JP2023118158A - Dihydroxy resin, epoxy resin, method for producing the same, and epoxy resin composition, and cured product - Google Patents
Dihydroxy resin, epoxy resin, method for producing the same, and epoxy resin composition, and cured product Download PDFInfo
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- JP2023118158A JP2023118158A JP2022020935A JP2022020935A JP2023118158A JP 2023118158 A JP2023118158 A JP 2023118158A JP 2022020935 A JP2022020935 A JP 2022020935A JP 2022020935 A JP2022020935 A JP 2022020935A JP 2023118158 A JP2023118158 A JP 2023118158A
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- Prior art keywords
- epoxy resin
- dihydroxy
- general formula
- resin
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 78
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 78
- 229920005989 resin Polymers 0.000 title claims abstract description 56
- 239000011347 resin Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000000203 mixture Substances 0.000 title claims description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- -1 methylcyclohexyl group Chemical group 0.000 claims description 8
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000005266 casting Methods 0.000 abstract description 3
- 238000003475 lamination Methods 0.000 abstract description 2
- 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
- 238000005259 measurement Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000002989 phenols Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 125000005462 imide group Chemical group 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-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
- 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 6
- 229920003986 novolac Polymers 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000463 material Substances 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 3
- IXCOKTMGCRJMDR-UHFFFAOYSA-N 9h-fluorene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 IXCOKTMGCRJMDR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 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
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000003918 potentiometric titration Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 2
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 2
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 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
- 239000007864 aqueous solution Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 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
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000004065 semiconductor 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
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-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
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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
- 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
- YRKVLGUIGNRYJX-UHFFFAOYSA-N 4-[9-(4-amino-3-methylphenyl)fluoren-9-yl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(N)=CC=2)=C1 YRKVLGUIGNRYJX-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 5-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=CC2=C1O ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 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
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- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 235000013539 calcium stearate Nutrition 0.000 description 1
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- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、耐熱性に優れるとともに、難燃性、耐湿性等にも優れた硬化物を与えるエポキシ樹脂、及びそれ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、炭素繊維複合材料等の分野で好適に使用される。 The present invention relates to an epoxy resin that provides a cured product having excellent heat resistance, flame retardancy, moisture resistance, etc., an epoxy resin composition using the epoxy resin composition, and a cured product thereof. It is suitably used in fields such as insulating materials in the electrical and electronic fields such as semiconductor encapsulation, and carbon fiber composite materials.
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おり、耐熱性、耐湿性等の機能向上に加えて、環境面および安全性向上の観点から、難燃性に優れた樹脂の開発が求められている。また、エポキシ樹脂組成物を調整する際の溶剤溶解性等の取扱性の向上も重要な課題となっている。 In recent years, especially with the progress in the field of advanced materials, there is a demand for the development of higher performance base resins. There is a demand for the development of resins with excellent properties. In addition, the improvement of handleability such as solvent solubility when preparing the epoxy resin composition is also an important issue.
しかしながら、これまで知られているエポキシ樹脂には、これらの要求を十分に満足するものは未だ知られていない。例えば、特許文献1にはスーパーエンプラに分類されるエーテルエーテルケトン構造を持つエポキシ樹脂が提案されているが、成形性に難があるとともに、依然、耐熱性が十分ではなかった。これらの特性を改善するために、特許文献2には、イミド構造を有するビスフェノール化合物を硬化剤としたエポキシ樹脂組成物が提案されているが、樹脂の相溶性および耐熱性の点で十分ではなかった。特許文献3には、溶剤溶解性が改善されたイミド構造を有するエポキシ樹脂が開示されているが、耐熱性の観点で十分に満足するものではなかった。
However, none of the known epoxy resins that sufficiently satisfy these requirements has yet been known. For example,
本発明の目的は、優れた耐熱性、耐湿性を有する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ジヒドロキシ樹脂、エポキシ樹脂およびそ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。 An object of the present invention is to obtain a cured product having excellent heat resistance and moisture resistance, and is useful for lamination, molding, casting, adhesion, etc. It is an object of the present invention to provide an epoxy resin composition and a cured product thereof.
すなわち、本発明は 下記一般式(1)で表されるジヒドロキシ樹脂である。
(ここで、Aは独立してベンゼン、ナフタレン、または下記一般式(2)、
(但し、Xは単結合、-CH2-、-O-、-CO-、-S-、-SO2-、-C(CF3)2-、-O-φ-O-を示す。ここでφはフェニレン基を示す。)
で表されるビスフェニレン骨格を有する4価の芳香族基を示し、Bは独立してナフタレン、または下記一般式(3)、
(但し、Yは単結合、-CH2-、-O-、-C(CH3)2-を示し、R1、R2は、それぞれ独立して水素原子、炭素数1~9の炭化水素基を示し、mは0~2の数を示す。)
で表される2価の芳香族基を示し、Dは独立にナフタレン、または下記一般式(4)、
(但し、Zは単結合、-CH2-、-O-、-C(CH3)2-、-C(CF3)2-、シクロヘキシル基、メチルシクロヘキシル基、フルオレニル基を示し、R3、R4は、それぞれ独立して水素原子、炭素数1~9の炭化水素基を示す。)
で表される2価の芳香族基を示し、nは0.1~25の数を表す。)
That is, the present invention is a dihydroxy resin represented by the following general formula (1).
(Here, A is independently benzene, naphthalene, or the following general formula (2),
(where X represents a single bond, -CH2-, -O-, -CO-, -S-, -SO2-, -C(CF3)2-, -O-φ-O-, where φ is indicates a phenylene group.)
A tetravalent aromatic group having a bisphenylene skeleton represented by B is independently naphthalene, or the following general formula (3),
(where Y represents a single bond, -CH2-, -O-, -C(CH3)2-, R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms, m indicates a number from 0 to 2.)
represents a divalent aromatic group represented by D is independently naphthalene, or the following general formula (4),
(where Z represents a single bond, -CH2-, -O-, -C(CH3)2-, -C(CF3)2-, a cyclohexyl group, a methylcyclohexyl group, a fluorenyl group, and R3 and R4 are each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms.)
represents a divalent aromatic group represented by n represents a number from 0.1 to 25. )
また、本発明は下記一般式(5)、
(ここで、A、B、Dおよびnは、式(1)と同義である。)
で表されるエポキシ樹脂であり、上記一般式(1)で表されるジヒドロキシ樹脂とエピクロルヒドリンを反応させることを特徴とする式(5)で表されるエポキシ樹脂の製造方法である。
Further, the present invention provides the following general formula (5),
(Here, A, B, D and n are synonymous with formula (1).)
A method for producing an epoxy resin represented by the formula (5), characterized by reacting a dihydroxy resin represented by the general formula (1) with epichlorohydrin.
さらに、本発明は上記一般式(1)のジヒドロキシ樹脂または、上記一般式(5)のエポキシ樹脂を、硬化剤成分中の硬化剤、またはエポキシ樹脂成分中のエポキシ樹脂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、これらのエポキシ樹脂組成物を硬化してなる硬化物である。 Further, in the present invention, the dihydroxy resin of the general formula (1) or the epoxy resin of the general formula (5) is blended as a curing agent in the curing agent component or as an essential component of the epoxy resin in the epoxy resin component. It is an epoxy resin composition and a cured product obtained by curing these epoxy resin compositions.
本発明のイミド構造を有するジヒドロキシ樹脂またはエポキシ樹脂を必須成分として含む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、耐湿性等に優れた特長を有し、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 containing the dihydroxy resin or epoxy resin having an imide structure of the present invention as an essential component has excellent heat resistance, moisture resistance, etc. It can be suitably used for applications such as molds and adhesion.
以下、本発明を詳細に説明する。
本発明のジヒドロキシ樹脂は、一般式(1)で表される。
ここで、Aは独立してベンゼン、ナフタレン、または下記一般式(2)、
で表されるビスフェニレン骨格を有する4価の芳香族基を示し、Xは単結合、-CH2-、-O-、-CO-、-S-、-SO2-、-C(CF3)2-、-O-φ-O-を示す。ここでφはフェニレン基を示す。
The present invention will be described in detail below.
The dihydroxy resin of the present invention is represented by general formula (1).
Here, A is independently benzene, naphthalene, or the following general formula (2),
represents a tetravalent aromatic group having a bisphenylene skeleton represented by X is a single bond, -CH2-, -O-, -CO-, -S-, -SO2-, -C(CF3)2- , -O-φ-O-. Here, φ represents a phenylene group.
耐熱性の点からは、式(1)のAがベンゼン、または式(2)のXが単結合、-CO-のものが好ましく、硬化剤との相溶性、溶剤溶解性等の観点からは、式(2)のXが-C(CF3)2-、-O-、-SO2-、-O-φ-O-のものが好ましい。 From the viewpoint of heat resistance, it is preferable that A in formula (1) is benzene, or X in formula (2) is a single bond, -CO-, and from the viewpoint of compatibility with the curing agent, solvent solubility, etc. , wherein X in formula (2) is -C(CF3)2-, -O-, -SO2-, -O-φ-O-.
式(1)において、Bはナフタレン、または下記一般式(3)、
で表される2価の芳香族基を示す。ここで、Yは単結合、-CH2-、-O-、-C(CH3)2-を示し、R1、R2は、それぞれ独立して水素原子、炭素数1~9の炭化水素基を示し、mは0~2の数を示す。
In formula (1), B is naphthalene, or the following general formula (3),
represents a divalent aromatic group represented by Here, Y represents a single bond, -CH2-, -O-, -C(CH3)2-, R1 and R2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, m represents a number from 0 to 2;
耐熱性の点から、Bはナフタレン、または式(3)におけるYが単結合のものが好ましく、エポキシ樹脂との相溶性、溶剤溶解性等の観点からは、Bはナフタレン、または式(3)におけるYは-CH2-、-O-、-C(CH3)2-が好ましい。特に、エポキシ樹脂との相溶性、溶剤溶解性等の観点から、Bがナフタレン、または式(3)においてイミド基が置換する炭素原子に隣接するR1またはR2の少なくともいずれか一方が炭素数1~9の炭化水素基であることが好ましい。望ましいナフタレン骨格としては、1,4-置換体、1,5-置換体、1,6-置換体、2,6-置換体、2,7-置換体等が例示されるが、溶剤溶解性および耐熱性の観点から、1,5-置換体である。また、式(3)の望ましいR1またはR2としては、メチル基、エチル基、フェニル基である。これらの構造とすることにより、その立体障害でイミド環とBの芳香環との平面性が低下し、分子間の配向が阻害されてエポキシ樹脂との相溶性、溶剤溶解性等が向上する。mは0~2の数であるが、好ましくは、0または1である。 From the viewpoint of heat resistance, B is preferably naphthalene, or Y in formula (3) is preferably a single bond, and from the viewpoint of compatibility with epoxy resins, solvent solubility, etc., B is naphthalene or formula (3) Y in is preferably -CH2-, -O- or -C(CH3)2-. In particular, from the viewpoint of compatibility with epoxy resins, solvent solubility, etc., B is naphthalene, or at least one of R1 or R2 adjacent to the carbon atom substituted by the imide group in formula (3) has 1 to 1 carbon atoms. 9 is preferably a hydrocarbon group. Desirable naphthalene skeletons include 1,4-substituted, 1,5-substituted, 1,6-substituted, 2,6-substituted and 2,7-substituted compounds. And from the viewpoint of heat resistance, it is a 1,5-substituted product. Desirable R1 or R2 in formula (3) is a methyl group, an ethyl group, or a phenyl group. With these structures, the steric hindrance reduces the planarity of the imide ring and the aromatic ring of B, inhibits the orientation between molecules, and improves compatibility with epoxy resins, solvent solubility, and the like. m is a number from 0 to 2, preferably 0 or 1;
式(1)において、Dは独立してナフタレン、または下記一般式(4)、
で表される2価の芳香族基を示す。ここで、Zは単結合、-CH2-、-O-、-C(CH3)2-、-C(CF3)2-、シクロヘキシル基、メチルシクロヘキシル基、フルオレニル基を示し、R3、R4は、それぞれ独立して水素原子、炭素数1~9の炭化水素基を示し、pは0~2の数を示す。
In formula (1), D is independently naphthalene, or the following general formula (4),
represents a divalent aromatic group represented by Here, Z represents a single bond, -CH2-, -O-, -C(CH3)2-, -C(CF3)2-, a cyclohexyl group, a methylcyclohexyl group, a fluorenyl group, and R3 and R4 are each Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, and p represents a number of 0 to 2.
耐熱性の点から、Dはナフタレン、または、式(4)におけるZが単結合、-CO-、フルオレニル基のものが好ましく、エポキシ樹脂との相溶性、溶剤溶解性等の観点から、-CH2-、-O-、-C(CH3)2-、-C(CF3)2-、シクロヘキシル基、メチルシクロヘキシル基、フルオレニル基のものが好ましい。特に、耐熱性および溶剤溶解性の観点から、Dがナフタレン骨格、または式(4)におけるZがフルオレニル基のものが好ましく、さらには式(4)でイミド基が置換した炭素原子に隣接するR3またはR4の少なくともいずれか一つが炭素数1~9の炭化水素基であることが特に好ましい。望ましいナフタレン骨格としては、1,5-置換体であり、式(4)の望ましいR3またはR4としては、メチル基、エチル基、フェニル基である。これらの構造とすることにより、その立体障害でイミド環とDの芳香環との平面性が低下し、分子間の配向が阻害されて硬化剤との相溶性、溶剤溶解性等が向上する。pは0~2の数であるが、好ましくは、1または2である。 From the viewpoint of heat resistance, D is naphthalene, or Z in formula (4) is preferably a single bond, -CO-, or a fluorenyl group. From the viewpoint of compatibility with epoxy resins, solvent solubility, etc., -CH2 -, -O-, -C(CH3)2-, -C(CF3)2-, cyclohexyl group, methylcyclohexyl group and fluorenyl group are preferred. In particular, from the viewpoint of heat resistance and solvent solubility, it is preferable that D is a naphthalene skeleton, or Z in formula (4) is a fluorenyl group, and further R3 adjacent to the carbon atom substituted with an imide group in formula (4) Alternatively, at least one of R4 is particularly preferably a hydrocarbon group having 1 to 9 carbon atoms. A preferable naphthalene skeleton is a 1,5-substituted compound, and preferable R3 or R4 in formula (4) is a methyl group, an ethyl group, or a phenyl group. These structures reduce the planarity of the imide ring and the aromatic ring of D due to the steric hindrance, inhibiting the orientation of the molecules and improving the compatibility with the curing agent and solvent solubility. p is a number from 0 to 2, preferably 1 or 2;
一般式(1)において、nは繰り返し数であり、0.1から25の数を表す。繰り返し数の異なる複数の化合物の混合物である場合は、nの平均値(Σn/Σ分子数)が0.1から25の範囲にあるものである。好ましいnの値又はその平均値は、適用する用途に応じて異なる。例えば、フィラーの高充填率化が要求される半導体封止材の用途には、低粘度であるものが望ましく、nの値又はその平均値は0.1~15、好ましくは0.5~10、さらに好ましくは1.0~7.0、特に好ましくは1.1~5.0のものである。また、回路材料、繊維強化複合材料等の用途に適用する場合には、フィルム性および靭性付与等の観点から、nの値又はその平均値は3~25、好ましくは5~25、さらに好ましくは8~25のものである。 In general formula (1), n is the number of repetitions and represents a number from 0.1 to 25. In the case of a mixture of a plurality of compounds with different repeating numbers, the average value of n (Σn/Σnumber of molecules) is in the range of 0.1 to 25. The preferred value of n or its average value depends on the application. For example, for applications of semiconductor encapsulating materials that require a high filler filling rate, low viscosity is desirable, and the value of n or its average value is 0.1 to 15, preferably 0.5 to 10 , more preferably 1.0 to 7.0, and particularly preferably 1.1 to 5.0. When applied to applications such as circuit materials and fiber-reinforced composite materials, the value of n or its average value is 3 to 25, preferably 5 to 25, more preferably 5 to 25, from the viewpoint of imparting film properties and toughness. 8 to 25.
本発明のジヒドロキシ化合物は、重量平均分子量が500~15,000であることが好ましい。低粘度が要求される用途には、500~2,500の範囲であることが望ましく、フィルム性および靭性付与が要求される用途においては、2,000~15,000の範囲にあることが望ましい。また、本発明のジヒドロキシ化合物の水酸基当量は、低粘度が要求される用途には、好ましくは300~3,000g/eq.、より好ましくは350~2,000g/eq.さらに好ましくは400~1,500g/eq.、さらに好ましくは500~1,300g/eq.の範囲である。また、軟化点は、好ましくは120~350℃、より好ましくは150~300℃の範囲である。 The dihydroxy compound of the present invention preferably has a weight average molecular weight of 500-15,000. The range of 500 to 2,500 is desirable for applications requiring low viscosity, and the range of 2,000 to 15,000 is desirable for applications requiring film properties and toughness. . Moreover, the hydroxyl equivalent of the dihydroxy compound of the present invention is preferably 300 to 3,000 g/eq. , more preferably 350 to 2,000 g/eq. More preferably 400 to 1,500 g/eq. , more preferably 500 to 1,300 g/eq. is in the range of Also, the softening point is preferably in the range of 120 to 350°C, more preferably 150 to 300°C.
また、本発明のエポキシ樹脂は、一般式(5)で表される。
ここで、A、B、Dおよびnは、式(1)と同義である。
Moreover, the epoxy resin of this invention is represented by General formula (5).
Here, A, B, D and n are synonymous with formula (1).
本発明のエポキシ樹脂の好ましい重量平均分子量は、600~18,000の範囲であり、より好ましくは600~3,000の範囲である。また、好ましいエポキシ当量は、400~9,000の範囲であり、より好ましくは400~5,000の範囲、さらに好ましくは400~3,000、特に好ましくは500~1,000の範囲である。これより大きいと、粘度および軟化点が高くなり、エポキシ樹脂組成物の調整が困難になるとともに、成形性が低下する。本発明のエポキシ樹脂の好ましい軟化点は、100~350℃、より好ましくは100~280℃の範囲である。また、加水分解性塩素は好ましくは1000ppm以下、より好ましくは500ppm以下である。 The preferred weight average molecular weight of the epoxy resin of the present invention is in the range of 600-18,000, more preferably in the range of 600-3,000. Also, the epoxy equivalent is preferably in the range of 400 to 9,000, more preferably in the range of 400 to 5,000, even more preferably in the range of 400 to 3,000, particularly preferably in the range of 500 to 1,000. If it is larger than this, the viscosity and softening point will increase, making it difficult to adjust the epoxy resin composition, and the moldability will deteriorate. The preferred softening point of the epoxy resin of the present invention is in the range of 100-350°C, more preferably 100-280°C. Also, hydrolyzable chlorine is preferably 1000 ppm or less, more preferably 500 ppm or less.
本発明のエポキシ樹脂は、特に限定されるものではないが、一般式(1)で表されるジヒドロキシ樹脂とエピクロルヒドリンを反応させることにより製造することができる。この反応は、通常のエポキシ化反応と同様に行うことができる。 Although the epoxy resin of the present invention is not particularly limited, it can be produced by reacting a dihydroxy resin represented by general formula (1) with epichlorohydrin. This reaction can be carried out in the same manner as a normal epoxidation reaction.
例えば、一般式(1)で表されるジ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、ジ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ジ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、ジ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、ジヒドロキシ化合物に対して、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、N-メチルピロリドン等の極性溶媒を用いても良く、その添加量は、ジ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。 For example, after dissolving the dihydroxy resin represented by the general formula (1) in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, the temperature is 50 to 150°C, preferably 60°C. A method of reacting at a temperature of up to 120° C. for 1 to 10 hours may be mentioned. In this case, the alkali metal hydroxide is used in an amount of 0.8 to 2 mol, preferably 0.9 to 1.2 mol, per 1 mol of hydroxyl group in the dihydroxy resin. Epichlorohydrin is used in an excess amount relative to the hydroxyl groups in the dihydroxy resin, usually in the range of 1.5 to 15 mol, preferably 2 to 8 mol, per 1 mol of hydroxyl groups in the dihydroxy resin. Moreover, a quaternary ammonium salt or the like can be added during the reaction. Quaternary ammonium salts include, for example, tetramethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride and the like, and the amount added is preferably in the range of 0.1 to 2.0 wt% with respect to the dihydroxy compound. . If the amount is less than this, the effect of adding the quaternary ammonium salt will be small, and if it is more than this, the generation of hardly hydrolyzable chlorine will increase, making it difficult to achieve high purity. Furthermore, a polar solvent such as dimethylsulfoxide, diglyme, N-methylpyrrolidone, etc. may be used, and the amount added is preferably in the range of 10 to 200 wt% with respect to the dihydroxy 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 economically unfavorable. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and the solvent is distilled off to obtain the desired epoxy. resin can be obtained.
本発明のエポキシ樹脂組成物は、エポキシ樹脂及び硬化剤よりなり、一般式(1)で表されるジヒドロキシ樹脂、または一般式(5)で表されるエポキシ樹脂を必須成分として配合したものである。 The epoxy resin composition of the present invention comprises an epoxy resin and a curing agent, and contains a dihydroxy resin represented by the general formula (1) or an epoxy resin represented by the general formula (5) as an essential component. .
一般式(1)で表されるジヒドロキシ樹脂を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において、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(5)で表される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。
一般式(1)で表される本発明のジヒドロキシ樹脂を本発明のエポキシ樹脂組成物の硬化成分の必須成分とする場合、以下に例示する他の硬化剤も混合して用いることができる。この場合、一般式(1)で表されるヒドロキシ樹脂の配合量は、硬化剤成分中、好ましくは5~100wt%の範囲、より好ましくは30~100wt%の範囲、さらに好ましくは50~100wt%の範囲、さらに好ましくは70~100wt%の範囲である。
In the epoxy resin composition obtained by blending the dihydroxy resin represented by the general formula (1) as an essential component of the curing agent component, the epoxy resin may be any ordinary epoxy resin having two or more epoxy groups in the molecule. Available. Examples include dihydric phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcinol, or tris-(4-hydroxyphenyl)methane. , 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolak, o-cresol novolak, and other trihydric or higher phenols, or halogenated bisphenols, such as tetrabromobisphenol A There are a glycidyl etherate, an epoxy resin represented by the above general formula (5), and the like. These epoxy resins can be used singly or in combination of two or more.
When the dihydroxy resin of the present invention represented by the general formula (1) is used as an essential component of the curing component of the epoxy resin composition of the present invention, other curing agents exemplified below can also be mixed and used. In this case, the amount of the hydroxy resin represented by the general formula (1) is preferably in the range of 5 to 100 wt%, more preferably in the range of 30 to 100 wt%, still more preferably in the range of 50 to 100 wt% in the curing agent component. , more preferably 70 to 100 wt %.
一般式(5)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(4)で表されるジヒドロキシ化合物がある。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。
一般式(5)で表される本発明のエポキシ樹脂を本発明のエポキシ樹脂組成物の必須成分とする場合、他のエポキシ樹脂を混合して用いることができる。他のエポキシ樹脂としては、前記一般式(1)で表されるジヒドロキシ樹脂を硬化成分の必須成分とする場合のエポキシ樹脂の例示化合物と同じであり、例示されたエポキシ樹脂の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、一般式(5)で表されるエポキシ樹脂の配合量は、エポキシ樹脂成分中、好ましくは5~100wt%の範囲、より好ましくは10~70%の範囲、さらに好ましくは20~50%の範囲である。
When the epoxy resin represented by the general formula (5) is used as an essential component, any curing agent generally known as a curing agent for epoxy resins can be used. Examples include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines, and the like. Specific examples of polyhydric phenols include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcinol, naphthalenediol, and the like. Dihydric phenols, or tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. Representative trihydric or higher phenols, further phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalene diols and other divalent phenols such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, and polyhydric phenolic compounds synthesized with condensing agents such as p-xylylene glycol. Phthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride, nadic anhydride, trimellitic anhydride and the like. As amines, aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine and p-xylylenediamine, Aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine, or dihydroxy compounds represented by general formula (4) are available. One or a mixture of two or more of these curing agents can be used in the resin composition of the present invention.
When the epoxy resin of the present invention represented by general formula (5) is used as an essential component of the epoxy resin composition of the present invention, other epoxy resins can be mixed and used. The other epoxy resins are the same as the exemplified compounds of the epoxy resins when the dihydroxy resin represented by the general formula (1) is an essential component of the curing component, and one or two of the exemplified epoxy resins. More than one species can be mixed and used. In this case, the amount of the epoxy resin represented by general formula (5) is preferably in the range of 5 to 100 wt%, more preferably in the range of 10 to 70%, still more preferably in the range of 20 to 50%, in the epoxy resin component. is in the range of
エポキシ樹脂と硬化剤の配合比率は、エポキシ基と硬化剤中の官能基が当量比で0.8~1.5の範囲であることが好ましい。この範囲外では硬化後も未反応のエポキシ基、又は硬化剤中の官能基が残留する可能性がある。
一般式(5)で表されるエポキシ樹脂と硬化剤の配合比率は、重量比で、0.2~1.0の範囲が好ましい。
The mixing ratio of the epoxy resin and the curing agent is preferably in the range of 0.8 to 1.5 in terms of the equivalent ratio of the epoxy groups to the functional groups in the curing agent. Outside this range, unreacted epoxy groups or functional groups in the curing agent may remain even after curing.
The weight ratio of the epoxy resin represented by formula (5) to the curing agent is preferably in the range of 0.2 to 1.0.
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。 In the epoxy resin composition of the present invention, oligomers or polymer compounds such as polyesters, polyamides, polyimides, polyethers, polyurethanes, petroleum resins, indene cumarone resins, and phenoxy resins may be appropriately blended, or inorganic fillers may be added. Additives such as agents, pigments, flame retardants, thixotropic agents, coupling agents, fluidity improvers and the like may be added. Examples of inorganic fillers include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. Examples thereof include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, organic bentonite-based, and the like.
本発明のエポキシ樹脂組成物中には、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、本発明のエポキシ樹脂組成物には、カルナバワックス、OPワックス等の離型剤、γ-グリシドキシプロピルトリメトキシシラン等のカップリング剤、カーボンブラック等の着色剤、三酸化アンチモン等の難燃剤、シリコンオイル等の低応力化剤、ステアリン酸カルシウム等の滑剤等を使用できる。 Conventionally known curing accelerators can be used in the epoxy resin composition of the present invention. 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 epoxy resin composition of the present invention may contain release agents such as carnauba wax and OP wax, coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, Flame retardants such as antimony trioxide, stress reducing agents such as silicone oil, and lubricants such as calcium stearate 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、120~280℃の範囲である。 The cured product of the present invention can be obtained by molding the epoxy resin composition by methods such as casting, compression molding and transfer molding. The temperature during molding is usually in the range of 120-280°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(ジヒドロキシ樹脂Aの製造)
セパラブルフラスコに4,4’-オキシジフタル酸二無水物31.7g(0.10モル)、4,4’-ジアミノジフェニルエーテル10.2g(0.05モル)、5-アミノ-1-ナフトール16.8g(0.10モル)をN-メチルピロリドン(NMP)200mLに溶解し、80℃にて2時間反応させた。反応液にトルエン120mLを加えて昇温しながら、共沸により生成した水を除いた。その後、160℃に昇温し3時間反応を行った。この間、生成する水は系外に除いた。常温に冷却した後、蒸留水1Lを加えて、析出物をろ過により回収した後、水洗、乾燥を行い、粉末状の生成物52gを得た(ジヒドロキシ樹脂A)。水酸基当量は820g/eq.、軟化点は180℃であった。GPC測定から、重量平均分子量は1,670、数平均分子量は1,070であった。チャートを図1、赤外吸収スペクトルを図2に示す。得られた樹脂の構造は、下式(6)であり、GPC測定からnの平均値は1.5であった。
ここで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(THF)、流速:0.35ml/分、温度:40℃、検出器:RIの条件で行った。また、水酸基当量は、塩化アセチル溶液中で、水酸化カリウムによる電位差滴定を行うことにより測定した。得られた樹脂のシクロペンタノンへの溶解度は20以上であった。赤外吸収スペクトルは日本分光製、FT/IR-6100型赤外吸収分析計を用いてKBr錠剤法により測定した。
The present invention will be specifically described below based on examples and comparative examples.
Example 1 (Production of dihydroxy resin A)
A separable flask was charged with 31.7 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride, 10.2 g (0.05 mol) of 4,4'-diaminodiphenyl ether, and 16.5 g (0.05 mol) of 5-amino-1-naphthol. 8 g (0.10 mol) was dissolved in 200 mL of N-methylpyrrolidone (NMP) and reacted at 80° C. for 2 hours. 120 mL of toluene was added to the reaction solution and the temperature was raised to remove water produced by azeotropy. After that, the temperature was raised to 160° C. and the reaction was carried out for 3 hours. During this time, the generated water was removed from the system. After cooling to room temperature, 1 L of distilled water was added, and the precipitate was collected by filtration, washed with water and dried to obtain 52 g of powdery product (dihydroxy resin A). The hydroxyl equivalent is 820 g/eq. , the softening point was 180°C. GPC measurement revealed a weight average molecular weight of 1,670 and a number average molecular weight of 1,070. A chart is shown in FIG. 1, and an infrared absorption spectrum is shown in FIG. The structure of the obtained resin was represented by the following formula (6), and the average value of n was 1.5 from GPC measurement.
Here, GPC measurement is performed using an apparatus: HLC-8320 (manufactured by Tosoh Corporation) and columns: TSKgel SuperHZ2500 × 2 and TSKgel SuperHZ2000 × 2 (both manufactured by Tosoh Corporation), solvent: tetrahydrofuran (THF) , flow rate: 0.35 ml/min, temperature: 40°C, detector: RI. Moreover, the hydroxyl group equivalent was measured by performing potentiometric titration with potassium hydroxide in an acetyl chloride solution. The solubility of the obtained resin in cyclopentanone was 20 or more. The infrared absorption spectrum was measured by the KBr tablet method using an FT/IR-6100 type infrared absorption spectrometer manufactured by JASCO Corporation.
実施例2(ジヒドロキシ樹脂Bの製造)
3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物53.7g(0.150モル)、1,5-ジアミノナフタレン12.2g(0.075モル),4-アミノ-m-クレゾール18.9g(0.150モル)を用いて、実施例1と同様の反応を行い、粉末状の生成物79gを得た(ジヒドロキシ樹脂B)。水酸基当量は642g/eq.、軟化点は273℃であった。GPC測定から、重量平均分子量は1,500、数平均分子量は1,090であった。得られた樹脂の構造は、下式(7)であり、GPC測定からnの平均値は1.3であった。
得られた樹脂のNMPへの溶解度は20以上であった。
Example 2 (Production of dihydroxy resin B)
3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride 53.7 g (0.150 mol), 1,5-diaminonaphthalene 12.2 g (0.075 mol), 4-amino-m- Using 18.9 g (0.150 mol) of cresol, the same reaction as in Example 1 was carried out to obtain 79 g of a powdery product (dihydroxy resin B). The hydroxyl equivalent is 642 g/eq. , the softening point was 273°C. GPC measurement revealed a weight average molecular weight of 1,500 and a number average molecular weight of 1,090. The structure of the obtained resin was represented by the following formula (7), and the average value of n was 1.3 from GPC measurement.
The solubility of the obtained resin in NMP was 20 or more.
実施例3(ジヒドロキシ樹脂Cの製造)
4,4’-ヘキサフルオロイソプロピリデンジフタル酸二無水物31.7g(0.070モル)、4,4’-ジアミノジフェニルエーテル7.2g(0.035モル),4-アミノ-m-クレゾール8.8g(0.070モル)を用いて、実施例1と同様の反応を行い、粉末状の生成物36gを得た(ジヒドロキシ樹脂C)。水酸基当量は657g/eq.、軟化点は155℃であった。GPC測定から、重量平均分子量は1,900、数平均分子量は1,270であった。得られた樹脂の構造は、下式(8)であり、GPC測定からnの平均値は1.3であった。
得られた樹脂のシクロペンタノンへの溶解度は20以上であった。
Example 3 (Production of dihydroxy resin C)
4,4′-hexafluoroisopropylidene diphthalic dianhydride 31.7 g (0.070 mol), 4,4′-diaminodiphenyl ether 7.2 g (0.035 mol), 4-amino-m-cresol 8 Using .8 g (0.070 mol), the same reaction as in Example 1 was carried out to obtain 36 g of a powdery product (dihydroxy resin C). The hydroxyl equivalent is 657 g/eq. , the softening point was 155°C. GPC measurement revealed a weight average molecular weight of 1,900 and a number average molecular weight of 1,270. The structure of the obtained resin was the following formula (8), and the average value of n was 1.3 from GPC measurement.
The solubility of the obtained resin in cyclopentanone was 20 or more.
実施例4(ジヒドロキシ樹脂Dの製造)
4,4’-オキシジフタル酸二無水物38.0g(0.120モル)、9,9-ビス(4-アミノ-3-メチルフェニル)フルオレン23.1g(0.060モル),4-アミノ-m-クレゾール15.1g(0.120モル)を用いて、実施例1と同様の反応を行い、粉末状の生成物70gを得た(ジヒドロキシ樹脂D)。水酸基当量は712g/eq.、軟化点は280℃であった。GPC測定から、重量平均分子量は2,020、数平均分子量は1,240であった。得られた樹脂の構造は、下式(9)であり、GPC測定からnの平均値は1.7であった。
得られた樹脂のシクロペンタノンへの溶解度は20以上であった。
Example 4 (Production of dihydroxy resin D)
4,4′-oxydiphthalic dianhydride 38.0 g (0.120 mol), 9,9-bis(4-amino-3-methylphenyl)fluorene 23.1 g (0.060 mol), 4-amino- Using 15.1 g (0.120 mol) of m-cresol, the same reaction as in Example 1 was carried out to obtain 70 g of a powdery product (dihydroxy resin D). The hydroxyl equivalent is 712 g/eq. , the softening point was 280°C. GPC measurement revealed a weight average molecular weight of 2,020 and a number average molecular weight of 1,240. The structure of the obtained resin was represented by the following formula (9), and the average value of n was 1.7 from GPC measurement.
The solubility of the obtained resin in cyclopentanone was 20 or more.
実施例5(ジヒドロキシ樹脂Eの製造)
4,4’-オキシジフタル酸二無水物44.3g(0.140モル)、4,4’-ジアミノジフェニルエーテル21.5g(0.105モル),4-アミノ-m-クレゾール8.8g(0.070モル)を用いて、実施例1と同様の反応を行い、粉末状の生成物68gを得た(ジヒドロキシ樹脂E)。水酸基当量は1,228g/eq.、軟化点は300℃以上であった。GPC測定から、重量平均分子量は4,290、数平均分子量は2,350であった。GPCチャートを図3に示す。得られた樹脂の構造は、下式(10)であり、GPC測定からnの平均値は4.5であった。
得られた樹脂のNMPへの溶解度は10であった。
Example 5 (Production of dihydroxy resin E)
44.3 g (0.140 mol) of 4,4'-oxydiphthalic dianhydride, 21.5 g (0.105 mol) of 4,4'-diaminodiphenyl ether, 8.8 g (0.105 mol) of 4-amino-m-cresol. 070 mol), the same reaction as in Example 1 was carried out to obtain 68 g of a powdery product (dihydroxy resin E). The hydroxyl equivalent is 1,228 g/eq. , the softening point was 300° C. or higher. GPC measurement revealed a weight average molecular weight of 4,290 and a number average molecular weight of 2,350. A GPC chart is shown in FIG. The structure of the obtained resin was the following formula (10), and the average value of n was 4.5 from GPC measurement.
The solubility of the resulting resin in NMP was 10.
実施例6(エポキシ樹脂Aの合成)
実施例1で得たジヒドロキシ樹脂A24gをエピクロルヒドリン90g及びNMP90gに溶解し、減圧下(約130mmHg)、65℃にて48.6%水酸化ナトリウム水溶液4.8gを4時間かけて滴下した。この間、生成する水はエピクロルヒドリンとの共沸により系外に除き、留出したエピクロルヒドリンは系内に戻した。反応後、エピクロルヒドリンを減圧留去した後、反応液を大量の蒸留水に滴下した。生成物のろ過、水洗を行った後、乾燥し、黄褐色のエポキシ樹脂21gを得た(エポキシ樹脂A)。GPC測定から、重量平均分子量は1,340、数平均分子量は950であった。エポキシ当量は980g/eq.、軟化点は145℃であった。得られた樹脂のシクロペンタノンへの溶解度は20以上であった。GPCチャートを図4、赤外吸収スペクトルを図5に示す。
ここでエポキシ当量は、臭化テトラエチルアンモニウムの酢酸溶液中で、過塩素酸による電位差滴定を行うことにより測定した。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 6 (synthesis of epoxy resin A)
24 g of the dihydroxy resin A obtained in Example 1 was dissolved in 90 g of epichlorohydrin and 90 g of NMP, and 4.8 g of a 48.6% sodium hydroxide aqueous solution was added dropwise at 65° C. under reduced pressure (about 130 mmHg) over 4 hours. During this time, the generated water was removed from the system by azeotroping with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the reaction, epichlorohydrin was distilled off under reduced pressure, and the reaction solution was added dropwise to a large amount of distilled water. After the product was filtered and washed with water, it was dried to obtain 21 g of a yellowish brown epoxy resin (epoxy resin A). GPC measurement revealed a weight average molecular weight of 1,340 and a number average molecular weight of 950. The epoxy equivalent is 980 g/eq. , the softening point was 145°C. The solubility of the obtained resin in cyclopentanone was 20 or more. A GPC chart is shown in FIG. 4, and an infrared absorption spectrum is shown in FIG.
Here, the epoxy equivalent was measured by performing potentiometric titration with perchloric acid in an acetic acid solution of tetraethylammonium bromide. Hydrolyzable chlorine was obtained by dissolving 0.5 g of a resin sample in 30 ml of 1,4-dioxane, boiling under reflux for 30 minutes in 5 ml of a 1N-KOH/methanol solution, and performing potentiometric titration with a silver nitrate solution. Ta.
実施例7(エポキシ樹脂Bの合成)
実施例2で得たジヒドロキシ化合物B30g、エピクロルヒドリン130g、NMP130g、48.6%水酸化ナトリウム水溶液7.7gを用いて実施例6と同様に反応を行い、茶白色のエポキシ樹脂32gを得た(エポキシ樹脂B)。GPC測定から、重量平均分子量は1,200、数平均分子量は940であった。エポキシ当量は710g/eq.、軟化点は266℃であった。得られた樹脂のシクロペンタノンへの溶解度は20以上であった。
Example 7 (Synthesis of epoxy resin B)
Using 30 g of the dihydroxy compound B obtained in Example 2, 130 g of epichlorohydrin, 130 g of NMP, and 7.7 g of a 48.6% sodium hydroxide aqueous solution, the reaction was carried out in the same manner as in Example 6 to obtain 32 g of a brownish white epoxy resin (epoxy Resin B). GPC measurement revealed a weight average molecular weight of 1,200 and a number average molecular weight of 940. The epoxy equivalent is 710 g/eq. , the softening point was 266°C. The solubility of the obtained resin in cyclopentanone was 20 or more.
実施例8~12及び比較例1~4
実施例3~5で合成した樹脂(ジヒドロキシ樹脂C~E)、実施例6、7で合成したエポキシ樹脂(エポキシ樹脂A、B)、ジフェニルエーテル型エポキシ樹脂(エポキシ樹脂C:日鉄ケミカル&マテリアル製、YSLV-80DE、エポキシ当量163g/eq.)、ビフェニル型エポキシ樹脂(エポキシ樹脂D:三菱化学製、YX-4000H、エポキシ当量193)、4,4’-ジヒドロキシジフェニルエーテル(硬化剤A:水酸基当量101g/eq.)、フェノールノボラック(硬化剤B;アイカ工業製、BRG-557、水酸基当量104、軟化点83℃)を用い、硬化促進剤として
1644818577457_1
(TPP)を用いて、表1に示す配合で樹脂組成物とした。
これを用いて成形(180℃、5分)した後、ポストキュア(180℃、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。結果を表1に示す。
Examples 8-12 and Comparative Examples 1-4
Resins synthesized in Examples 3 to 5 (dihydroxy resins C to E), epoxy resins synthesized in Examples 6 and 7 (epoxy resins A and B), diphenyl ether type epoxy resins (epoxy resin C: manufactured by Nippon Steel Chemical & Material , YSLV-80DE, epoxy equivalent 163 g / eq.), biphenyl type epoxy resin (epoxy resin D: YX-4000H manufactured by Mitsubishi Chemical, epoxy equivalent 193), 4,4'-dihydroxydiphenyl ether (curing agent A: hydroxyl equivalent 101 g / eq.), using phenol novolac (curing agent B; manufactured by Aica Kogyo Co., Ltd., BRG-557, hydroxyl equivalent 104, softening point 83 ° C.), as a curing accelerator
1644818577457_1
(TPP) was used to prepare a resin composition according to the formulation shown in Table 1.
After molding (180° C., 5 minutes) using this, post-curing (180° C., 4 hours) was performed to obtain test pieces, which were subjected to various physical property tests. The test method is as follows. Table 1 shows the results.
[評価]
(1)ガラス転移温度(Tg)、線膨張係数
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℃/分にて測定した。
(2)熱分解開始温度、残炭率
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℃/分の条件で測定し、10wt%重量減少温度を熱分解開始温度とし、残炭率は700℃における重量残存率とした。
(3)吸水率
直径50mm、厚さ3mmの円盤を成形し、ポストキュア後、85℃、相対湿度85%の条件で100時間吸湿させた後の重量変化率とした。
[evaluation]
(1) Glass transition temperature (Tg), coefficient of linear expansion Measured at a heating rate of 10°C/min using a TMA7100 type thermomechanical measurement device manufactured by Hitachi High-Tech Science.
(2) Pyrolysis start temperature, residual carbon rate Measured under nitrogen flow with a TG/DTA7300 type thermogravimetry device manufactured by Hitachi High-Tech Science under conditions of a temperature increase rate of 10 ° C./min, and a 10 wt% weight loss temperature is pyrolyzed. The starting temperature was used, and the residual carbon ratio was defined as the weight residual ratio at 700°C.
(3) Water Absorption A disk having a diameter of 50 mm and a thickness of 3 mm was formed, and after post-curing, it was subjected to moisture absorption for 100 hours under the conditions of 85° C. and 85% relative humidity, and the weight change rate was obtained.
Claims (6)
(ここで、Aは独立してベンゼン、ナフタレン、または下記一般式(2)、
(但し、Xは単結合、-CH2-、-O-、-CO-、-S-、-SO2-、-C(CF3)2-、-O-φ-O-を示す。ここでφはフェニレン基を示す。)
で表されるビスフェニレン骨格を有する4価の芳香族基を示し、Bは独立してナフタレン、または下記一般式(3)、
(但し、Yは単結合、-CH2-、-O-、-C(CH3)2-を示し、R1、R2は、それぞれ独立して水素原子、炭素数1~9の炭化水素基を示し、mは0~2の数を示す。)
で表される2価の芳香族基を示し、Dは独立にナフタレン、または下記一般式(4)、
(但し、Zは単結合、-CH2-、-O-、-C(CH3)2-、-C(CF3)2-、シクロヘキシル基、メチルシクロヘキシル基、フルオレニル基を示し、R3、R4は、それぞれ独立して水素原子、炭素数1~9の炭化水素基を示し、pは0~2の数を示す。)
で表される2価の芳香族基を示し、nは0.1~25の数を表す。) A dihydroxy resin represented by the following general formula (1).
(Here, A is independently benzene, naphthalene, or the following general formula (2),
(where X represents a single bond, -CH2-, -O-, -CO-, -S-, -SO2-, -C(CF3)2-, -O-φ-O-, where φ is indicates a phenylene group.)
A tetravalent aromatic group having a bisphenylene skeleton represented by B is independently naphthalene, or the following general formula (3),
(where Y represents a single bond, -CH2-, -O-, -C(CH3)2-, R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms, m indicates a number from 0 to 2.)
represents a divalent aromatic group represented by D is independently naphthalene, or the following general formula (4),
(where Z represents a single bond, -CH2-, -O-, -C(CH3)2-, -C(CF3)2-, a cyclohexyl group, a methylcyclohexyl group, a fluorenyl group, and R3 and R4 are each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, and p represents a number of 0 to 2.)
represents a divalent aromatic group represented by n represents a number from 0.1 to 25. )
(ここで、A、B、Dおよびnは、式(1)と同義である。) An epoxy resin represented by the following general formula (5).
(Here, A, B, D and n are synonymous with formula (1).)
A cured product obtained by curing the epoxy resin composition according to claim 4 or 5.
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