JP2022093044A - Polyhydric hydroxy resin, epoxy resin, production methods of them, and epoxy resin composition and cured product that employ them - Google Patents
Polyhydric hydroxy resin, epoxy resin, production methods of them, and epoxy resin composition and cured product that employ them Download PDFInfo
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- JP2022093044A JP2022093044A JP2020206111A JP2020206111A JP2022093044A JP 2022093044 A JP2022093044 A JP 2022093044A JP 2020206111 A JP2020206111 A JP 2020206111A JP 2020206111 A JP2020206111 A JP 2020206111A JP 2022093044 A JP2022093044 A JP 2022093044A
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- Prior art keywords
- epoxy resin
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- group
- resin
- general formula
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 69
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 69
- 229920005989 resin Polymers 0.000 title claims abstract description 68
- 239000011347 resin Substances 0.000 title claims abstract description 68
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 aromatic fluorine compound Chemical class 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 6
- 238000005266 casting Methods 0.000 abstract description 3
- 238000003475 lamination Methods 0.000 abstract description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 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 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 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 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 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 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 description 5
- 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
- 229930185605 Bisphenol Natural products 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 235000011181 potassium carbonates Nutrition 0.000 description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 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
- 239000002244 precipitate Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 229960001755 resorcinol Drugs 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000008065 acid anhydrides Chemical class 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 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 3
- 239000000155 melt Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 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
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 101001059734 Thermococcus litoralis (strain ATCC 51850 / DSM 5473 / JCM 8560 / NS-C) Trehalose/maltose-binding protein MalE Proteins 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates 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
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000004023 quaternary phosphonium compounds Chemical group 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- SNMWBQJABJVKSR-UHFFFAOYSA-N (2,6-dichlorophenyl)-(2-methylimidazol-1-yl)methanone Chemical compound CC1=NC=CN1C(=O)C1=C(Cl)C=CC=C1Cl SNMWBQJABJVKSR-UHFFFAOYSA-N 0.000 description 1
- QLRYDIRQUQZTKB-UHFFFAOYSA-N (2-ethylimidazol-1-yl)-(2,4,6-trimethylphenyl)methanone Chemical compound CCC1=NC=CN1C(=O)C1=C(C)C=C(C)C=C1C QLRYDIRQUQZTKB-UHFFFAOYSA-N 0.000 description 1
- VMJMWKXIBQKPPO-UHFFFAOYSA-N (2-methylimidazol-1-yl)-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=NC=CN1C(=O)C1=C(C)C=C(C)C=C1C VMJMWKXIBQKPPO-UHFFFAOYSA-N 0.000 description 1
- MGNFFUHBTQWOSG-UHFFFAOYSA-N (2-phenylimidazol-1-yl)-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)N1C(C=2C=CC=CC=2)=NC=C1 MGNFFUHBTQWOSG-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-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
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-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
- 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 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
- 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
- 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
- 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 description 1
- JWLJBISFJGEYMT-UHFFFAOYSA-M benzyl(triethyl)azanium;iodide Chemical compound [I-].CC[N+](CC)(CC)CC1=CC=CC=C1 JWLJBISFJGEYMT-UHFFFAOYSA-M 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- LRRJQNMXIDXNIM-UHFFFAOYSA-M benzyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CC1=CC=CC=C1 LRRJQNMXIDXNIM-UHFFFAOYSA-M 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- HZZUMXSLPJFMCB-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;acetate Chemical class CC([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 HZZUMXSLPJFMCB-UHFFFAOYSA-M 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 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
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- SRLHDBRENZFCIN-UHFFFAOYSA-N n,n-di(butan-2-yl)butan-2-amine Chemical compound CCC(C)N(C(C)CC)C(C)CC SRLHDBRENZFCIN-UHFFFAOYSA-N 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical group O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
- TWWBIMNLBUYJKB-UHFFFAOYSA-N phosphanyl acetate Chemical group CC(=O)OP TWWBIMNLBUYJKB-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- NJFUXFRJVIXVSG-UHFFFAOYSA-M tetramethylphosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C NJFUXFRJVIXVSG-UHFFFAOYSA-M 0.000 description 1
- CRUVUWATNULHFA-UHFFFAOYSA-M tetramethylphosphanium;hydroxide Chemical compound [OH-].C[P+](C)(C)C CRUVUWATNULHFA-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
Description
本発明は、低誘電性に優れるとともに、高熱伝導性、耐湿性、耐熱性等にも優れた硬化物を与えるエポキシ樹脂、その中間体、硬化剤及びそれらを用いたエポキシ樹脂組成物並びにその硬化物に関するものであり、プリント配線板、半導体封止等の電気電子分野の絶縁材料等に好適に使用される。 INDUSTRIAL APPLICABILITY The present invention provides an epoxy resin, an intermediate thereof, a curing agent, an epoxy resin composition using them, and curing thereof, which provide a cured product having excellent low dielectric constant, high thermal conductivity, moisture resistance, heat resistance, and the like. It relates to a thing, and is suitably used for an insulating material in the electric and electronic fields such as a printed wiring board and a semiconductor encapsulation.
近年、特に先端材料分野の進歩にともない、より高性能なベース樹脂の開発が求められている。例えば、半導体封止の分野においては、近年の高密度実装化に対応したパッケージの薄形化、大面積化、更には表面実装方式の普及により、パッケージクラックの問題が深刻化しており、これらのベース樹脂としては、耐湿性、耐熱性、金属基材との接着性等の向上が強く求められている。最近では、パワーデバイス分野を中心とした耐熱性および放熱性向上の観点から熱分解安定性や熱伝導率の高い材料が必要とされることに加えて、高速通信の観点からは誘電特性に優れた材料が要求されている。 In recent years, there has been a demand for the development of higher performance base resins, especially with the progress in the field of advanced materials. For example, in the field of semiconductor encapsulation, the problem of package cracks has become more serious due to the thinning and large area of packages corresponding to the recent high-density mounting, and the widespread use of surface mounting methods. As the base resin, improvement in moisture resistance, heat resistance, adhesiveness to a metal base material, and the like is strongly required. Recently, materials with high thermal decomposition stability and thermal conductivity are required from the viewpoint of improving heat resistance and heat dissipation mainly in the field of power devices, and in addition, they have excellent dielectric properties from the viewpoint of high-speed communication. Materials are required.
しかしながら、従来より知られているエポキシ樹脂には、これらの要求を満足するものは未だ知られていない。例えば、周知のビスフェノール型エポキシ樹脂は、常温で液状であり、作業性に優れていることや、硬化剤、添加剤等との混合が容易であることから広く使用されているが、耐熱性、耐湿性の点で問題がある。また、耐熱性を改良したものとして、フェノールノボラック型エポキシ樹脂が知られているが、耐湿性や耐衝撃性に問題がある。また、特許文献１には耐湿性、耐衝撃性の向上を目的に、フェノールアラルキル樹脂のエポキシ化合物が提案されているが、耐熱性や難燃性の点で十分でない。
However, none of the conventionally known epoxy resins satisfy these requirements is yet known. For example, the well-known bisphenol type epoxy resin is widely used because it is liquid at room temperature, has excellent workability, and can be easily mixed with a curing agent, an additive, etc., but has heat resistance. There is a problem in terms of moisture resistance. Further, a phenol novolac type epoxy resin is known as one having improved heat resistance, but there is a problem in moisture resistance and impact resistance. Further,
特許文献２には、ビフェニル構造を有するアラルキル型エポキシ樹脂を半導体封止材料に応用した例が提案されているが、耐熱性の点で十分ではない。特許文献３、特許文献４及び特許文献５には、剛直なメソゲン基を有する液晶性のエポキシ樹脂及びそれを用いたエポキシ樹脂組成物が提案されているが、成形性に課題があるとともに、十分な熱伝導率向上効果は得られていなかった。
Patent Document 2 proposes an example in which an aralkyl type epoxy resin having a biphenyl structure is applied to a semiconductor encapsulating material, but it is not sufficient in terms of heat resistance. Patent Document 3, Patent Document 4, and
特許文献６には、種々のフッ素原子を有するエポキシ樹脂が開示されているが、電気絶縁材料用としては耐熱性、熱伝導性等の面で十分なものはなかった。非特許文献１には、フッ素原子を持つ芳香族エーテル構造の高分子が示されているが、高分子量体の開示にとどまり、オリゴマーやそれを用いたエポキシ樹脂に関わるものではない。
Patent Document 6 discloses an epoxy resin having various fluorine atoms, but none of them is sufficient in terms of heat resistance, thermal conductivity, etc. for an electrically insulating material. Non-Patent
従って、本発明の目的は、成形性に優れるとともに、耐熱性、高熱伝導性、低誘電性等にも優れた硬化物を得ることができ、積層、成形、注型、接着等の用途に有用な多価ヒドロキシ樹脂及びそのエポキシ樹脂、更にはそれらの製造方法並びにそれらを用いたエポキシ樹脂組成物、更にはその硬化物を提供することにある。 Therefore, it is an object of the present invention that a cured product having excellent moldability and excellent heat resistance, high thermal conductivity, low dielectric property, etc. can be obtained, which is useful for applications such as lamination, molding, casting, and adhesion. It is an object of the present invention to provide a polyvalent hydroxy resin and an epoxy resin thereof, a method for producing the same, an epoxy resin composition using the same, and a cured product thereof.
すなわち、本発明は下記一般式（１）で表される新規多価ヒドロキシ樹脂である。
（但し、Ａは独立に二価の芳香族基を示す。ｎは１～１０の繰返し数、ｍは０～１の数を示し、ｐ、ｑ、ｘおよびｙは独立に０～４の置換数を示す。ｘ、ｙのいずれかは０ではない。）
That is, the present invention is a novel polyvalent hydroxy resin represented by the following general formula (1).
(However, A independently indicates a divalent aromatic group. N indicates a number of repetitions of 1 to 10, m indicates a number of 0 to 1, and p, q, x and y independently substitute 0 to 4. Indicates a number. Either x or y is not 0.)
また、本発明は、芳香族ジヒドロキシ化合物１モルに対して、芳香族フッ素化合物０．１～０．９モルを反応させることを特徴とする上記一般式（１）の多価ヒドロキシ樹脂の製造方法である。 Further, the present invention is a method for producing a polyvalent hydroxy resin according to the above general formula (1), which comprises reacting 1 mol of an aromatic dihydroxy compound with 0.1 to 0.9 mol of an aromatic fluorine compound. Is.
更に、本発明は、下記一般式（３）で表される新規エポキシ樹脂である。
（但し、Ａは独立に二価の芳香族基、Ｇはグリシジル基を示す。Ａ、ｎは１～１０の繰返し数、ｍは０～１の数を示し、ｐ、ｑ、ｘおよびｙは独立に０～４の置換数を示す。ｘ、ｙのいずれかは０ではない。）
Further, the present invention is a novel epoxy resin represented by the following general formula (3).
(However, A independently indicates a divalent aromatic group, G indicates a glycidyl group. A and n indicate the number of repetitions of 1 to 10, m indicates the number of 0 to 1, and p, q, x and y are. Independently indicates the number of substitutions from 0 to 4. Either x or y is not 0.)
さらに、本発明は上記一般式（１）で表される多価ヒドロキシ樹脂をエピクロルヒドリンと反応させることを特徴とする上記一般式（３）で表される新規エポキシ樹脂の製造方法である。 Further, the present invention is a method for producing a novel epoxy resin represented by the general formula (3), which comprises reacting a polyvalent hydroxy resin represented by the general formula (1) with epichlorohydrin.
さらにまた、本発明は上記のエポキシ樹脂又は多価ヒドロキシ樹脂の少なくともいずれか一方を、エポキシ樹脂成分又は硬化剤成分の必須成分として配合してなるエポキシ樹脂組成物であり、また、このエポキシ樹脂組成物を硬化してなる硬化物である。 Furthermore, the present invention is an epoxy resin composition in which at least one of the above epoxy resin or polyvalent hydroxy resin is blended as an essential component of an epoxy resin component or a curing agent component, and the epoxy resin composition. It is a cured product made by curing an object.
本発明のエポキシ樹脂又は多価ヒドロキシ樹脂から得られるエポキシ樹脂組成物を硬化して得られる硬化物は、耐熱性、低誘電性および耐湿性に優れた性能を有し、積層、成形、注型、接着等の用途に好適に使用することができる。 The cured product obtained by curing the epoxy resin composition obtained from the epoxy resin or the polyvalent hydroxy resin of the present invention has excellent heat resistance, low dielectric property and moisture resistance, and is laminated, molded and cast. , Can be suitably used for applications such as adhesion.
以下、本発明を詳細に説明する。
本発明の多価ヒドロキシ樹脂は、上記一般式（１）で表される。
ここで、Ａは独立に二価の芳香族基を示す。二価の芳香族基としては、ベンゼン環、ナフタレン環、または下記式（２）、
（但しＸは単結合、酸素原子、硫黄原子、－ＳＯ２－、－ＣＯ－、－ＣＨ2－、－ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２－、－ＣＨ（φ）－、－Ｃφ（ＣＨ３）－、１，１－シクロアルカン基、９，９－フルオレニル基を示す。ここでφはフェニレン基を示す。Ｒ１、Ｒ２は、それぞれ独立して、水素原子、炭素数１～８のアルキル基、アリール基、アルコキシ基、アラルキル基又はハロゲン原子を示し、ｎは１～５０の数を示す。）
で表されるビスフェニレン基を挙げることができる。
好ましくは無置換もしくはメチル基で置換されたベンゼン環、ナフタレン環、またはビフェニル環である。
ｎは平均の繰り返し数を示し、１～５０であるが、好ましくは１～１０である。これより小さいとフッ素原子導入による低誘電性等の効果が小さく、これより大きいと粘度難くなり取扱性が低下する。
ｍは０～２の数を表すが、好ましくは０または１である。これより大きいと粘度が高くなり取扱性が低下する。
また、ｐ、ｑ、ｘおよびｙは独立に０～４の置換数を示す。ｘ、ｙのいずれかは０ではなく、好ましくはいずれも１以上、より好ましくは２～４である。望ましくはｐ＋ｘ＝４、ｑ＋ｙ＝４を満たすものであり、望ましいｐおよびｑは、独立に０または１である。
Hereinafter, the present invention will be described in detail.
The polyvalent hydroxy resin of the present invention is represented by the above general formula (1).
Here, A independently represents a divalent aromatic group. Examples of the divalent aromatic group include a benzene ring, a naphthalene ring, or the following formula (2).
(However, X is a single bond, oxygen atom, sulfur atom, -SO 2- , -CO-, -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -CH (φ)- , -Cφ (CH 3 )-, 1,1-cycloalkane group, 9,9-fluorenyl group. Where φ indicates a phenylene group. R 1 and R 2 are independent hydrogen atoms, respectively. It indicates an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom having 1 to 8 carbon atoms, and n indicates a number of 1 to 50 carbon atoms.)
The bisphenylene group represented by is mentioned.
It is preferably an unsubstituted or methyl group-substituted benzene ring, naphthalene ring, or biphenyl ring.
n indicates an average number of repetitions, which is 1 to 50, preferably 1 to 10. If it is smaller than this, the effect of low dielectric property due to the introduction of fluorine atoms is small, and if it is larger than this, the viscosity becomes difficult and the handleability deteriorates.
m represents a number from 0 to 2, but is preferably 0 or 1. If it is larger than this, the viscosity becomes high and the handleability is lowered.
Further, p, q, x and y independently indicate the number of substitutions from 0 to 4. Any of x and y is not 0, preferably 1 or more, and more preferably 2 to 4. Desirably, p + x = 4 and q + y = 4 are satisfied, and desirable p and q are 0 or 1 independently.
本発明の多価ヒドロキシ樹脂は、単一の化合物でもよいが、式（１）を満たす化合物の混合物であってもよく、この場合、ｐ＝ｑ＝０、ｘ＝ｙ＝４のものが５０ｗｔ％以上であることが望ましい。
ＧＰＣ分析によれば、好ましくは、未反応の芳香族ジヒドロキシ化合物を７０面積％以下、ｎ＝１体を１０～５０面積％、ｎ＝２体を１０～４０面積％、ｎ＝３体以上を５０面積％以下の分布にて含有する。
The polyvalent hydroxy resin of the present invention may be a single compound or a mixture of compounds satisfying the formula (1). In this case, the one having p = q = 0 and x = y = 4 is 50 wt. It is desirable that it is% or more.
According to GPC analysis, preferably, unreacted aromatic dihydroxy compounds are 70 area% or less, n = 1 body is 10 to 50 area%, n = 2 bodies are 10 to 40 area%, and n = 3 bodies or more. It is contained in a distribution of 50 area% or less.
本発明の多価ヒドロキシ樹脂は、好ましくは、水酸基当量が１５０～１５００ｇ／ｅｑ．であり、融点が１３０～３００℃である。 The polyvalent hydroxy resin of the present invention preferably has a hydroxyl group equivalent of 150 to 1500 g / eq. It has a melting point of 130 to 300 ° C.
本発明の多価ヒドロキシ樹脂は、芳香族ジヒドロキシ化合物と芳香族フッ素化合物を反応させることにより得られる。ここで芳香族ジヒドロキシ化合物とは、炭素数１～６のアルキル基置換又は未置換の２価のジヒドロキシベンゼン類、ジヒドロキシナフタレン類または、下記式（４）、
（但し、Ｘ、Ｒ１およびＲ２は、一般式（２）と同じ意味である。）
で表されるビスフェノール化合物である。具体的には、ジヒドロキシベンゼン類としては、ハイドロキノン、２，５－ジメチルハイドロキノン、２，３，５－トリメチルハイドロキノン、レゾルシノール、カテコール等が挙げられ、ジヒドロキシナフタレン類としては、１，４－ナフタレンジオール、１，５－ナフタレンジオール、１，６－ナフタレンジオール、１，７－ナフタレンジオール、２，６－ナフタレンジオール、２，７－ナフタレンジオール等が挙げられる。また、ビスフェノール化合物としては、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’－ジヒドロキシビフェニル、３，３’，５，５’－テトラメチル－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’－ジヒドロキシベンゾフェノン、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、フルオレンビスフェノール等が挙げられる。
The polyvalent hydroxy resin of the present invention is obtained by reacting an aromatic dihydroxy compound with an aromatic fluorine compound. Here, the aromatic dihydroxy compound is an alkyl group-substituted or unsubstituted divalent dihydroxybenzenes having 1 to 6 carbon atoms, dihydroxynaphthalene, or the following formula (4).
(However, X, R 1 and R 2 have the same meaning as the general formula (2).)
It is a bisphenol compound represented by. Specifically, examples of dihydroxybenzenes include hydroquinone, 2,5-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, resorcinol, catechol and the like, and examples of dihydroxynaphthalene include 1,4-naphthalenediol. Examples thereof include 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, and 2,7-naphthalenediol. The bisphenol compounds include bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxybiphenyl, 3,3', 5,5. '-Tetramethyl-4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, fluorenbisphenol, etc. Can be mentioned.
ジヒドロキシ基の置換位置については、ジヒドロキシベンゼン類としては、１，４－ジヒドロキシ体又は１，３－ジヒドロキシ体が好ましく、ジヒドロキシナフタレン類としては、１，５－ジヒドロキシ体、１，６－ジヒドロキシ体、２，６－ジヒドロキシ体、又は２，７－ジヒドロキシ体が好ましく、ビスフェノール化合物としては、４，４’－ジヒドロキシ体が好ましい。使用する芳香族ジヒドロキシ化合物において、これらのジヒドロキシ置換体が５０モル％以上であることが好ましい。 Regarding the substitution position of the dihydroxy group, the dihydroxybenzenes are preferably 1,4-dihydroxy-forms or 1,3-dihydroxy-forms, and the dihydroxynaphthalenes are 1,5-dihydroxy-forms and 1,6-dihydroxy-forms. The 2,6-dihydroxy form or the 2,7-dihydroxy form is preferable, and the bisphenol compound is preferably the 4,4'-dihydroxy form. In the aromatic dihydroxy compound used, these dihydroxy substituents are preferably 50 mol% or more.
耐熱性、熱伝導性及び力学強度等の観点から、これらの芳香族ジヒドロキシ化合物のなかではジヒドロキシベンゼン類、ジヒドロキシナフタレン類、ジヒドロキシビフェニル類が好ましい。上記の芳香族ジヒドロキシ化合物は単独で用いてもよいし、２種以上を併用してもよい。 Among these aromatic dihydroxy compounds, dihydroxybenzenes, dihydroxynaphthalene, and dihydroxybiphenyls are preferable from the viewpoints of heat resistance, thermal conductivity, mechanical strength, and the like. The above aromatic dihydroxy compounds may be used alone or in combination of two or more.
芳香族フッ素化合物としては、下記一般式（５）、
（但し、ｍは０～１の数を示し、ｒおよびｓは独立に０～４の数を示す。）
で表されるものであるが、好ましくはヘキサフルオロベンゼンまたは、デカフルオロビフェニルである。
Examples of the aromatic fluorine compound include the following general formula (5),
(However, m indicates a number from 0 to 1, and r and s independently indicate a number from 0 to 4.)
Although it is represented by, hexafluorobenzene or decafluorobiphenyl is preferable.
芳香族ジヒドロキシ化合物と芳香族フッ素化合物の反応においては、芳香族フッ素化合物に対して過剰量の芳香族ジヒドロキシ化合物が使用される。芳香族フッ素化合物の使用量は、芳香族ジヒドロキシ化合物１モルに対して０．１～０．９モルの範囲であるが、好ましくは、０．１～０．６モルの範囲である。これより多いと樹脂の軟化点が高くなり成形作業性に支障をきたす。さらには、ゲル化を引き起こす場合がある。また、これより少ないと反応終了後、過剰に用いた芳香族ジヒドロキシ化合物の量が多くなる。残った過剰量の芳香族ジヒドロキシ化合物は、取り除くことなく、そのままエポキシ樹脂の原料または硬化剤として使用できるが、一般式（１）または、（３）の樹脂の含有量が少なくなるため、耐熱性、低誘電性及び低吸水性等の特性改善の効果が低くなる。 In the reaction between the aromatic dihydroxy compound and the aromatic fluorine compound, an excess amount of the aromatic dihydroxy compound is used with respect to the aromatic fluorine compound. The amount of the aromatic fluorine compound used is in the range of 0.1 to 0.9 mol, preferably in the range of 0.1 to 0.6 mol, with respect to 1 mol of the aromatic dihydroxy compound. If it is more than this, the softening point of the resin becomes high and the molding workability is hindered. In addition, it may cause gelation. If it is less than this, the amount of the aromatic dihydroxy compound used in excess will increase after the reaction is completed. The remaining excess amount of the aromatic dihydroxy compound can be used as it is as a raw material or a curing agent for an epoxy resin without removing it, but since the content of the resin of the general formula (1) or (3) is reduced, it has heat resistance. , The effect of improving properties such as low dielectric property and low water absorption is reduced.
この反応は塩基性触媒の存在下に行うことがよく、三級アミン化合物、四級アンモニウム化合物、イミダゾール化合物、三級ホスフィン化合物、四級ホスホニウム化合物、および水酸化アルカリ金属化合物、水酸化アルカリ土類金属化合物、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩からなる群より選ばれる少なくとも１種の化合物を使用することができる。 This reaction is often carried out in the presence of a basic catalyst, such as tertiary amine compounds, quaternary ammonium compounds, imidazole compounds, tertiary phosphine compounds, quaternary phosphonium compounds, and alkali metal hydroxide compounds, alkaline earth hydroxides. At least one compound selected from the group consisting of a metal compound, an alkali metal carbonate, and an alkali metal hydrogen carbonate can be used.
三級アミン化合物としては、例えば、トリエチルアミン、トリ－ｎ－プロピルアミン、トリイソプロピルアミン、トリ－ｎ－ブチルアミン、トリ－ｓｅｃ－ブチルアミン、トリ－ｎ－ヘキシルアミン、ジメチルベンジルアミン、ジエチルベンジルアミン、トリベンジルアミン、１，８－ジアザビシクロ［５．４．０］ウンデセ－７－エンなどを挙げることができる。 Examples of the tertiary amine compound include triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-sec-butylamine, tri-n-hexylamine, dimethylbenzylamine, diethylbenzylamine, and g. Examples thereof include tribenzylamine, 1,8-diazabicyclo [5.4.0] undeceth-7-ene and the like.
四級アンモニウム化合物としては、例えば、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラ－ｎ－プロピルアンモニウム、水酸化テトラ－ｎ－ブチルアンモニウム、水酸化トリメチルベンジルアンモニウム、水酸化トリエチルベンジルアンモニウム等の水酸化四級アンモニウム化合物、塩化テトラメチルアンモニウム、塩化テトラエチルアンモニウム、塩化テトラ－ｎ－プロピルアンモニウム、塩化テトラ－ｎ－ブチルアンモニウム、塩化トリメチルベンジルアンモニウム、塩化トリエチルベンジルアンモニウム等の塩化四級アンモニウム化合物、臭化テトラメチルアンモニウム、臭化テトラエチルアンモニウム、臭化テトラ－ｎ－プロピルアンモニウム、臭化テトラ－ｎ－ブチルアンモニウム、臭化トリメチルベンジルアンモニウム、臭化トリエチルベンジルアンモニウム等の臭化四級アンモニウム化合物、沃化テトラメチルアンモニウム、沃化テトラエチルアンモニウム、沃化テトラ－ｎ－プロピルアンモニウム、沃化テトラ－ｎ－ブチルアンモニウム、沃化トリメチルベンジルアンモニウム、沃化トリエチルベンジルアンモニウム等の沃化四級アンモニウム化合物などを挙げることができる。 Examples of the quaternary ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, and triethylbenzylammonium hydroxide. Quaternary ammonium chloride compounds such as tetramethylammonium chloride, tetraethylammonium chloride, tetra-n-propylammonium chloride, tetra-n-butylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, etc. Quaternary ammonium bromide compounds such as tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-propylammonium bromide, tetra-n-butylammonium bromide, trimethylbenzylammonium bromide, triethylbenzylammonium bromide, etc. Examples include quaternary ammonium iodide compounds such as tetramethylammonium oxide, tetraethylammonium iodide, tetra-n-propylammonium iodide, tetra-n-butylammonium iodide, trimethylbenzylammonium iodide, and triethylbenzylammonium iodide. be able to.
イミダゾール化合物としては、２－メチルイミダゾール、２－エチルイミダゾール、２－フェニルイミダゾールおよび２－エチル－４－メチルイミダゾール、１－（２’、４’、６’－トリメチルベンゾイル）－２－エチルイミダゾール、１－（２'、６’－ジクロロベンゾイル）－２－メチルイミダゾール、１－（２’、４’、６’－トリメチルベンゾイル）－２－メチルイミダゾール、１－（２’、４’、６’－トリメチルベンゾイル）－２－フェニルイミダゾールなどを挙げることができる。 Examples of the imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole, 1- (2', 4', 6'-trimethylbenzoyl) -2-ethylimidazole, 1- (2', 6'-dichlorobenzoyl) -2-methylimidazole, 1- (2', 4', 6'-trimethylbenzoyl) -2-methylimidazole, 1- (2', 4', 6' -Trimethylbenzoyl) -2-phenylimidazole and the like can be mentioned.
三級ホスフィン化合物としては、例えば、トリエチルホスフィン、トリ－ｎ－ブチルホスフィン、トリフェニルホスフィン、トリノニルフェニルホスフィンなどを挙げることが出来る。四級ホスホニウム化合物としては、例えば、水酸化テトラメチルホスホニウムなどの水酸化四級ホスホニウム化合物；塩化テトラメチルホスホニウム、塩化テトラ－ｎ－ブチルホスホニウム、塩化テトラフェニルホスホニウム、臭化テトラ－ｎ－ブチルホスホニウム、臭化メチルトリフェニルホスホニウム、臭化－ｎ－ブチルトリフェニルホスホニウム、臭化メチルトリフェニルホスホニウム、臭化エチルトリフェニルホスホニウムなどのハロゲン化四級ホスホニウム化合物；エチルトリフェニルホスホニウムアセテートなどの酢酸四級ホスホニウム化合物などを挙げることができる。 Examples of the tertiary phosphine compound include triethylphosphine, tri-n-butylphosphine, triphenylphosphine, and trinonylphenylphosphine. Examples of the quaternary phosphonium compound include quaternary phosphonium hydroxide compounds such as tetramethylphosphonium hydroxide; tetramethylphosphonium chloride, tetra-n-butylphosphonium chloride, tetraphenylphosphonium chloride, tetra-n-butylphosphonium bromide, and the like. Tertiary halogenated phosphonium compounds such as methyltriphenylphosphonium bromide, -n-butyltriphenylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide; quaternary phosphonium acetate such as ethyltriphenylphosphonium acetate Compounds and the like can be mentioned.
水酸化アルカリ金属化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどを挙げることができる。水酸化アルカリ土類金属としては、例えば水酸化マグネシウム、水酸化カルシウム、水酸化バリウムなどを挙げることができる。 Examples of the alkali metal hydroxide compound include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide and barium hydroxide.
アルカリ金属炭酸塩としては、炭酸リチウム、炭酸ナトリウム、炭酸カリウムなどを挙げることができ、アルカリ金属炭酸水素塩としては、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウムなどを挙げることができる。 Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate and the like, and examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like.
これら塩基性触媒はそれぞれ単独、あるいは水または溶媒にあらかじめ溶解させておき、しかる後に反応系内に投入してもよい。塩基性触媒の使用割合は、芳香族ジヒドロキシ化合物のフェノール性水酸基１モルに対して、通常０．００１～１０モル％、好ましくは０．０５～５モル％である。 Each of these basic catalysts may be dissolved alone or in water or a solvent in advance, and then put into the reaction system. The ratio of the basic catalyst used is usually 0.001 to 10 mol%, preferably 0.05 to 5 mol%, based on 1 mol of the phenolic hydroxyl group of the aromatic dihydroxy compound.
通常、この反応は１０～２５０℃で１～２０時間行う。更に、反応溶媒として、メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、メチルセロソルブ、エチルセロソルブ等のアルコール類や、ベンゼン、トルエン、クロロベンゼン、ジクロロベンゼン等を使用することができる。 Usually, this reaction is carried out at 10 to 250 ° C. for 1 to 20 hours. Further, as the reaction solvent, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, benzene, toluene, chlorobenzene, dichlorobenzene and the like can be used.
反応終了後、場合により、中和、水洗等の方法により、触媒を除去し、必要に応じて残存する溶媒を水洗、減圧留去等の方法により系外に除き、ヒドロキシ樹脂とする。未反応の芳香族ジヒドロキシ化合物は、水洗、減圧留去等の方法により系外に除いてもよいし、除かなくてもよい。 After completion of the reaction, the catalyst may be removed by a method such as neutralization or washing with water, and if necessary, the remaining solvent may be removed from the system by a method such as washing with water or distillation under reduced pressure to obtain a hydroxy resin. The unreacted aromatic dihydroxy compound may or may not be removed from the system by a method such as washing with water or distillation under reduced pressure.
本発明のエポキシ樹脂は、多価ヒドロキシ樹脂のフェノール性水酸基がグリシジル基となっているが、多価ヒドロキシ樹脂の分子量分布をほぼ反映する。
本発明のエポキシ樹脂は、好ましくは、エポキシ当量が１７０～２０００ｇ／ｅｑ．、より好ましくは１８０～５００ｇ／ｅｑ．であり、加水分解性塩素が５００ｐｐｍ以下である。
In the epoxy resin of the present invention, the phenolic hydroxyl group of the polyvalent hydroxy resin is a glycidyl group, which substantially reflects the molecular weight distribution of the polyvalent hydroxy resin.
The epoxy resin of the present invention preferably has an epoxy equivalent of 170 to 2000 g / eq. , More preferably 180-500 g / eq. The hydrolyzable chlorine is 500 ppm or less.
本発明のエポキシ樹脂は、上記一般式（１）で表される多価ヒドロキシ樹脂をエピクロルヒドリンと反応させることにより得られる。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。 The epoxy resin of the present invention can be obtained by reacting the polyvalent hydroxy resin represented by the above general formula (1) with epichlorohydrin. This reaction can be carried out in the same manner as a normal epoxidation reaction.
例えば、上記一般式（１）で表される多価ヒドロキシ樹脂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、６０～１２０℃の範囲で１～１０時間反応させる方法が挙げられる。この際、アルカリ金属水酸化物の使用量は、多価ヒドロキシ樹脂中の水酸基１モルに対して０．８～２モル、好ましくは０．９～１．２モルの範囲である。また、エピクロルヒドリンは多価ヒドロキシ樹脂中の水酸基に対して過剰に用いられるが、通常、多価ヒドロキシ樹脂中の水酸基１モルに対して、１．５～１５モル、好ましくは２～８モルの範囲である。また、反応の際、四級アンモニウム塩等を添加することができる。四級アンモニウム塩としては、たとえばテトラメチルアンモニウムクロライド、テトラブチルアンモニウムクロライド、ベンジルトリエチルアンモニウムクロライド等があり、その添加量としては、多価ヒドロキシ樹脂に対して、０．１～２．０ｗｔ％の範囲が好ましい。これより少ないと四級アンモニウム塩添加の効果が小さく、これより多いと難加水分解性塩素の生成が多くなり、高純度化が困難になる。更には、ジメチルスルホキシド、ジグライム等の極性溶媒を用いても良く、その添加量は、多価ヒドロキシ樹脂に対して、１０～２００ｗｔ％の範囲が好ましい。これより少ないと添加の効果が小さく、これより多いと容積効率が低下し経済上好ましくない。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、濾過した後、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。このエポキシ樹脂は一般式（３）で表されるものを主成分とするが、一般式（１）の新規多価ヒドロキシ樹脂の芳香族環にナフチルメタン基が1つ又はそれ以上付加した化合物のグリシジルエーテル化物が含まれていてもよい。更に、本発明のエポキシ樹脂中のエポキシ基がエーテル結合としてオリゴマー化したものもが含まれていてもよい。 For example, after dissolving the polyvalent hydroxy resin represented by the above general formula (1) in excess epichlorohydrin, it is preferably 50 to 150 ° C. in the presence of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide. Is a method of reacting in the range of 60 to 120 ° C. for 1 to 10 hours. At this time, the amount of the alkali metal hydroxide used is in the range of 0.8 to 2 mol, preferably 0.9 to 1.2 mol, with respect to 1 mol of the hydroxyl group in the polyvalent hydroxy resin. In addition, epichlorohydrin is used in excess with respect to the hydroxyl group in the polyvalent hydroxy resin, but is usually in the range of 1.5 to 15 mol, preferably 2 to 8 mol, with respect to 1 mol of the hydroxyl group in the polyvalent hydroxy resin. Is. In addition, a quaternary ammonium salt or the like can be added during the reaction. Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride and the like, and the amount of the quaternary ammonium salt added is in the range of 0.1 to 2.0 wt% with respect to the polyvalent hydroxy resin. Is preferable. If it is less than this, the effect of adding the quaternary ammonium salt is small, and if it is more than this, the production of poorly hydrolyzable chlorine increases, which makes it difficult to purify. Further, a polar solvent such as dimethyl sulfoxide or diglyme may be used, and the addition amount thereof is preferably in the range of 10 to 200 wt% with respect to the polyvalent hydroxy resin. If it is less than this, the effect of addition is small, and if it is more than this, the volumetric efficiency is lowered, which is not economically preferable. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene and methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off to obtain the desired epoxy. Resin can be obtained. This epoxy resin is mainly composed of the one represented by the general formula (3), but is a compound in which one or more naphthylmethane groups are added to the aromatic ring of the novel polyvalent hydroxy resin of the general formula (1). A glycidyl etherified product may be contained. Further, the epoxy group in the epoxy resin of the present invention may be oligomerized as an ether bond.
本発明のエポキシ樹脂組成物は、エポキシ樹脂及び硬化剤よりなり、エポキシ樹脂成分として一般式（３）で表されるエポキシ樹脂又は硬化剤成分として上記一般式（１）で表される多価ヒドロキシ樹脂の少なくともいずれか一方を必須成分として配合したものである。
エポキシ樹脂成分として一般式（３）で表されるエポキシ樹脂を配合し、かつ、硬化剤成分として一般式（１）で表される多価ヒドロキシ樹脂を配合してもよい。
The epoxy resin composition of the present invention comprises an epoxy resin and a curing agent, and the epoxy resin represented by the general formula (3) as an epoxy resin component or the polyvalent hydroxy represented by the above general formula (1) as a curing agent component. It contains at least one of the resins as an essential ingredient.
The epoxy resin represented by the general formula (3) may be blended as the epoxy resin component, and the polyvalent hydroxy resin represented by the general formula (1) may be blended as the curing agent component.
一般式（３）で表されるエポキシ樹脂を必須成分とする場合の硬化剤としては、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る。例えば、ジシアンジアミド、多価フェノール類、酸無水物類、芳香族及び脂肪族アミン類等がある。具体的に例示すれば、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、更にはフェノール類、ナフトール類又は、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価のフェノール類のホルムアルデヒド、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、等があり、酸無水物としては、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、無水ナジック酸、無水トリメリット酸等がある。また、アミン類としては、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、あるいは一般式（１）で表される多価ヒドロキシ樹脂がある。本発明の樹脂組成物には、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。
この場合、本発明のエポキシ樹脂の配合量は、エポキシ樹脂全体中、好ましくは５～１００ｗｔ％の範囲、より好ましくは５０～１００ｗｔ％の範囲、さらに好ましくは８０～１００ｗｔ％の範囲である。
As the curing agent when the epoxy resin represented by the general formula (3) is an essential component, any curing agent generally known as an epoxy resin curing agent can be used. For example, there are dicyandiamides, polyhydric phenols, acid anhydrides, aromatics and aliphatic amines. Specifically, examples of the polyhydric phenols include, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol and the like. For divalent phenols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac, naphthol novolac, polyvinylphenol, etc. Representative trivalent or higher phenols, as well as phenols, naphthols, or bisphenol A, bisphenol F, bisphenol S, fluoren bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalene. There are polyhydric phenolic compounds synthesized by condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol and the like, which are divalent phenols such as diols, and the acid anhydride is anhydrous. There are phthalic acid, tetrahydroan phthalic acid, methyltetrahydroan phthalic acid, hexahydroan phthalic acid, methylhexahydroan phthalic acid, methyl bisphenol anhydride, nagic acid anhydride, trimellitic anhydride and the like. Examples of amines 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, or polyvalent hydroxy resins represented by the general formula (1). In the resin composition of the present invention, one kind or a mixture of two or more kinds of these curing agents can be used.
In this case, the blending amount of the epoxy resin of the present invention is preferably in the range of 5 to 100 wt%, more preferably in the range of 50 to 100 wt%, and further preferably in the range of 80 to 100 wt% in the entire epoxy resin.
一般式（１）で表される多価ヒドロキシ樹脂を硬化剤成分の必須成分とする場合のエポキシ樹脂としては、分子中にエポキシ基を２個以上有する通常のエポキシ樹脂はすべて使用できる。例を挙げれば、ビスフェノールＡ、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等の３価以上のフェノール類、又は、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ルシジルエーテル化物、あるいは上記一般式（１）で表される多官能エポキシ樹脂等がある。これらのエポキシ樹脂は、１種又は、２種以上を混合して用いることができる。
この場合、本発明の多価ヒドロキシ樹脂の配合量は、硬化剤全体中、好ましくは５～１００ｗｔ％の範囲、より好ましくは５０～１００ｗｔ％の範囲、さらに好ましくは８０～１００ｗｔ％の範囲である。
As the epoxy resin when the polyvalent hydroxy resin represented by the general formula (1) is an essential component of the curing agent component, any ordinary epoxy resin having two or more epoxy groups in the molecule can be used. For example, divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, or tris- (4-hydroxyphenyl) methane. , 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak and other trivalent or higher phenols, or tetrabromobisphenol A and other halogenated bisphenols. There are glucidyl etherified products, polyfunctional epoxy resins represented by the above general formula (1), and the like. These epoxy resins can be used alone or in admixture of two or more.
In this case, the blending amount of the multivalent hydroxy resin of the present invention is preferably in the range of 5 to 100 wt%, more preferably in the range of 50 to 100 wt%, and further preferably in the range of 80 to 100 wt% in the entire curing agent. ..
また、一般式（３）で表されるエポキシ樹脂又は一般式（１）で表される多価ヒドロキシ樹脂の一方又は両者を必須成分とする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適宜配合してもよいし、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、等の添加剤を配合してもよい。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、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。更に必要に応じて、従来より公知の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、ルイス酸等がある。添加量としては、通常、エポキシ樹脂１００重量部に対して、０．２～５重量部の範囲である。また更に必要に応じて、本発明の樹脂組成物には、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。 Further, in the epoxy resin composition of the present invention containing one or both of the epoxy resin represented by the general formula (3) and the polyhydric hydroxy resin represented by the general formula (1) as essential components, polyester and polyamide are included. , Polyethylene, Polyurethane, Polyurethane, Petroleum Resin, Indenkumaron Resin, Phenoxy Resin and other oligomers or polymer compounds may be appropriately blended, and inorganic fillers, pigments, difficult-to-reach agents, shake-modifying agents, cups, etc. may be blended as appropriate. Additives such as a ring agent and a fluidity improver may be blended. Examples of the inorganic filler include spherical or crushed molten silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like, and pigments. Examples include organic or inorganic extender pigments and scaly pigments. Examples of the rocking denaturing agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, organic bentonite-based, and the like. Further, if necessary, a conventionally known curing accelerator can be used. Examples include amines, imidazoles, organic phosphines, Lewis acids and the like. The amount to be added is usually in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin. Further, if necessary, the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, and a colorant such as carbon black. Flame retardant agents such as antimony oxide, low stress agents such as silicone oil, lubricants such as calcium stearate, and the like can be used.
本発明の硬化物は、上記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。成形する際の温度は、通常、１２０～２２０℃の範囲である。 The cured product of the present invention can be obtained by molding the epoxy resin composition by a method such as casting, compression molding, or transfer molding. The temperature at the time of molding is usually in the range of 120 to 220 ° C.
以下、実施例及び比較例に基づき、本発明を具体的に説明する。
実施例１（多価ヒドロキシ樹脂Ａの製造）
１Ｌ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９０．２ｇをＮ－メチルピロリドン（ＮＭＰ）３６０ｇに溶解した後、炭酸カリウム１９．９ｇを加え、窒素気流下、攪拌しながら５０℃に昇温した。その後、デカフルオロビフェニル（ＤＦＢＰ）４０．９ｇを加え、６０℃で２時間反応させた。反応液に酢酸１７．３ｇを加えて中和した後、大量の水に投入し、析出物をろ過にて回収した。水洗した後、乾燥して、粉末状の多価ヒドロキシ樹脂９６ｇを得た（多価ヒドロキシ樹脂Ａ）。
得られたヒドロキシ樹脂Ａの水酸基当量は１３６ｇ／ｅｑ.、融点は２６９℃であった。ＧＰＣチャートを図１に示す。未反応の４，４’－ジヒドロキシビフェニルが５２．６％、式（１）でｎ＝１、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが３０．３％、ｎ＝２、、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが１４．０％、ｎ＝３、、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが１．５％であった。
ここで溶融粘度は、ＢＲＯＯＫＦＩＥＬＤ社製ＣＡＰ２０００Ｈを用い、ＧＰＣ測定は、装置：ＨＬＣ－８３２０（東ソー（株）製）及びカラム：ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２５００×２本及びＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２０００×２本（何れも東ソー（株）製）を用い、溶媒：テトラヒドロフラン、流速：０．３５ｍｌ/分、温度：４０℃、検出器：ＲＩの条件で行った。
Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples.
Example 1 (Production of Multivalent Hydroxy Resin A)
After dissolving 90.2 g of 4,4'-dihydroxybiphenyl in 360 g of N-methylpyrrolidone (NMP) in a 1 L 4-port separable flask, 19.9 g of potassium carbonate is added, and the temperature is increased to 50 ° C. with stirring under a nitrogen stream. The temperature was raised. Then, 40.9 g of decafluorobiphenyl (DFBP) was added, and the mixture was reacted at 60 ° C. for 2 hours. After neutralizing by adding 17.3 g of acetic acid to the reaction solution, the mixture was poured into a large amount of water and the precipitate was recovered by filtration. After washing with water, it was dried to obtain 96 g of a powdery polyvalent hydroxy resin (polyvalent hydroxy resin A).
The obtained hydroxy resin A had a hydroxyl group equivalent of 136 g / eq. And a melting point of 269 ° C. The GPC chart is shown in FIG. Unreacted 4,4'-dihydroxybiphenyl is 52.6%, formula (1) is n = 1, m = 1, p = q = 0, x = y = 4 is 30.3%, n = 2, m = 1, p = q = 0, x = y = 4 is 14.0%, n = 3, m = 1, p = q = 0, x = y = 4 is 1. It was 5.5%.
Here, the melt viscosity uses CAP2000H manufactured by BROOKFIELD, and the GPC measurement is performed by the device: HLC-8320 (manufactured by Tosoh Corporation) and the column: TSKgel SuperHZ2500 × 2 and TSKgel SuperHZ2000 × 2 (both are Tosoh Corporation). The test was carried out under the conditions of solvent: tetrahydrofuran, flow velocity: 0.35 ml / min, temperature: 40 ° C., and detector: RI.
実施例２（多価ヒドロキシ樹脂Ｂの製造）
１Ｌの４口セパラブルフラスコに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（ＴＭＢＰＦ）９３．２ｇをＮＭＰ３６０ｇに溶解した後、炭酸カリウム１９．９ｇを加え、窒素気流下、攪拌しながら５０℃に昇温した。その後、ＤＦＢＰ４０．９ｇを加え、６０℃で２時間反応させた。反応液に酢酸１７．３ｇを加えて中和した後、大量の水に投入し、析出物をろ過にて回収した。水洗した後、乾燥して、粉末状の多価ヒドロキシ樹脂６０ｇを得た（多価ヒドロキシ樹脂Ｂ）。
得られたヒドロキシ樹脂Ｃの水酸基当量は２９０ｇ／ｅｑ.、融点は１５７℃であった。ＧＰＣ測定の結果、未反応のＴＭＢＰＦが３９．９％、式（１）でｎ＝１、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが２６．０％、ｎ＝２、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが１６．５％、ｎ＝３、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが９．０％、ｎ＝４、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが４．６％、ｎ＝５、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが２．２％、ｎ＝６、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが１．１％、ｎ＝７、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが０．５％、ｎ＝８、ｍ＝１，ｐ＝ｑ＝０，ｘ＝ｙ＝４のものが０．２％であった。
Example 2 (Production of Multivalent Hydroxy Resin B)
After dissolving 93.2 g of 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane (TMBPF) in 360 g of NMP in a 1 L 4-port separable flask, 19.9 g of potassium carbonate is added and nitrogen is added. The temperature was raised to 50 ° C. with stirring under an air flow. Then, 40.9 g of DFBP was added, and the reaction was carried out at 60 ° C. for 2 hours. After neutralizing by adding 17.3 g of acetic acid to the reaction solution, the mixture was poured into a large amount of water and the precipitate was recovered by filtration. After washing with water, it was dried to obtain 60 g of a powdery polyvalent hydroxy resin (polyvalent hydroxy resin B).
The obtained hydroxy resin C had a hydroxyl group equivalent of 290 g / eq. And a melting point of 157 ° C. As a result of GPC measurement, unreacted TMBPF was 39.9%, formula (1) was n = 1, m = 1, p = q = 0, x = y = 4, 26.0%, n = 2. , M = 1, p = q = 0, x = y = 4 is 16.5%, n = 3, m = 1, p = q = 0, x = y = 4 is 9.0% , N = 4, m = 1, p = q = 0, x = y = 4, 4.6%, n = 5, m = 1, p = q = 0, x = y = 4. 2.2%, n = 6, m = 1, p = q = 0, x = y = 4 is 1.1%, n = 7, m = 1, p = q = 0, x = y = The value of 4 was 0.5%, that of n = 8, m = 1, p = q = 0, and x = y = 4 was 0.2%.
実施例３（多価ヒドロキシ樹脂Ｃの製造）
１Ｌの４口セパラブルフラスコにＴＭＢＰＦ１３７．８ｇをＮＭＰ２８０ｇに溶解した後、炭酸カリウム５５．１ｇを加え、窒素気流下、攪拌しながら５０℃に昇温した。その後、ヘキサフルオロベンゼン（ＨＦＢＺ）２５．０ｇを加え、５５℃で８時間反応させた。反応液に酢酸４７．９ｇを加えて中和した後、大量の水に投入し、析出物をろ過にて回収した。水洗した後、乾燥して、粉末状の多価ヒドロキシ樹脂１４２ｇを得た（多価ヒドロキシ樹脂Ｃ）。
得られたヒドロキシ樹脂Ｃの水酸基当量は１７２ｇ／ｅｑ.、融点は１７０℃であった。ＧＰＣ測定の結果、未反応のＴＭＢＰＦが６９．５％、式（１）でｎ＝１、ｍ＝０，ｐ＝０，ｘ＝４のものが２２．１％、ｎ＝２、ｍ＝０，ｐ＝０，ｘ＝４のものが６．０％、ｎ＝３、ｍ＝０，ｐ＝０，ｘ＝４のものが１．４％であった。
Example 3 (Production of Multivalent Hydroxy Resin C)
After dissolving 137.8 g of TMBPF in 280 g of NMP in a 1 L 4-port separable flask, 55.1 g of potassium carbonate was added, and the temperature was raised to 50 ° C. with stirring under a nitrogen stream. Then, 25.0 g of hexafluorobenzene (HFBZ) was added, and the mixture was reacted at 55 ° C. for 8 hours. After neutralizing by adding 47.9 g of acetic acid to the reaction solution, the mixture was poured into a large amount of water and the precipitate was recovered by filtration. After washing with water, it was dried to obtain 142 g of a powdery polyvalent hydroxy resin (polyvalent hydroxy resin C).
The obtained hydroxy resin C had a hydroxyl group equivalent of 172 g / eq. And a melting point of 170 ° C. As a result of GPC measurement, unreacted TMBPF was 69.5%, and in formula (1), n = 1, m = 0, p = 0, x = 4 was 22.1%, n = 2, m = 0. , P = 0, x = 4 was 6.0%, n = 3, m = 0, p = 0, x = 4 was 1.4%.
実施例４（多価ヒドロキシ樹脂Ｄの製造）
１Ｌの４口セパラブルフラスコに３，３’，５，５’－テトラメチル－４，４’－ジヒドロキシビフェニル（ＴＭＢＰ）４９．５ｇをＮＭＰ２５０ｇに溶解した後、炭酸カリウム２０．７ｇを加え、窒素気流下、攪拌しながら１２０℃に昇温した。その後、ＤＦＢＰ１７．０ｇを加え、１４０℃に昇温し２時間反応させた。反応液に酢酸１８．０ｇを加えて中和した後、大量の水に投入し、析出物をろ過にて回収した。水洗した後、乾燥して、粉末状の多価ヒドロキシ樹脂４２ｇを得た（多価ヒドロキシ樹脂ＣＤ）。
得られた多価ヒドロキシ樹脂Ｂの融点は２５５℃、水酸基当量は３９２ｇ／ｅｑ．であった。未反応のＴＭＢＰが４．１％であった。
ＧＰＣチャートを図２、赤外吸収スペクトルを図３、電界脱離イオン化質量分析（ＦＤ－ＭＳ）スペクトルを図４に示す。赤外吸収スペクトルは日立製作所製２７０－５０型赤外吸収分析計を用いて、ＫＢｒ錠剤法により測定した。ＦＤ－ＭＳスペクトルは、日本電子製、ＪＭＳ－ＡＸ５０５ＨＡ型質量分析装置によりｍ／Ｚ＝１００～１６００の範囲で測定した。
Example 4 (Production of Multivalent Hydroxy Resin D)
After dissolving 49.5 g of 3,3', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl (TMBP) in 250 g of NMP in a 1 L 4-port separable flask, add 20.7 g of potassium carbonate and nitrogen. The temperature was raised to 120 ° C. with stirring under an air flow. Then, 17.0 g of DFBP was added, the temperature was raised to 140 ° C., and the reaction was carried out for 2 hours. After neutralizing by adding 18.0 g of acetic acid to the reaction solution, the mixture was poured into a large amount of water and the precipitate was recovered by filtration. After washing with water, it was dried to obtain 42 g of a powdery polyvalent hydroxy resin (multivalent hydroxy resin CD).
The obtained multivalent hydroxy resin B has a melting point of 255 ° C. and a hydroxyl group equivalent of 392 g / eq. Met. The unreacted TMBP was 4.1%.
The GPC chart is shown in FIG. 2, the infrared absorption spectrum is shown in FIG. 3, and the field desorption / ionization mass spectrometry (FD-MS) spectrum is shown in FIG. The infrared absorption spectrum was measured by the KBr tablet method using a 270-50 type infrared absorption analyzer manufactured by Hitachi, Ltd. The FD-MS spectrum was measured in the range of m / Z = 100 to 1600 by a JMS-AX505HA type mass spectrometer manufactured by JEOL.
実施例５（エポキシ樹脂Ａの製造）
実施例１で得た多価ヒドロキシ樹脂Ａ３０ｇをエピクロルヒドリン（ＥＣＨ）３００ｇ及びジグライム６０ｇに溶解し、減圧下（約１００ｍｍＨｇ）、６０℃にて４８．８％水酸化ナトリウム水溶液２１．６ｇを４時間かけて滴下した。この間、生成する水はＥＣＨとの共沸により系外に除き、留出したＥＣＨは系内に戻した。滴下終了後、更に１時間反応を継続した。その後、ＥＣＨ及びジグライムを減圧留去し、トルエン１２０ｍＬに溶解した後、濾過により生成した塩を除いた。水洗を行った後、トルエンを減圧留去し、白色粉末状のエポキシ樹脂２０ｇを得た（エポキシ樹脂Ａ）。
得られたエポキシ樹脂ＡのＤＳＣ測定から融点に対応した１２５℃と１５４℃にピークが観測された。赤外吸収スペクトルを図５に示す。エポキシ当量は１９４ｇ／ｅｑ．、加水分解性塩素は３５０ｐｐｍであった。なお、ここで加水分解性塩素は、樹脂試料０.５ｇを１，４－ジオキサン３０ｍｌに溶解させたものを１Ｎ－ＫＯＨ／メタノール溶液５ｍｌで３０分間煮沸還流したものを、硝酸銀溶液で電位差滴定を行うことにより求めた。
Example 5 (Manufacturing of Epoxy Resin A)
30 g of the polyhydric hydroxy resin A obtained in Example 1 was dissolved in 300 g of epichlorohydrin (ECH) and 60 g of diglyme, and 21.6 g of a 48.8% sodium hydroxide aqueous solution was added at 60 ° C. over 4 hours under reduced pressure (about 100 mmHg). And dropped. During this period, the generated water was removed from the system by azeotropic boiling with ECH, and the distilled ECH was returned to the inside of the system. After the completion of the dropping, the reaction was continued for another 1 hour. Then, ECH and diglyme were distilled off under reduced pressure, dissolved in 120 mL of toluene, and then the salt produced by filtration was removed. After washing with water, toluene was distilled off under reduced pressure to obtain 20 g of a white powdery epoxy resin (epoxy resin A).
From the DSC measurement of the obtained epoxy resin A, peaks were observed at 125 ° C and 154 ° C corresponding to the melting point. The infrared absorption spectrum is shown in FIG. The epoxy equivalent is 194 g / eq. The hydrolyzable chlorine was 350 ppm. Here, the hydrolyzable chlorine is obtained by dissolving 0.5 g of a resin sample in 30 ml of 1,4-dioxane, boiling it in 5 ml of a 1N-KOH / methanol solution for 30 minutes, and then performing potentiometric titration with a silver nitrate solution. Asked by doing.
実施例６（エポキシ樹脂Ｂの製造）
実施例２で得た多価ヒドロキシ樹脂Ｂ３０ｇをＥＣＨ２００ｇ及びジグライム３０ｇに溶解し、減圧下（約１００ｍｍＨｇ）、６０℃にて４８．８％水酸化ナトリウム水溶液９．４ｇを４時間かけて滴下した。この間、生成する水はＥＣＨとの共沸により系外に除き、留出したＥＣＨは系内に戻した。滴下終了後、更に１時間反応を継続した。その後、ＥＣＨ及びジグライムを減圧留去し、トルエン１２０ｍＬに溶解した後、濾過により生成した塩を除いた。水洗を行った後、トルエンを減圧留去し、常温でやや粘性のあるエポキシ樹脂３２ｇを得た（エポキシ樹脂Ｂ）。
エポキシ当量は３２９ｇ／ｅｑ．、１５０℃での溶融粘度は０．０５Ｐａ・ｓ、加水分解性塩素は８０ｐｐｍであった。
Example 6 (Manufacturing of Epoxy Resin B)
30 g of the polyvalent hydroxy resin B obtained in Example 2 was dissolved in 200 g of ECH and 30 g of diglyme, and 9.4 g of a 48.8% sodium hydroxide aqueous solution was added dropwise at 60 ° C. over 4 hours under reduced pressure (about 100 mmHg). During this period, the generated water was removed from the system by azeotropic boiling with ECH, and the distilled ECH was returned to the inside of the system. After the completion of the dropping, the reaction was continued for another 1 hour. Then, ECH and diglyme were distilled off under reduced pressure, dissolved in 120 mL of toluene, and then the salt produced by filtration was removed. After washing with water, toluene was distilled off under reduced pressure to obtain 32 g of a slightly viscous epoxy resin at room temperature (epoxy resin B).
The epoxy equivalent is 329 g / eq. The melt viscosity at 150 ° C. was 0.05 Pa · s, and the hydrolyzable chlorine was 80 ppm.
実施例７（エポキシ樹脂Ｃの製造）
実施例３で得た多価ヒドロキシ樹脂Ｃ５０ｇをＥＣＨ４００ｇ及びジグライム６０ｇに溶解し、減圧下（約１００ｍｍＨｇ）、６０℃にて４８．８％水酸化ナトリウム水溶液２６．３ｇを４時間かけて滴下した。この間、生成する水はＥＣＨとの共沸により系外に除き、留出したＥＣＨは系内に戻した。滴下終了後、更に１時間反応を継続した。その後、ＥＣＨ及びジグライムを減圧留去し、トルエン２００ｍＬに溶解した後、濾過により生成した塩を除いた。水洗を行った後、トルエンを減圧留去し、常温で粘稠なエポキシ樹脂３２ｇを得た（エポキシ樹脂Ｃ）。エポキシ当量は２１９ｇ／ｅｑ．，１５０℃での溶融粘度は０．０１Ｐa・ｓ，加水分解性塩素は３０ｐｐｍであった。
Example 7 (Manufacturing of Epoxy Resin C)
50 g of the polyvalent hydroxy resin C obtained in Example 3 was dissolved in 400 g of ECH and 60 g of diglyme, and 26.3 g of a 48.8% sodium hydroxide aqueous solution was added dropwise at 60 ° C. over 4 hours under reduced pressure (about 100 mmHg). During this period, the generated water was removed from the system by azeotropic boiling with ECH, and the distilled ECH was returned to the inside of the system. After the completion of the dropping, the reaction was continued for another 1 hour. Then, ECH and diglyme were distilled off under reduced pressure, dissolved in 200 mL of toluene, and then the salt produced by filtration was removed. After washing with water, toluene was distilled off under reduced pressure to obtain 32 g of a viscous epoxy resin at room temperature (epoxy resin C). The epoxy equivalent is 219 g / eq. The melt viscosity at 150 ° C. was 0.01 Pa · s, and the hydrolyzable chlorine was 30 ppm.
実施例８～１１及び比較例１
実施例１～７で合成した多価ヒドロキシ樹脂又はエポキシ樹脂、ビフェニル系エポキシ樹脂（エポキシ樹脂Ｄ：三菱化学製、ＹＸ－４０００Ｈ、エポキシ当量１９３、融点１０５℃）、フェノールノボラック（多価ヒドロキシ樹脂Ｅ；ＯＨ当量１０４、軟化点８３℃、１５０℃での溶融粘度０．３Ｐａ・ｓ；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に示す配合で樹脂組成物とした。
これを用いて成形（１５０℃、５分）した後、ポストキュア（１７５℃、４時間）を行って試験片を得て、種々の物性試験に供した。試験方法は、以下のとおり。ガラス転移点及び熱膨張係数は、（株）日立ハイテクサイエンス製ＴＭＡ７１００型熱機械測定装置を用いて、昇温速度１０℃／分の条件で求めた。熱分解温度及び残炭率は、（株）日立ハイテクサイエンス製ＴＧ／ＤＴＡ７３００型熱重量測定装置により、窒素気流下、昇温速度１０℃／分の条件にて５ｗｔ％重量減少時の熱分解温度及び７００℃での残炭率を求めた。吸水率は、直径５０mm、厚さ３mmの試験片を用い、ポストキュア後８５℃８５％ＲＨの条件で１００時間吸湿させた時の重量変化率とした。
結果を表１に示す。
Examples 8 to 11 and Comparative Example 1
Polyvalent hydroxy resin or epoxy resin synthesized in Examples 1 to 7, biphenyl-based epoxy resin (epoxy resin D: manufactured by Mitsubishi Chemical, YX-4000H, epoxy equivalent 193, melting point 105 ° C.), phenol novolac (polyvalent hydroxy resin E). OH equivalent 104, softening point 83 ° C., melt viscosity at 150 ° C. 0.3 Pa · s; BRG-557, manufactured by Aika Kogyo), using triphenylphosphine as a curing accelerator, and resin with the formulation shown in Table 1. It was made into a composition.
After molding (150 ° C., 5 minutes) using this, post-cure (175 ° C., 4 hours) was performed to obtain test pieces, which were subjected to various physical property tests. The test method is as follows. The glass transition point and the coefficient of thermal expansion were determined using a TMA7100 type thermomechanical measuring device manufactured by Hitachi High-Tech Science Co., Ltd. under the condition of a heating rate of 10 ° C./min. The pyrolysis temperature and residual coal rate are determined by the TG / DTA7300 type thermogravimetric measuring device manufactured by Hitachi High-Tech Science Co., Ltd. under the condition of a nitrogen stream and a heating rate of 10 ° C./min when the weight is reduced by 5 wt%. And the residual coal rate at 700 ° C. was determined. The water absorption rate was the weight change rate when a test piece having a diameter of 50 mm and a thickness of 3 mm was absorbed for 100 hours under the condition of 85 ° C. and 85% RH after post-cure.
The results are shown in Table 1.
Claims (8)
（但し、Ａは独立に二価の芳香族基を示す。ｎは１～１０の繰返し数、ｍは０～１の数を示し、ｐ、ｑ、ｘおよびｙは独立に０～４の置換数を示す。ｘ、ｙのいずれかは０ではない。）で表されることを特徴とする多価ヒドロキシ樹脂。 The following general formula (1),
(However, A independently indicates a divalent aromatic group. N indicates a number of repetitions of 1 to 10, m indicates a number of 0 to 1, and p, q, x and y independently substitute 0 to 4. A polyvalent hydroxy resin comprising a number; any of x and y is not 0).
（但しＸは単結合、酸素原子、硫黄原子、－ＳＯ２－、－ＣＯ－、－ＣＨ２－、－ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２－、－ＣＨ（φ）－、－Ｃφ（ＣＨ３）－、１，１－シクロアルカン基、９，９－フルオレニル基を示す。ここでφはフェニレン基を示す。Ｒ1、Ｒ2は、それぞれ独立して、水素原子、炭素数１～８のアルキル基、アリール基、アルコキシ基、アラルキル基又はハロゲン原子を示し、ｎは１～５０の数を示す。）
で表されるビスフェニレン基である請求項１に記載の多価ヒドロキシ樹脂。 A in the general formula (1) is a benzene ring, a naphthalene ring, or the following formula (2),
(However, X is a single bond, oxygen atom, sulfur atom, -SO 2- , -CO-, -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -CH (φ)- , -Cφ (CH 3 )-, 1,1-cycloalkane group, 9,9-fluorenyl group. Where φ indicates a phenylene group. R 1 and R 2 are independent hydrogen atoms, respectively. It indicates an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom having 1 to 8 carbon atoms, and n indicates a number of 1 to 50 carbon atoms.)
The multivalent hydroxy resin according to claim 1, which is a bisphenylene group represented by.
（但し、Ａは独立に二価の芳香族基、Ｇはグリシジル基を示す。ｎは１～１０の繰返し数、ｍは０～１の数を示し、ｐ、ｑ、ｘおよびｙは独立に０～４の置換数を示す。ｘ、ｙのいずれかは０ではない。）で表されることを特徴とするエポキシ樹脂。 The following general formula (3),
(However, A independently indicates a divalent aromatic group, G indicates a glycidyl group. N indicates a number of repetitions of 1 to 10, m indicates a number of 0 to 1, and p, q, x and y independently. The number of substitutions from 0 to 4 is shown. Any of x and y is not 0.) An epoxy resin.
A cured product obtained by curing the epoxy resin composition according to claim 7.
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