＆
、＋Ｅ チ＃ −４，４’−ジヒドロキシジフェニル
グロノ臂ンなどがあげられ、またノ１０ｒン置換ビスフ
ェノール類としては、たとえば３，３′−ジブロモ−４
，４′−ジヒドロ中ジメタン、 ３．３’ノデ四モー４
，４′−ジヒドロキシグロノやンなどがあげられる。Also, bis78 having an alkyl substituent having 1 to 9 carbon atoms
Examples of the nols include 2,2'-dimethyl-4,
4'-dihydroxydiphenylmethane, 3.3'-&
, +E -4,4'-dihydroxydiphenylglobin, etc., and examples of -10rn-substituted bisphenols include, for example, 3,3'-dibromo-4
, dimethane in 4'-dihydro, 3.3'nodetetramo4
, 4'-dihydroxygulon, and the like.
また、ジヒド・ワキシビフェニル類としては、たとえば
４，４′−ジヒドロキシビフェニル、３ 、３’−ジヒ
ドロキシビフェニルなどがあげられ、炭素数１〜９のア
ルキル置換基を有するピフェニル類としては、たとえば
３，３′−ジメチル−４，４′−ジヒドロキシビフェニ
ル、３，３′−ジプチル−４，４’−ジヒドロキシビフ
ェニルなどがあげられる。また、ハロダン置換ビフェニ
ル類としては、たとえば３．３′−ジブロモ−４，４′
−ジヒドロキシビフェニルなどがあげられる。Examples of dihydro-waxybiphenyls include 4,4'-dihydroxybiphenyl and 3,3'-dihydroxybiphenyl, and examples of piphenyls having an alkyl substituent having 1 to 9 carbon atoms include 3,4'-dihydroxybiphenyl, etc. , 3'-dimethyl-4,4'-dihydroxybiphenyl, 3,3'-diptyl-4,4'-dihydroxybiphenyl, and the like. In addition, examples of halodane-substituted biphenyls include 3,3'-dibromo-4,4'
-dihydroxybiphenyl, etc.
これらのフェノール類（４）は、１種類を単独で、又は
２種以上を併用して用いることができるし、さらＫこれ
らの７エノール類（４）に、さらに他の７エノール類を
、少量であれば併用しても差支えがない。These phenols (4) can be used alone or in combination of two or more, and in addition to these 7 enols (4), other 7 enols can be used in small amounts. If so, there is no problem in using them together.
次に、前記−数式（Ｂ）で表わされるヒドロキシ芳香族
アルデヒド類としては、たとえばサリチルアルデヒド、
４−ヒドロキシベンズアルデヒド、バニリン、３−ヒド
ロキシベンズアルデヒド、２−ヒドロキシ−３−二トロ
ペンズアルデヒド、４−クロロ−２−ヒドロキシベンズ
アルデヒド、４−プロモー３−ヒドロキシベンズアルデ
ヒド、３−プロモー４−ヒドロキシベンズアルデヒドナ
Ｅｉ）Ｅあげられる。Next, examples of the hydroxy aromatic aldehydes represented by formula (B) include salicylaldehyde,
4-hydroxybenzaldehyde, vanillin, 3-hydroxybenzaldehyde, 2-hydroxy-3-nitropenzaldehyde, 4-chloro-2-hydroxybenzaldehyde, 4-promo-3-hydroxybenzaldehyde, 3-promo-4-hydroxybenzaldehyde (Ei) E can be given.
これらのヒドロキシ芳香族アルデヒド類（Ｂ）も、１２
１類を単独で、又は２種以上を併用して用いることがで
きる。These hydroxy aromatic aldehydes (B) also have 12
Type 1 can be used alone or in combination of two or more types.
類（Ｂ）１モルに対して、フェノール類（４）を０．５
〜５０モル、好ましくは１．０〜３０モルの割合で反応
させる０反応温度は５０〜１８０℃、好ましくは８０〜
１５０℃で１〜８時間反応させる。反応終了後、酸触媒
を留去するか、アルカリで中和して不活性化するか、又
は水不溶性溶剤を加えて水洗してから、脱水及び脱溶剤
のために蒸留をしてそれらを除くと目的の多価フェノー
ル類が得られる。前記の脱水、脱溶剤のための蒸留は２
３０℃以下の温度で行なわせるのが望ましい。0.5 phenols (4) per 1 mole of class (B)
The reaction temperature is 50-180°C, preferably 80-180°C, preferably 1.0-30 mol.
React at 150°C for 1 to 8 hours. After the reaction is complete, the acid catalyst is distilled off, neutralized with an alkali to inactivate it, or a water-insoluble solvent is added and washed with water, followed by distillation for dehydration and solvent removal to remove them. and the desired polyhydric phenols are obtained. The above-mentioned distillation for dehydration and solvent removal is 2
It is desirable to carry out the process at a temperature of 30°C or lower.
との縮合反応における酸触媒としては、たとえば硫酸、
壇酸、硝酸、臭化水素、過塩素酸などのｍｌ！［、）４
’） ）ルエンスルホン駿、ベンゼンスルホン酸等のス
ルホン酸類、シ為り酸、コノ）り酸、マロン酸、モノク
ロル酢酸、ジクロル酢酸などのカルメン類などが用いら
れる。酸触媒の使用量は、反応条件によっても異なるが
、通常、フェノール類囚の１００！量部に対して０．０
１〜２０重量部、好ましくは０．１〜１０重量部である
。Examples of acid catalysts in the condensation reaction with
ml of dinic acid, nitric acid, hydrogen bromide, perchloric acid, etc.! [,)4
Sulfonic acids such as luenesulfonic acid and benzenesulfonic acid, carmenes such as cylindrical acid, conolinic acid, malonic acid, monochloroacetic acid, and dichloroacetic acid are used. The amount of acid catalyst used varies depending on the reaction conditions, but is usually 100% of the amount of phenols. 0.0 per part
The amount is 1 to 20 parts by weight, preferably 0.1 to 10 parts by weight.
この縮合反応には、特に反応溶媒を必要としないが、ベ
ンゼン、トルエン、キシレン、ブチルエーテル、グライ
ム、テトラヒドロフラン、アルコールなどのような反応
溶媒を用いてもよい。This condensation reaction does not particularly require a reaction solvent, but reaction solvents such as benzene, toluene, xylene, butyl ether, glyme, tetrahydrofuran, alcohol, etc. may be used.
このような縮合反応で得られる多価フェノール類は、
ＧＰＣクロマトグラムで求めた数平均分子量が３００〜
５０００程度のものが好ましいが、この範囲に限定され
るものでない。Polyhydric phenols obtained through such condensation reactions are
Number average molecular weight determined by GPC chromatogram is 300~
A value of about 5,000 is preferable, but it is not limited to this range.
次に、以上のようにして製造された多価フェノール類に
、アルカリ金属水酸化物の存在下でエビハロヒドリンを
反応させれば、目的とする本発明のエポキシ樹脂が得ら
れるが、そのエポキシ樹脂の製造方法としては、次の二
つの方法が代表的な方法としてあげられる。Next, by reacting the polyhydric phenols produced as described above with shrimp halohydrin in the presence of an alkali metal hydroxide, the desired epoxy resin of the present invention can be obtained. The following two methods are representative as manufacturing methods.
■ 多価フェノール類と過剰量のエビハロヒドリンとを
アルカリ金属水酸化物の共存下で反応させ、多価フェノ
ール類へのエピノ１０ヒドリンの付加反応と、エポキシ
環を形成する閉環反応とを同時に行なわせてエポキシ樹
脂を得る一段法。■ Polyhydric phenols and an excess amount of shrimp halohydrin are reacted in the presence of an alkali metal hydroxide to simultaneously perform the addition reaction of epino-10hydrin to the polyhydric phenols and the ring-closing reaction to form an epoxy ring. A one-step method to obtain epoxy resin.
■ 多価フェノール類と過剰のエピノ１０ヒドリンとを
ホスホニウム塩又は四級アンモニウム塩等の触媒の存在
下で付加反応させ、次いでアルカリ金属水酸化物を添加
して閉環反応を行なわせてエポキシ樹脂を得る二段法。■ Polyhydric phenols and excess epino-10hydrin are subjected to an addition reaction in the presence of a catalyst such as a phosphonium salt or a quaternary ammonium salt, and then an alkali metal hydroxide is added to perform a ring-closing reaction to form an epoxy resin. Two step method to get.
これらの二つの方法のうち、エポキシ樹脂収率カ高１／
ｉこと、生成エポキシ樹脂中の高分子量体含量が低いこ
とからして、二段法の方が好ましい。Among these two methods, the epoxy resin yield is 1/
In particular, the two-stage method is preferred because the content of polymers in the produced epoxy resin is low.
前記の一段法における反応温度は６０〜１５０℃、好ま
しくは８０〜１２０℃の範囲であシ、反応割合は多価フ
ェノール類に含まれるフェノール性水酸基に対し、エビ
ハロヒドリンが２倍〜２０倍モル、好ましくは４倍〜１
２倍モルである。また、アルカリ金属水酸化物は、多価
フェノール類のフェノール性水酸基に対して少なくとも
等モル、好ましくは１．０５〜１．５倍モルである。The reaction temperature in the one-step method is 60 to 150°C, preferably 80 to 120°C, and the reaction ratio is 2 to 20 times the mole of shrimp halohydrin to the phenolic hydroxyl group contained in the polyhydric phenol. Preferably 4 times to 1
It is twice the mole. Moreover, the alkali metal hydroxide is at least equimolar, preferably 1.05 to 1.5 times the molar amount of the phenolic hydroxyl group of the polyhydric phenol.
また、後者の二段法においては、前段の付加反応温度が
４０〜１５０℃、好ましくは７０〜１４０℃であシ、後
段の閉環反応温度が２０−１５０℃、好ましくは４０〜
１００℃である。触媒量は多価フェノール類に対して０
．１〜５モル慢でアシ、エピハロヒドリン及びアルカリ
金属水酸化物量は一段法と同様である。In the latter two-stage method, the addition reaction temperature in the first stage is 40-150°C, preferably 70-140°C, and the ring-closing reaction temperature in the second stage is 20-150°C, preferably 40-140°C.
The temperature is 100°C. The amount of catalyst is 0 for polyhydric phenols.
．． The amount of acetic acid, epihalohydrin and alkali metal hydroxide is the same as in the one-stage method.
一段法の反応及び二段法における後段の閉環反応は、常
圧又は減圧下（５０〜２００ ｓｍＨｙ）で、生成する
水をエビハロヒドリンとの共沸により連続的に系外に除
去しながら行なわせてもよい。The reaction in the one-stage method and the subsequent ring-closing reaction in the two-stage method are carried out under normal pressure or reduced pressure (50 to 200 smHy) while continuously removing the generated water from the system by azeotroping with shrimp halohydrin. Good too.
原料のエビハロヒドリンとしては、たとえばエピクロル
ヒドリン、エビブロモヒドリン、β−メグ・ルエピクロ
ルヒドリン及びβ−メチルエピブロモヒドリン等があげ
られる。Examples of the raw shrimp halohydrin include epichlorohydrin, shrimp bromohydrin, β-meg-rue epichlorohydrin, and β-methyl epibromohydrin.
また、アルカリ金属水酸化物としては、水酸化カリウム
、水酸化ナトリウムがあげられる。Further, examples of the alkali metal hydroxide include potassium hydroxide and sodium hydroxide.
二段法における前段の付加反応において使用される触媒
としては、たとえば第四級アンモニウム塩、ホスファイ
ト等があげられる。その第四級アンそニクム塩としては
、たと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クロリド、トリエチルメチルアンモ
ニウムクロリド、テトラエチルアンモニウムアイオダイ
ド、セチルトリエチルアンモニウムプロミド等がアケラ
れる。そのホスファイトとしては、たとえばトリフェニ
ルホスホニウムハライド（たとえばアイオダイド、プロ
ミド、クロリド）、トリフェニルエチルホスホニクムジ
エチルホスフェイト及びホスホネート等があげられる。Examples of the catalyst used in the first addition reaction in the two-stage process include quaternary ammonium salts and phosphites. Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium chloride, triethylmethylammonium chloride, tetraethylammonium iodide, cetyltriethylammonium bromide, and the like. Examples of the phosphite include triphenylphosphonium halides (eg, iodide, bromide, chloride), triphenylethylphosphonicum diethyl phosphate, and phosphonates.
これらのうち、特に好ましい触媒はテトラメチルアンモ
ニウムクロリド及びナト２エテルアルアンモニウムプロ
ミドである。Among these, particularly preferred catalysts are tetramethylammonium chloride and nato-2etheralammonium bromide.
これらの−段法又は二段法の反応終了後、反応液を一過
助剤（たとえば上２イト等）を用いてｒ過して副生する
塩を除去したのち、未反応のエビハロヒドリンを減圧下
で回収してエポキシ樹脂を得るか、又は反応液を減圧し
て未反応のエビハロヒドリンを回収したのち、水に難溶
性の有機溶媒、たとえばメチルイソグチルケトン、シク
ロヘキサ有機溶媒を留去して精製して、精製エポキシ樹
脂を得る。また、生成エポキシ樹脂は、ジオキサン、テ
トラヒドロフランなどのような水溶性溶剤中に溶解させ
て少量のアルカリ金属水酸化物を加えて脱塩酸し、５〜
１０倍量の水中に攪拌しながらその樹脂溶液を投入し、
再沈澱させて精製してもよい。After the reaction of these one-stage or two-stage methods is completed, the reaction solution is filtered using a passing aid (for example, Kami-2ite, etc.) to remove by-product salts, and unreacted shrimp halohydrin is removed under reduced pressure. Either collect the epoxy resin under vacuum, or reduce the pressure of the reaction solution to collect unreacted ebihalohydrin, and then purify by distilling off organic solvents that are poorly soluble in water, such as methyl isobutyl ketone and cyclohexa organic solvents. A purified epoxy resin is obtained. In addition, the produced epoxy resin is dissolved in a water-soluble solvent such as dioxane, tetrahydrofuran, etc., and a small amount of alkali metal hydroxide is added to remove hydrochloric acid.
Pour the resin solution into 10 times the amount of water while stirring,
It may be purified by reprecipitation.
本発明のエポキシ樹脂は、それを単独で又は他のエポキ
シ樹脂と併用して種々の用途に供するととができる。す
なわち、本発明のエポキシ樹脂を単独で用いて、又はこ
れに他のエポキシ化合物の１種又は２種以上を適宜に併
用して、適当な硬化剤で硬化（架橋）反応させれば、耐
熱性、耐水性、機械強度に優れた硬化物となる。The epoxy resin of the present invention can be used alone or in combination with other epoxy resins for various uses. That is, if the epoxy resin of the present invention is used alone or in combination with one or more other epoxy compounds as appropriate and subjected to a curing (crosslinking) reaction with an appropriate curing agent, heat resistance can be achieved. , resulting in a cured product with excellent water resistance and mechanical strength.
本発明のエポキシ樹脂に併用される他のエポキシ化合物
には格別の制限がなく、用途等に応じて種々の工４キシ
化合物が用いられる。その併用される他のエポキシ化合
物としては、たとえばビスフェノール人若しくはブロモ
ビスフェノールＡ等のポリグリシジルエーテル類、フェ
ノールノボラックやクレゾールツメラック樹脂等のポリ
グリシジルエーテル類、７タル酸やシクロヘキサンジカ
ルゲン酸等のポリグリシジルエステル類、アニリンやト
ルイジン等とのポリグリシジルアミン類等があげられる
。これらの他のエポキシ化合物は、全ニーキシ化合物中
の５０重量％以下、好ましくは２０重量％以下の範囲内
で、本発明のエポキシ樹脂に併用される。Other epoxy compounds to be used in combination with the epoxy resin of the present invention are not particularly limited, and various epoxy compounds may be used depending on the intended use. Examples of other epoxy compounds used in combination include polyglycidyl ethers such as bisphenol or bromobisphenol A, polyglycidyl ethers such as phenol novolac and cresol tumerac resin, and polyglycidyl ethers such as heptalic acid and cyclohexanedicargenic acid. Examples include glycidyl esters, polyglycidyl amines with aniline, toluidine, etc. These other epoxy compounds are used in combination with the epoxy resin of the present invention within a range of 50% by weight or less, preferably 20% by weight or less based on the total Nyxy compound.
本発明のニーキシ樹脂を硬化させる硬化剤としては、種
々の硬化剤が使用できる。たとえば脂肪族アミン類、芳
香族アンン類、複素環式アミン類、三７フ化ホウ素等の
ルイス酸、及びこれらの塩類、有機酸類、有機酸無水物
類、尿素若しくはそれらの誘導体類、及びポリメルカプ
タン類等があげられる。その具体例としては、たとえば
ジアミノジフェニルメタン、ジアミノジフェニルスルホ
ン゛、２．４−ジアミノ−ｍ−キシレン等の芳香族アミ
ン；２−メチルイミダゾール、２，４．５− ）リフェ
ニルイミダゾール、１−シアンエチル−２−メチルイミ
ダゾール等のイミダゾール若しくはイミダゾール置換体
、又はこれらと有機酸との塩；フマル酸、トリメリット
酸、ヘキサヒドロフタル酸等の有機カルボン酸；無水フ
タル酸、無水エンドメチレンテトラヒドロフタル酸、無
水へキサヒドロフタル酸等の有機酸無水物；ジシアンジ
アミド、メラミン、グアナミン等の尿素誘導体ニトリエ
チレンテトラミン、ジエチレントリアミン、キシリレン
ジアミン、インホロンジアミン等の脂肪族ポリアミン類
、及びこれらのエチレンオキシド、プロピレンオキシド
等のエポキシ化合物、若しくはアクリルニトリル、アク
リル酸等のアクリル化合物などとの付加物が使用できる
。Various curing agents can be used as the curing agent for curing the NIXY resin of the present invention. For example, aliphatic amines, aromatic ammoniums, heterocyclic amines, Lewis acids such as boron trifluoride, and their salts, organic acids, organic acid anhydrides, urea or their derivatives, and polystyrene. Examples include mercaptans. Specific examples include aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone, 2,4-diamino-m-xylene; 2-methylimidazole, 2,4.5-)riphenylimidazole, 1-cyanethyl - Imidazole or imidazole substitutes such as 2-methylimidazole, or salts of these with organic acids; organic carboxylic acids such as fumaric acid, trimellitic acid, hexahydrophthalic acid; phthalic anhydride, endomethylenetetrahydrophthalic anhydride, Organic acid anhydrides such as hexahydrophthalic anhydride; urea derivatives such as dicyandiamide, melamine, and guanamine; aliphatic polyamines such as nitriethylenetetramine, diethylenetriamine, xylylenediamine, and inphorondiamine; and their ethylene oxide, propylene oxide, etc. Epoxy compounds, or adducts with acrylic compounds such as acrylonitrile and acrylic acid can be used.
また、硬化剤としてフェノールノゲラック樹脂、クレゾ
ールノボラック樹脂、テトラヒドロキ７フェニルエタン
、本発明における前記のフェノール類（４）とヒドロキ
シ芳香族アルデヒド類（Ｂ）との縮合物のような多価フ
ェノール類等を用い、これに必要に応じて促進剤として
アミン類を併用することができる。In addition, as a curing agent, polyhydric phenols such as phenol nogelac resin, cresol novolak resin, tetrahydroxephenylethane, and a condensate of the above-mentioned phenol (4) and hydroxyaromatic aldehyde (B) in the present invention are used. etc., and if necessary, amines can be used in combination as a promoter.
本発明のエポキシ樹脂には、前記の硬化剤のほかに、必
要に応じて可凰剤、有機溶剤、反応性希釈剤、増量剤、
充てん剤、補強剤、顔料、難燃化剤、増粘剤及び可撓性
付与剤等の種々の添加剤を配合することができる。In addition to the above-mentioned curing agent, the epoxy resin of the present invention may optionally contain a sintering agent, an organic solvent, a reactive diluent, an extender,
Various additives such as fillers, reinforcing agents, pigments, flame retardants, thickeners, and flexibility agents can be blended.
本発明のエポキシ樹脂は、特異な構造をもった多官能エ
ポキシ樹脂であシ、その硬化物は従来のエポキシ樹脂硬
化物に較べて耐熱性、機械強度及び耐水性に優れている
。したがって、このエポキシ樹脂は、積層材、成形材料
、接着剤、塗料、封止材等の各種の分野において有利に
使用することができる。The epoxy resin of the present invention is a multifunctional epoxy resin with a unique structure, and its cured product has superior heat resistance, mechanical strength, and water resistance compared to conventional cured epoxy resin products. Therefore, this epoxy resin can be advantageously used in various fields such as laminated materials, molding materials, adhesives, paints, and sealants.
特に１本発明のエポキシ樹脂に硬化剤を配合して硬化性
樹脂組成物とし、これをテトラヒドロフラン、メチルエ
チルケト／、ジメチルホルムアミド等の溶剤に溶解した
フェスをガラス布に含浸、乾燥してプリプレグとし、さ
らにこのプリプレグを数枚重ねたものを鋼箔と重ねて加
熱プレスすることによシ、耐熱性のプリント配線基板用
銅張シ積層板を製造するととができる。Particularly, 1. A curable resin composition is obtained by blending a curing agent with the epoxy resin of the present invention, and a curable resin composition is obtained by dissolving this in a solvent such as tetrahydrofuran, methyl ethyl keto/dimethyl formamide, impregnated into a glass cloth, and dried to obtain a prepreg. A heat-resistant copper-clad laminate for printed wiring boards can be manufactured by stacking several sheets of this prepreg with steel foil and hot pressing.
また、前記の硬化性樹脂組成物に、硬化促進剤、シリカ
等の充填材、滑剤を加え、加温したロール上で混練すれ
ば成形用コンパウンドが得られる。Moreover, a molding compound can be obtained by adding a curing accelerator, a filler such as silica, and a lubricant to the curable resin composition and kneading the mixture on a heated roll.
このコンパウンドは、トランスファー成形機等を用いて
成形して半導体封止や機械部品の製造に使用するととが
でき、それにょシ高＠特性及び耐グレッシャークッヵー
テスト性に優れた硬化樹脂を与えるととができる。This compound can be molded using a transfer molding machine and used for semiconductor encapsulation and manufacturing of mechanical parts, and is also a cured resin with excellent properties and glacier cooker test resistance. Giving brings good.
また、前記の硬化性樹脂組成物に、ナイロン、ポリエス
テル、ポリビニルブチラール、カルメキシル基含有ツタ
ジエンニトリルゴム等の樹脂を配合し、必要に応じて充
填材を加えることにょ）、耐熱性接着剤を得ることがで
きる。In addition, a heat-resistant adhesive is obtained by blending a resin such as nylon, polyester, polyvinyl butyral, or carmexyl group-containing tutadiene nitrile rubber with the above-mentioned curable resin composition, and adding a filler if necessary. be able to.
さらに、前記の硬化性樹脂組成物に充填材を加え、加熱
ロールで混練し、冷却後粉砕機で分砕し、篩で分級して
耐熱性粉体塗料を調製することができる。Furthermore, a heat-resistant powder coating can be prepared by adding a filler to the curable resin composition, kneading it with heated rolls, cooling it, crushing it with a crusher, and classifying it with a sieve.
実験例をあげてさらに詳述する。This will be explained in further detail by giving an experimental example.
多価フェノール合成例１
還流冷却器、攪拌器、温度計、還流冷却水分離器を備え
た反ろ器に、ビスフェノール人（すなわチ４，４’−シ
ヒド四キシジフェニルプロノヤン）２２８０Ｊ（１０モ
ル）と、サリチルアルデヒド９７６１（８モル）を混合
し、さらに溶剤としてメチルイソブチルケトン２０００
Ｊ、触媒としてｐ−）シアンスルホン酸１５．Ｐを加え
、内容物を攪拌しながら、激しい発熱を起さないように
徐々Ｋ１００℃まで昇温した。その後、さらに昇温をつ
づけ、生成する水をメチルイソブチルケトンとφ共沸さ
せて、還流冷却水分離機を用いて系外に分離した。Polyhydric Phenol Synthesis Example 1 In a condenser equipped with a reflux condenser, a stirrer, a thermometer, and a reflux cooling water separator, 2280 J (10 mol) and salicylaldehyde 9761 (8 mol), and then added methyl isobutyl ketone 2000 mol as a solvent.
J, p-)cyansulfonic acid as catalyst15. P was added, and while stirring the contents, the temperature was gradually raised to K100°C so as not to cause severe heat generation. Thereafter, the temperature was further increased, and the produced water was azeotroped with methyl isobutyl ketone, and was separated from the system using a reflux cooling water separator.
系内を約１１８℃に上げ６時間反応させた。The temperature inside the system was raised to about 118°C, and the reaction was carried out for 6 hours.
反応終了後、温度を７００まで下げ、メチルイソブチル
ケトン１００ＯＦを加え、さらに水６０００Ｉを加えた
のち、苛性ソーダを加えてｐ−トルエンスルホン酸を中
和し、攪拌後装置して有機層を分離し、さらにその有機
層を６０００９の水で２回洗浄した。次いで、加熱して
溶剤を留去し、さらに５−Ｈｐの減圧下で１９０℃まで
昇温して水及び溶剤を除き、多価フェノール２８００＃
を得た。After the reaction was completed, the temperature was lowered to 700℃, 100OF of methyl isobutyl ketone was added, and 6000I of water was added, and then caustic soda was added to neutralize p-toluenesulfonic acid, and after stirring, the organic layer was separated by apparatus. Furthermore, the organic layer was washed twice with 60009 water. Next, the solvent was distilled off by heating, and the temperature was further raised to 190°C under a reduced pressure of 5-Hp to remove water and solvent, and polyhydric phenol 2800 #
I got it.
この多価フェノールは、顕微鏡による軟化点（以下、単
に「軟化点」という）が９９℃であった。This polyhydric phenol had a softening point (hereinafter simply referred to as "softening point") of 99° C. under a microscope.
多価フェノール合成例２
サリチルアルデヒドの代シに、ｐ−ヒドロキシベンズア
ルデヒド９７６ＪＦ（８モル）を用い、そのほかは合成
例１と同様にして多価フェノール３０４５１１を得た。Polyhydric Phenol Synthesis Example 2 Polyhydric phenol 304511 was obtained in the same manner as Synthesis Example 1 except that p-hydroxybenzaldehyde 976JF (8 mol) was used in place of salicylaldehyde.
この多価フェノールの軟化点は１０４℃であった。The softening point of this polyhydric phenol was 104°C.
多価フェノール合成例３
サリチルアルデヒドの代シに、バニリン１２１６Ｊ（８
モル）を用い、そのほかは合成例１と同様にして多価フ
ェノール３０２０Ｆを得た。この多価フェノールの軟化
点は１０７℃であった。Polyhydric phenol synthesis example 3 In place of salicylaldehyde, vanillin 1216J (8
Polyhydric phenol 3020F was obtained in the same manner as in Synthesis Example 1 except that mol) was used. The softening point of this polyhydric phenol was 107°C.
多価フェノール合成例４
ビスフェノール人の代りに、４．４’−ジヒドロキシジ
フェニルエーテル２０２０°＃（１０モル）ヲ用い、そ
のほかは合成例１と同様にして多価フェノール２５７Ｏ
Ｎを得た。この多価フェノールの軟化点は１１０℃で６
っ九。Polyhydric phenol synthesis example 4 Polyhydric phenol 257O was prepared in the same manner as in synthesis example 1 except that 4,4'-dihydroxydiphenyl ether 2020°# (10 mol) was used instead of the bisphenol.
I got N. The softening point of this polyhydric phenol is 6 at 110℃.
Nine.
多価フェノール合成例５
ビスフェノールＡの代シに、３．３’−ツメチル−４，
４′−ジヒドロキシジフェニルプロパン２０５０Ｆ（１
０モル）を用い、そのほかは合成例１と同様にして多価
フェノール３３９０．Ｆを得た。この多価フェノールの
軟化点は８５℃であった。Polyhydric phenol synthesis example 5 In place of bisphenol A, 3,3'-trimethyl-4,
4'-dihydroxydiphenylpropane 2050F (1
Polyhydric phenol 3390.0 mol) was used in the same manner as in Synthesis Example 1. I got an F. The softening point of this polyhydric phenol was 85°C.
多価フェノール合成例６
ビスフェノールＡの代シに、４．４’−ジヒドロキシジ
フェニルメタンｚｏｏｏｙ（ｉｏモル）を用い、またサ
リチルアルデヒドの代シにｐ−ヒドロキシベンズアルデ
ヒド９７６＃（８モル）ｔ−用い、そのほかは合成例１
と同様にして多価フェノール２５５ＯＮを得た。この多
価フェノールの軟化点は９４℃でありた。Polyhydric phenol synthesis example 6 4,4'-dihydroxydiphenylmethane zoooy (io mol) was used as a substitute for bisphenol A, and p-hydroxybenzaldehyde 976# (8 mol) was used as a substitute for salicylaldehyde, etc. is synthesis example 1
Polyhydric phenol 255ON was obtained in the same manner as above. The softening point of this polyhydric phenol was 94°C.
多価フェノール合成例７
ビスフエノール人の代シに、３．３’−ジヒドロキシビ
フェニル１８６ ＯＮ、（１０モル）を用い、そのほか
は合成例１と同様にして多価フェノール２４２０１を得
た。この多価フェノールの軟化点は１１４℃でありた。Polyhydric Phenol Synthesis Example 7 Polyhydric phenol 24201 was obtained in the same manner as in Synthesis Example 1 except that 3,3'-dihydroxybiphenyl 186 ON (10 mol) was used as the bisphenol substitute. The softening point of this polyhydric phenol was 114°C.
多価フェノール合成例８
この例は、比較例１のエポキシ樹脂製造原料の多価フェ
ノールを製造した例である。Polyhydric Phenol Synthesis Example 8 This example is an example in which polyhydric phenol, which is a raw material for producing an epoxy resin in Comparative Example 1, was produced.
還流冷却器、攪拌器、温度計及び滴下Ｐ斗を備えた反応
器内に、フェノール１５０４＃（１６モル）と、サリチ
ルアルデヒド２４４１１（２モル）を加え、内容物を攪
拌しながら８０℃に加温した。Phenol 1504# (16 mol) and salicylaldehyde 24411 (2 mol) were added to a reactor equipped with a reflux condenser, stirrer, thermometer, and dropping port, and the contents were heated to 80°C with stirring. It was warm.
滴下ロートから濃塩酸２６Ｉを徐々に滴下し、激しい発
熱を起さないようにコントロールしなから１００’Ｃま
で昇温し、１００℃で３時間反応させた。26I of concentrated hydrochloric acid was gradually added dropwise from the dropping funnel, and the temperature was raised to 100'C while controlling so as not to cause intense heat generation, and the mixture was allowed to react at 100°C for 3 hours.
次いで、還流冷却器を冷却分離器に取り替えて、系内を
１５０℃まで昇温し、さらに５ ｍＨＪの減圧下で１９
０℃まで加熱して、塩醒、水、未反応フェノールを留去
し、多価フェノール５５２ｇを得た。この多価フェノー
ルの軟化点は９８℃であった。Next, the reflux condenser was replaced with a cooling separator, the temperature of the system was raised to 150 °C, and the temperature was further increased to 19 °C under a reduced pressure of 5 mHJ.
The mixture was heated to 0° C. to remove salt, water, and unreacted phenol, and 552 g of polyhydric phenol was obtained. The softening point of this polyhydric phenol was 98°C.
実施例１
攪拌装置、還流冷却器を備えた反応器内に、合成例１で
得られた多価フェノールＩＩＩＪ’、エピクロルヒドリ
ン９２５１．テトラメチルアンモニウムクロリド１９を
仕込み、加熱還流下（１１７℃）で２時間付加反応させ
た０次いで、内容物を６０℃に冷却し、水分除去装置を
取付けて水酸化ナトリウム４２Ｉｉｔ加え、反応温度５
５〜６０℃、減圧度１００〜１５０ ｍＨｊｌで、生成
する水を連続的に共沸除去しなから閉環反応を行なわせ
た。生成水が１８１７に達した時点で反応終了点とした
。Example 1 In a reactor equipped with a stirring device and a reflux condenser, polyhydric phenol IIIJ' obtained in Synthesis Example 1 and epichlorohydrin 9251. Tetramethylammonium chloride 19 was charged and the addition reaction was carried out for 2 hours under heating and reflux (117°C).Next, the contents were cooled to 60°C, a water removal device was attached, 42 Iit of sodium hydroxide was added, and the reaction temperature was 5.
The ring-closing reaction was carried out at a temperature of 5 to 60° C. and a reduced pressure of 100 to 150 mHjl, while the produced water was continuously removed azeotropically. The reaction was terminated when the amount of produced water reached 1817.
反応性成物をｒ過して食塩を除去したのち、水洗してさ
らに食塩を除去してから、減圧蒸留して残存エピク四ル
ヒドリンを回収した。得られた工Ｉキシ樹脂は、エポキ
シ当量が２０１であシ、軟化点が４８℃であり九。The reactive product was filtered to remove salt, washed with water to further remove salt, and then distilled under reduced pressure to recover residual epictetrahydrin. The obtained epoxy resin had an epoxy equivalent of 201 and a softening point of 48°C.
実施例２〜７
比較例１
合成例１で得られた多価フェノールの代りに、表１に示
すように合成例２〜８で得られた各多価７８ノールをそ
れぞれ使用し、そのほかは実施例１と同様くして各エポ
キシ樹脂を製造した。Examples 2 to 7 Comparative Example 1 In place of the polyhydric phenol obtained in Synthesis Example 1, each polyhydric 78nol obtained in Synthesis Examples 2 to 8 was used as shown in Table 1, and the other cases were as follows. Each epoxy resin was produced in the same manner as in Example 1.
得られた各エポキシ樹脂のエポキシ当量及び軟化点は、
表１にそれぞれ示すとおシであった。The epoxy equivalent and softening point of each epoxy resin obtained are:
The results are shown in Table 1.
表
実験例１〜９
表２に示すように、実施例１〜７、比較例１で得られた
各エポキシ樹脂、及びフェノールツメラックエポキシ樹
脂の市販品エピコート１５４（油化シェルポキシ株式会
社商品名）に、硬化剤としてジアミノジフェニルスルホ
ンを表２に示す割合でそれぞれ配合し、１８０℃で溶融
混合したのち、充分に脱泡し、金盟内に注臘して、１８
０℃で１時間加熱して硬化させ、さらに２４０℃で４時
間後硬化させた。Table Experimental Examples 1 to 9 As shown in Table 2, the epoxy resins obtained in Examples 1 to 7 and Comparative Example 1, and the commercially available phenolic tumerac epoxy resin Epicoat 154 (trade name of Yuka Shellpoxy Co., Ltd.) and diaminodiphenylsulfone as a curing agent in the proportions shown in Table 2, melted and mixed at 180°C, thoroughly degassed, poured into a metal container, and heated to 180°C.
It was cured by heating at 0°C for 1 hour, and was further post-cured at 240°C for 4 hours.
得られた各硬化樹脂の物性を測定した結果は表２に示す
とおシであった。The physical properties of each cured resin obtained were measured and the results are shown in Table 2.
以下
表２の注：
＊ｌ・・・ＴＭＡ Ｋよシ線膨張を測定し、その変極点
より Ｔｇを求めた。Notes to Table 2 below: *l...TMA K linear expansion was measured, and Tg was determined from its inflection point.
＊２・・・ＪＩＳＫ−６９１１による。*2: According to JISK-6911.
本３・・・油化シェルエポキシ株式会社商品名、フェノ
ールツメラック樹脂、ニーキシ当量８０
表２の結果から明らかなように、各実施例のエポキシ樹
脂を用いた硬化物は、比較例１やフェノールノ？ラック
エポキシ樹脂を用いた硬化物と較べて、７！／クス転移
点が著しく高く、常温及び２００℃の曲げ強度が著しく
大で、かつ吸水後の曲げ強度も著しく大である。Book 3...Product name of Yuka Shell Epoxy Co., Ltd., Phenol Tumelac resin, Niexy equivalent: 80 As is clear from the results in Table 2, the cured products using the epoxy resins of each Example were different from those of Comparative Example 1 and of? Compared to a cured product using lac epoxy resin, 7! /Cu transition point is extremely high, the bending strength at room temperature and 200°C is extremely high, and the bending strength after water absorption is also extremely high.
実験例１０〜１８
実施例１〜７で得られた各エポキシ樹脂、比較例１で得
られたエポキシ樹脂、又は市販の０−クレゾールノＩラ
ック樹脂（エピニー） １８０．エポキシ当量２１０）
をそれぞれ用い、これらに、臭素化フェノールノゲラッ
クエポキシ樹脂（日本化某社商品名プレン、エポキシ当
量２８５）、硬化剤としてフェノールノゲラック樹脂（
荒用化学社商品名タマノール７５２、水酸基当量１０４
）、硬化促進剤としてトリフェニルホスフィン、可撓性
付与剤としてジメチルジメトキシシランとγ−グリシド
キシグロビルトリメトキシシランを縮合して得られたシ
リコン樹脂、溶融シリカ、シランカップリング剤（日本
ユニカー社商品名ＮＵＣシリコーンＡ−１８６）、離型
剤としてカルナバワックス、難燃性付与剤として三酸化
アン゛チモンを、それぞれ表３に示す割合で配合し、二
本ロールを用いて７０〜１１０℃で混練したのち冷却し
て粉砕し、タブレフトマシーンでタブレットに加圧成形
し、成形材料を得た。Experimental Examples 10 to 18 Each epoxy resin obtained in Examples 1 to 7, the epoxy resin obtained in Comparative Example 1, or commercially available 0-cresol no Ilac resin (Epiny) 180. Epoxy equivalent 210)
In addition to these, brominated phenol nogelac epoxy resin (trade name: Prene, epoxy equivalent: 285, manufactured by Nippon Kaisha) and phenol nogelac resin (as a curing agent) were used.
Arayo Kagakusha trade name: Tamanol 752, hydroxyl equivalent: 104
), triphenylphosphine as a curing accelerator, silicone resin obtained by condensing dimethyldimethoxysilane and γ-glycidoxyglobyltrimethoxysilane as a flexibility imparting agent, fused silica, and a silane coupling agent (Nippon Unicar Co., Ltd.) Product name NUC Silicone A-186), carnauba wax as a mold release agent, and antimony trioxide as a flame retardant agent were blended in the proportions shown in Table 3, and heated at 70 to 110°C using two rolls. After kneading, the mixture was cooled, crushed, and pressure-molded into tablets using a tablet left machine to obtain a molding material.
得られた各成形材料を、トランスファー成形機を用いて
１８０℃、圧カフ０ｋｇ／Ｊで３分間成形したのち、１
８０℃で６時間ポストキエアさせた。Each of the obtained molding materials was molded for 3 minutes at 180°C using a transfer molding machine with a pressure cuff of 0 kg/J, and then
Post-quenching was performed at 80°C for 6 hours.
その硬化物のガラス転移温度、曲げ強度、曲げ弾性率、
線膨張係数は表３に示すとおシであった。The glass transition temperature, bending strength, bending modulus of the cured product,
The coefficient of linear expansion was as shown in Table 3.
また、上記の各成形材料を、用い、８ ｗ Ｘ ８ ｍ
のダイメンディングプレート上に素子を置き、１４ｗｍ
Ｘ ２０ ｗｓ Ｘ ２．２５ ｗｍの大きさの８０
ピンＱｕａｄフラツトノ譬ツケージの成形を行なった。In addition, using each of the above molding materials, 8 w x 8 m
Place the element on the diemending plate of 14 wm.
x 20 ws x 2.25 wm size 80
A pin Quad flat cage was molded.
成形したパッケージを８５℃、８５１ＲＨの条件下で７
２時間吸湿させたのち、２１５℃のべ一ノ平−フエース
ハンダ処理を９０秒行ない、クラックの有無を調べた結
果は表３に示すとおシであった。The molded package was heated at 85℃ and 851RH for 7 days.
After absorbing moisture for 2 hours, it was subjected to flat-face soldering at 215° C. for 90 seconds, and the presence or absence of cracks was examined. The results are shown in Table 3.
さらに、同様に６．４ ｗｍ Ｘ ６．４ ｗｉ、のダ
イメンディンググレート上に半導体素子を置き、フラッ
ト・母ッケージを成形し、同様の吸湿処理後に２６０℃
のハンダ浴で１０秒間浸漬処理し、り２ツクの発生を調
べた結果は表３に示すとおシであった。Furthermore, the semiconductor device was similarly placed on a 6.4 wm x 6.4 wi die-mending grate, a flat mother package was formed, and after the same moisture absorption treatment, it was heated at 260°C.
The results were shown in Table 3.
以下余白
表３の注：
＊１・・・油化シェルエポキシ株式会社商品名、０−ク
レゾールノボラックエポキシ樹脂、エポキシ当量２１０
本２・・・日本化某社商品名プレン、エポキシ当量８５
＊３・・・荒用化学社商品名タマノール７５２、水酸基
当量１０４
＄４・・・ジメチルジメトキシシランとγ−グリシドキ
シプロビルトリメトキシシ２ンの縮合によって得られた
シリコン樹脂
本５・・・８本二二、’７−社商品名ＮＵＣシリコーン
Ａ−８６
＊６・・・評価は下記のとお〕である。Notes to the following margin table 3: *1...Product name of Yuka Shell Epoxy Co., Ltd., 0-cresol novolac epoxy resin, epoxy equivalent: 210 2...Product name of Nippon Ka Co., Ltd., Prene, epoxy equivalent: 85 *3...・Arayo Chemical Co., Ltd. trade name: Tamanol 752, hydroxyl equivalent: 104 $4...Silicon resin obtained by condensation of dimethyldimethoxysilane and γ-glycidoxypropyltrimethoxysilane 2...8 bottles 2 2. '7-Company product name: NUC Silicone A-86 *6...Evaluation is as follows].
０・・・合格
×・・・不合格
表３の結果から明らかなように、各実施例のエポキシ樹
脂の硬化物は、比較例１のエポキシ樹脂やＯ−クレゾー
ルツメラックエポキシ樹脂の硬化物と較べて、ガラス転
移点が高く耐熱性に優れ、また機械的強度が大で、かつ
吸湿性が少なくて、成形ノ譬ツケージの吸湿後のハンダ
処理においてもクラックの発生が少いから、トランジス
タやＩＣなどの電子部品、特に耐熱性の要求される部品
の封止用に適する。0...Pass x...Fail As is clear from the results in Table 3, the cured products of the epoxy resins of each example were different from the cured products of the epoxy resin of Comparative Example 1 and the O-cresol Tumerac epoxy resin. In comparison, it has a high glass transition point, excellent heat resistance, high mechanical strength, and low moisture absorption, and less cracks occur during soldering after moisture absorption in molding cages. Suitable for sealing electronic components such as ICs, especially components that require heat resistance.
実験例１９及び２０
実施例１で得られたエポキシ樹脂、又は比較例１で得ら
れたエポキシ樹脂を用い、かつ表４に示す配合を用いて
エポキシ樹脂ワニスを調製した。Experimental Examples 19 and 20 Epoxy resin varnishes were prepared using the epoxy resin obtained in Example 1 or the epoxy resin obtained in Comparative Example 1 and using the formulations shown in Table 4.
得られた各ワニスを、シラン処理した厚さ０．１８繻の
平織ガラス布に含浸させ、１４０℃で５分間加熱してＢ
−ステージ状態のプリプレグを製造した。このプリプレ
グ８枚とその両面に厚さ３５μの鋼箔を重ねて、１７５
℃で６０分間、４０ゆ／ｅｓ”の加熱加圧下で成形し、
さらに２００℃で１時間加熱し、板厚１．６−の銅張積
層板を得た。その特性は表４に示すとおシであった。Each of the obtained varnishes was impregnated into a silane-treated plain-woven glass cloth with a thickness of 0.18, and heated at 140°C for 5 minutes to obtain B.
- A prepreg in a stage state was produced. 8 sheets of prepreg and steel foil with a thickness of 35 μm are layered on both sides, and 175
℃ for 60 minutes under heat and pressure of 40 Yu/es",
It was further heated at 200° C. for 1 hour to obtain a copper-clad laminate with a thickness of 1.6 mm. Its properties are shown in Table 4.
表
表４の注：
＊１・・・油化シェルエポキシ株式会社商品名エピコー
ト１０４５、エポキシ当量４５０
＊２・・・荒用化学社商品名タマノール７５２、水酸基
当量１０４
本３・・・ＪＩ８Ｃ−６４８１のはんだ耐熱性に準じた
試験方法を用い、ふくれ、はがれ等が発生しない時間を
測定した。Notes to Table 4: *1... Yuka Shell Epoxy Co., Ltd. trade name Epicote 1045, epoxy equivalent 450 *2... Aurayo Kagakusha trade name Tamanol 752, hydroxyl equivalent 104 Book 3... JI8C-6481 Using a test method similar to that of solder heat resistance, the time required for no blistering, peeling, etc. to occur was measured.
表４から明らかなように実施例１のニーキシ樹脂を用い
た鋼張積層板は、比較例１のエポキシ樹脂を用いたもの
と較べて、耐熱性、曲げ強度及び耐水性に優れている。As is clear from Table 4, the steel clad laminate using the Nixi resin of Example 1 is superior in heat resistance, bending strength, and water resistance compared to the steel clad laminate using the epoxy resin of Comparative Example 1.
（＋り発明の効果
本発明のエポキシ樹脂は、耐熱性、機械強度及び耐水性
に著しく優れた硬化物を与える。(+Effects of the Invention The epoxy resin of the present invention provides a cured product with extremely excellent heat resistance, mechanical strength, and water resistance.
Claims (2)
あります▼、▲数式、化学式、表等があります▼、炭素
数１〜９のアルキレン基、又は直接結合を示し、Ｒ′は
炭素数１〜９のアルキル基又はハロゲン原子を示し、各
Ｒ′は互いに同一であっても異なっていてもよく、ｐ及
びｑはそれぞれ０、１又は２を示す。） で表わされるフェノール類の少なくとも１種と、一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＾２は水素原子、メトキシ基、炭素数１〜９
のアルキル基、ハロゲン原子、又はニトロ基を示す。） で表わされるヒドロキシ芳香族アルデヒド類の少なくと
も１種との縮合物である多価フェノール類をエピハロヒ
ドリンと反応させなるエポキシ樹脂。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is -O-, -S-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. , represents an alkylene group having 1 to 9 carbon atoms, or a direct bond, R' represents an alkyl group having 1 to 9 carbon atoms or a halogen atom, each R' may be the same or different from each other, p and q represent 0, 1, or 2, respectively.) At least one type of phenol represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^2 is a hydrogen atom, a methoxy group, Carbon number 1-9
represents an alkyl group, a halogen atom, or a nitro group. ) An epoxy resin obtained by reacting a polyhydric phenol, which is a condensation product with at least one hydroxy aromatic aldehyde represented by the following formula, with epihalohydrin.
あります▼、▲数式、化学式、表等があります▼、炭素
数１〜９のアルキレン基、又は直接結合を示し、Ｒ′は
炭素数１〜９のアルキル基又はハロゲン原子を示し、各
Ｒ′は互いに同一であっても異なっていてもよく、ｐ及
びｑはそれぞれ０、１又は２を示す。） で表わされるフェノール類の少なくとも１種と、一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＾２は水素原子、メトキシ基、炭素数１〜９
のアルキル基、ハロゲン原子、又はニトロ基を示す。） で表わされるヒドロキシ芳香族アルデヒド類の少なくと
も１種とを縮合反応させて多価フェノール類とし、得ら
れた多価フェノール類とエピハロヒドリンとをアルカリ
金属水酸化物の存在下で反応させることを特徴とするエ
ポキシ樹脂の製造法。(2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is -O-, -S-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. , represents an alkylene group having 1 to 9 carbon atoms, or a direct bond, R' represents an alkyl group having 1 to 9 carbon atoms or a halogen atom, each R' may be the same or different from each other, p and q represent 0, 1, or 2, respectively.) At least one type of phenol represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^2 is a hydrogen atom, a methoxy group, Carbon number 1-9
represents an alkyl group, a halogen atom, or a nitro group. ) is subjected to a condensation reaction with at least one type of hydroxy aromatic aldehyde represented by the formula to form a polyhydric phenol, and the resulting polyhydric phenol and epihalohydrin are reacted in the presence of an alkali metal hydroxide. A method for producing epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18377489A JPH0350229A (en) | 1989-07-18 | 1989-07-18 | Epoxy resin and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18377489A JPH0350229A (en) | 1989-07-18 | 1989-07-18 | Epoxy resin and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0350229A true JPH0350229A (en) | 1991-03-04 |
Family
ID=16141716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18377489A Pending JPH0350229A (en) | 1989-07-18 | 1989-07-18 | Epoxy resin and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0350229A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259662A (en) * | 1995-03-27 | 1996-10-08 | Nippon Kayaku Co Ltd | Production of epoxy resin |
-
1989
- 1989-07-18 JP JP18377489A patent/JPH0350229A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259662A (en) * | 1995-03-27 | 1996-10-08 | Nippon Kayaku Co Ltd | Production of epoxy resin |
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