JP2022132514A - Polyester resin, curable resin composition, and cured product thereof, printed wiring board and semiconductor sealing material - Google Patents
Polyester resin, curable resin composition, and cured product thereof, printed wiring board and semiconductor sealing material Download PDFInfo
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- JP2022132514A JP2022132514A JP2022114681A JP2022114681A JP2022132514A JP 2022132514 A JP2022132514 A JP 2022132514A JP 2022114681 A JP2022114681 A JP 2022114681A JP 2022114681 A JP2022114681 A JP 2022114681A JP 2022132514 A JP2022132514 A JP 2022132514A
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- Prior art keywords
- group
- polyester resin
- acid
- resin composition
- curable resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 61
- 239000004645 polyester resin Substances 0.000 title claims abstract description 61
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- 239000004065 semiconductor Substances 0.000 title claims abstract description 15
- 239000003566 sealing material Substances 0.000 title abstract description 6
- -1 aromatic monocarboxylic acid Chemical class 0.000 claims abstract description 58
- 239000002253 acid Substances 0.000 claims abstract description 40
- 150000004820 halides Chemical class 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 7
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 description 47
- 229920005989 resin Polymers 0.000 description 34
- 239000011347 resin Substances 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000003822 epoxy resin Substances 0.000 description 24
- 229920000647 polyepoxide Polymers 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 14
- 125000003545 alkoxy group Chemical group 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 13
- 125000005843 halogen group Chemical group 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 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 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 125000003710 aryl alkyl group Chemical group 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000005199 aryl carbonyloxy group Chemical group 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
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 5
- 239000005350 fused silica glass Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000000958 aryl methylene group Chemical group 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 125000002993 cycloalkylene group Chemical group 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000412 polyarylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VERMEZLHWFHDLK-UHFFFAOYSA-N tetrahydroxybenzene Natural products OC1=CC=C(O)C(O)=C1O VERMEZLHWFHDLK-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- UTCOUOISVRSLSH-UHFFFAOYSA-N 1,2-Anthracenediol Chemical compound C1=CC=CC2=CC3=C(O)C(O)=CC=C3C=C21 UTCOUOISVRSLSH-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- WMPGCOIUVFJFMG-UHFFFAOYSA-N 1-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)naphthalene-2,7-diol Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=C(O)C=CC2=CC=C(O)C=C21 WMPGCOIUVFJFMG-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- NWDURASZIAUTSB-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetrol Chemical group OC1=C(O)C(O)=CC(C=2C=CC=CC=2)=C1O NWDURASZIAUTSB-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
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- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 239000005696 Diammonium phosphate Substances 0.000 description 1
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- 239000002841 Lewis acid Substances 0.000 description 1
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- 239000000539 dimer Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
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- 230000020169 heat generation Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- PYNVYLAZKQQFLK-UHFFFAOYSA-N naphthalene-1,2,3,4-tetrol Chemical compound C1=CC=CC2=C(O)C(O)=C(O)C(O)=C21 PYNVYLAZKQQFLK-UHFFFAOYSA-N 0.000 description 1
- NCIAGQNZQHYKGR-UHFFFAOYSA-N naphthalene-1,2,3-triol Chemical compound C1=CC=C2C(O)=C(O)C(O)=CC2=C1 NCIAGQNZQHYKGR-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BCMKHWMDTMUUSI-UHFFFAOYSA-N tetrahydroxynaphthalene Natural products OC1=CC(O)=CC2=CC(O)=CC(O)=C21 BCMKHWMDTMUUSI-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
本発明は、硬化物における耐熱性や誘電特性に優れるポリエステル樹脂、これを含有する硬化性樹脂組成物、その硬化物、プリント配線基板及び半導体封止材料に関する。 TECHNICAL FIELD The present invention relates to a polyester resin having excellent heat resistance and dielectric properties in a cured product, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor encapsulating material.
半導体や多層プリント基板等に用いられる絶縁材料の技術分野では、各種電子部材の薄型化や信号の高速化及び高周波数化に伴い、これらの市場動向に合わせた新たな樹脂材料の開発が求められている。樹脂材料に求められる性能としては、耐熱性や耐吸湿性、基材密着性等の基本的な性能はもちろんのこと、信号の高速や高周波数化が進む中、発熱等によるエネルギー損失を低減させるために、硬化物における誘電率と誘電正接との両値が低いことも重要な性能の一つである。 In the technical field of insulating materials used in semiconductors and multilayer printed circuit boards, the development of new resin materials that meet these market trends is required as various electronic components become thinner and signal speeds and frequencies increase. ing. The performance required for resin materials is not only the basic performance such as heat resistance, moisture absorption resistance, and substrate adhesion, but also the reduction of energy loss due to heat generation as the speed and frequency of signals are increasing. For this reason, it is one of the important performances that both the dielectric constant and the dielectric loss tangent of the cured product are low.
硬化物における誘電率と誘電正接とが比較的低い樹脂材料として、ジシクロペンタジエンフェノール樹脂とα-ナフトールとをフタル酸クロライドでエステル化して得られる活性エステル樹脂をエポキシ樹脂の硬化剤として用いる技術が知られている(下記特許文献1参照)。特許文献1記載の活性エステル樹脂は、フェノールノボラック樹脂のような従来型の硬化剤を用いた場合と比較すると、硬化物における誘電率や誘電正接が低い特徴を有するが、昨今の市場要求を満たすものではなかった。また、硬化物のガラス転移温度で評価される耐熱性等々の性能についても更なる向上が求められていた。 As a resin material having a relatively low dielectric constant and dielectric loss tangent in a cured product, there is a technique of using an active ester resin obtained by esterifying a dicyclopentadiene phenol resin and α-naphthol with phthaloyl chloride as a curing agent for an epoxy resin. known (see Patent Document 1 below). The active ester resin described in Patent Document 1 has a low dielectric constant and dielectric loss tangent in the cured product compared to the case of using a conventional curing agent such as a phenol novolak resin, but it meets the recent market demand. It was nothing. In addition, there is a demand for further improvement in performance such as heat resistance, which is evaluated by the glass transition temperature of the cured product.
従って、本発明が解決しようとする課題は、硬化物における耐熱性や誘電特性に優れるポリエステル樹脂、これを含有する硬化性樹脂組成物を提供することにある。 Accordingly, the problem to be solved by the present invention is to provide a polyester resin which is excellent in heat resistance and dielectric properties in a cured product, and a curable resin composition containing the same.
本発明者らは前記課題を解決すべく鋭意検討した結果、分子末端にアリールカルボニルオキシ構造を有し、分子中に少なくとも一つの重合性不飽和結合を有する芳香族ポリエステル樹脂は、硬化物における耐熱性が高く、誘電特性にも優れることを見出し、本発明を完成するに至った。 As a result of intensive studies by the present inventors to solve the above problems, an aromatic polyester resin having an arylcarbonyloxy structure at the molecular end and at least one polymerizable unsaturated bond in the molecule has a heat resistance in a cured product. The inventors have found that it has high properties and excellent dielectric properties, and have completed the present invention.
即ち、本発明は、分子末端にアリールカルボニルオキシ構造を有する芳香族ポリエステル樹脂であって、分子構造中に存在する芳香環の少なくとも一つが、芳香環上の置換基として重合性不飽和結合含有基(P)を有することを特徴とするポリエステル樹脂に関する。 That is, the present invention provides an aromatic polyester resin having an arylcarbonyloxy structure at the molecular end, wherein at least one of the aromatic rings present in the molecular structure is a polymerizable unsaturated bond-containing group as a substituent on the aromatic ring. It relates to a polyester resin characterized by having (P).
本発明は更に、前記ポリエステル樹脂と、硬化剤とを含有する硬化性樹脂組成物に関する。 The present invention further relates to a curable resin composition containing the polyester resin and a curing agent.
本発明は更に、前記硬化性樹脂組成物の硬化物に関する。 The present invention further relates to a cured product of the curable resin composition.
本発明は更に、前記硬化性樹脂組成物を用いてなるプリント配線基板に関する。 The present invention further relates to a printed wiring board using the curable resin composition.
本発明は更に、前記硬化性樹脂組成物を用いてなる半導体封止材料に関する。 The present invention further relates to a semiconductor sealing material using the curable resin composition.
本発明によれば、硬化物における耐熱性や誘電特性に優れるポリエステル樹脂、これを含有する硬化性樹脂組成物、その硬化物、プリント配線基板及び半導体封止材料を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the polyester resin which is excellent in the heat resistance and dielectric property in hardened|cured material, the curable resin composition containing the same, its hardened|cured material, a printed wiring board, and a semiconductor sealing material can be provided.
以下、本発明を詳細に説明する。
本発明のポリエステル樹脂は、分子末端にアリールカルボニルオキシ構造を有する芳香族ポリエステル樹脂であって、分子構造中に存在する芳香環の少なくとも一つが、芳香環上の置換基として重合性不飽和結合含有基(P)を有することを特徴とする。
The present invention will be described in detail below.
The polyester resin of the present invention is an aromatic polyester resin having an arylcarbonyloxy structure at the molecular end, wherein at least one of the aromatic rings present in the molecular structure contains a polymerizable unsaturated bond as a substituent on the aromatic ring. It is characterized by having a group (P).
本発明において前記芳香族ポリエステル樹脂とは、芳香環間のエステル結合部位を複数有するポリエステル樹脂のことを指し、分子鎖の一部に脂肪族炭化水素基等を含んでいて
もよい。
In the present invention, the aromatic polyester resin refers to a polyester resin having a plurality of ester bond sites between aromatic rings, and may contain an aliphatic hydrocarbon group or the like in part of the molecular chain.
本発明のポリエステル樹脂は、分子構造中に存在する芳香環の少なくとも一つが、芳香環上の置換基として重合性不飽和結合含有基(P)を有することを特徴の一つとする。前記重合性不飽和結合含有基(P)において重合性不飽和結合とは、例えば、炭素間二重結合や炭素間三重結合等が挙げられる。前記重合性不飽和結合含有基(P)のうち、炭素間二重結合を有するものの具体例としては、例えば、ビニル基、ビニルオキシ基、(メタ)アリル基、(メタ)アリルオキシ基、1-プロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、1-ヘキセニル基、2-ヘキセニル基、3-ヘキセニル基、4-ヘキセニル基、5-ヘキセニル基、1-オクテニル基、2-オクテニル基、1-ウンデセニル基、1-ペンタデセニル基、3-ペンタデセニル基、7-ペンタデセニル基、1-オクタデセニル基、2-オクタデセニル基、シクロペンテニル基、シクロヘキセニル基、シクロオクテニル基、1,3-ブタジエニル基、1,4-ブタジエニル基、ヘキサ-1,3-ジエニル基、ヘキサ-2,5-ジエニル基、ペンタデカ-4,7-ジエニル基、ヘキサ-1,3,5-トリエニル基、ペンタデカ-1,4,7-トリエニル基、(メタ)アクリル基、(メタ)アクリロイルオキシ基、(メタ)アクリロイルオキシ(ポリ)アルキレンオキシ基等が挙げられる。また、炭素間三重結合を有するものの具体例としては、例えば、エチニル基、プロパルギル基、1-ブチニル基、2-ブチニル基、3-ブチニル基、3-ペンチニル基、4-ペンチニル基、1,3-ブタジイニル基等が挙げられる。これらの中でも、硬化物における耐熱性が特に高く、誘電特性にも優れるポリエステル樹脂となることから、ビニル基、(メタ)アリル基、1-プロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、1,3-ブタジエニル基の何れか一種類以上であることが好ましい。 One of the characteristics of the polyester resin of the present invention is that at least one of the aromatic rings present in the molecular structure has a polymerizable unsaturated bond-containing group (P) as a substituent on the aromatic ring. Examples of the polymerizable unsaturated bond in the polymerizable unsaturated bond-containing group (P) include carbon-carbon double bonds and carbon-carbon triple bonds. Among the polymerizable unsaturated bond-containing groups (P), specific examples of those having a carbon-carbon double bond include, for example, a vinyl group, a vinyloxy group, a (meth)allyl group, a (meth)allyloxy group, and 1-propenyl. group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, 1-undecenyl group, 1-pentadecenyl group, 3-pentadecenyl group, 7-pentadecenyl group, 1-octadecenyl group, 2-octadecenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1,3-butadienyl group, 1,4-butadienyl group, hexa-1,3-dienyl group, hexa-2,5-dienyl group, pentadeca-4,7-dienyl group, hexa-1,3,5-trienyl group, pentadeca-1,4 , 7-trienyl group, (meth)acryl group, (meth)acryloyloxy group, (meth)acryloyloxy (poly)alkyleneoxy group and the like. Further, specific examples of those having a carbon-carbon triple bond include, for example, ethynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1,3 -Butadiynyl group and the like. Among these, the heat resistance in the cured product is particularly high, and the polyester resin has excellent dielectric properties. It is preferably one or more of -butenyl group and 1,3-butadienyl group.
本発明のポリエステル樹脂は、硬化物における耐熱性が特に高く、誘電特性にも優れるポリエステル樹脂となることから、前記重合性不飽和結合含有基(P)の含有量が150~450g/モルの範囲であることが好ましい。なお、本発明において前記重合性不飽和結合含有基(P)の含有量は、ポリエステル樹脂の反応原料から算出される計算値である。 The polyester resin of the present invention has particularly high heat resistance in the cured product and is a polyester resin having excellent dielectric properties, so the content of the polymerizable unsaturated bond-containing group (P) is in the range of 150 to 450 g / mol. is preferably In the present invention, the content of the polymerizable unsaturated bond-containing group (P) is a calculated value calculated from the reaction raw material of the polyester resin.
本発明のポリエステル樹脂は、分子末端にアリールカルボニルオキシ構造を有する。即ち、本発明のポリエステル樹脂は、当該構造部位を形成するための反応原料として、芳香族モノカルボン酸又はその酸ハロゲン化物(a1)等を必須の反応原料とする。 The polyester resin of the present invention has an arylcarbonyloxy structure at the molecular end. That is, the polyester resin of the present invention uses an aromatic monocarboxylic acid or its acid halide (a1) as an essential reaction raw material for forming the structural portion.
前記アリールカルボニルオキシ構造中のアリール基は、例えば、フェニル基、ナフチル器、アントリル基、及びこれらの芳香核上に前記重合性不飽和結合含有基(P)、アルキル基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基等の置換基を一つ乃至複数有する構造部位等が挙げられる。前記アルキル基は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基等のアルキル基;シクロへキシル基等のシクロアルキル基等が挙げられる。前記アルコキシ基は、例えば、メトキシ基、エトキシ基、プロピルオキシ基、ブトキシ基等が挙げられる。前記ハロゲン原子は、フッ素原子、塩素原子、臭素原子等が挙げられる。前記アリール基は、フェニル基、ナフチル基、アントリル基、及びこれらの芳香核上に前記脂肪族炭化水素基やアルコキシ基、ハロゲン原子等が置換した構造部位等が挙げられる。前記アラルキル基は、ベンジル基、フェニルエチル基、ナフチルメチル基、ナフチルエチル基、及びこれらの芳香核上に前記アルキル基やアルコキシ基、ハロゲン原子等が置換した構造部位等が挙げられる。これらの中でも、硬化物における耐熱性と誘電特性とに一層優れるポリエステル樹脂となることから、フェニル基又はその芳香核上に前述の置換基を一つ乃至複数有するものが好ましい。また、芳香核上の置換基としては、重合性不飽和結合含有基(P)、炭素原子数1~4のアルキル基、炭素原子数1~4のアルコキシ基、ハロゲン原子、ベンジル基を一つ乃至複数有するものが好ましい。即ち、本発明のポリエステル樹脂は、分子末端に下記構造式(5)で表される構造部位を有することが好ましい。 The aryl group in the arylcarbonyloxy structure includes, for example, a phenyl group, a naphthyl group, an anthryl group, and the polymerizable unsaturated bond-containing group (P), alkyl group, alkoxy group, halogen atom, Structural moieties having one or more substituents such as aryl groups and aralkyl groups are exemplified. Examples of the alkyl group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; and cycloalkyl groups such as cyclohexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. A fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned as the said halogen atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and structural sites in which the aromatic nuclei of these groups are substituted with the aliphatic hydrocarbon group, alkoxy group, halogen atom, or the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and structural sites in which the aromatic nuclei of these groups are substituted with the alkyl group, alkoxy group, halogen atom, or the like. Among these, those having one or more of the aforementioned substituents on the phenyl group or its aromatic nucleus are preferable, since the polyester resin will be more excellent in heat resistance and dielectric properties in the cured product. In addition, the substituent on the aromatic nucleus includes a polymerizable unsaturated bond-containing group (P), an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a benzyl group. It is preferable to have one or more than one. That is, the polyester resin of the present invention preferably has a structural site represented by the following structural formula (5) at the molecular terminal.
本発明のポリエステル樹脂は、分子末端にアリールカルボニルオキシ構造を有する芳香族ポリエステル樹脂であって、分子構造中に存在する芳香環の少なくとも一つが、芳香環上の置換基として重合性不飽和結合含有基(P)を有するものであれば、他の具体構造は特に限定されない。また、どのような方法で製造されたものであってもよい。以下、本発明のポリエステル樹脂の具体例を2つ挙げるが、本発明はこれに限定されるものではない。 The polyester resin of the present invention is an aromatic polyester resin having an arylcarbonyloxy structure at the molecular end, wherein at least one of the aromatic rings present in the molecular structure contains a polymerizable unsaturated bond as a substituent on the aromatic ring. Other specific structures are not particularly limited as long as they have a group (P). Moreover, it may be manufactured by any method. Two specific examples of the polyester resin of the present invention are shown below, but the present invention is not limited thereto.
本発明のポリエステル樹脂の具体例としては、例えば、以下のようなものが挙げられる。
・芳香族モノカルボン酸又はその酸ハロゲン化物(a1)と分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)とのエステル化物であって、前記芳香族モノカルボン酸又はその酸ハロゲン化物(a1)及び前記分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)の少なくとも一方が芳香環上の置換基として重合性不飽和結合含有基(P)を有する化合物
・芳香族モノカルボン酸又はその酸ハロゲン化物(a1)、分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)、及び芳香族ポリカルボン酸又はその酸ハロゲン化物(a3)のエステル化物であって、前記芳香族モノカルボン酸又はその酸ハロゲン化物(a1)、前記分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)、及び前記芳香族ポリカルボン酸又はその酸ハロゲン化物(a3)の少なくとも一つが芳香環上の置換基として重合性不飽和結合含有基(P)を有する化合物
Specific examples of the polyester resin of the present invention include the following.
- An ester of an aromatic monocarboxylic acid or its acid halide (a1) and a compound (a2) having two or more phenolic hydroxyl groups in its molecular structure, said aromatic monocarboxylic acid or its acid halide A compound in which at least one of (a1) and a compound (a2) having two or more phenolic hydroxyl groups in the molecular structure has a polymerizable unsaturated bond-containing group (P) as a substituent on the aromatic ring ・Aromatic monocarboxylic An ester of an acid or an acid halide thereof (a1), a compound (a2) having two or more phenolic hydroxyl groups in the molecular structure, and an aromatic polycarboxylic acid or an acid halide thereof (a3), wherein the aromatic at least one of the group monocarboxylic acid or its acid halide (a1), the compound (a2) having two or more phenolic hydroxyl groups in the molecular structure, and the aromatic polycarboxylic acid or its acid halide (a3) A compound having a polymerizable unsaturated bond-containing group (P) as a substituent on the aromatic ring
前記芳香族モノカルボン酸又はその酸ハロゲン化物(a1)は、例えば、安息香酸、ハロゲン化ベンゾイル、ナフタレンカルボン酸、ハロゲン化ナフトイル、これらの芳香核上に前記重合性不飽和結合含有基(P)、アルキル基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基等の置換基を一つ乃至複数有する構造部位等が挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。 The aromatic monocarboxylic acid or its acid halide (a1) is, for example, benzoic acid, benzoyl halide, naphthalenecarboxylic acid, naphthoyl halide, the polymerizable unsaturated bond-containing group (P) on the aromatic nucleus of these , an alkyl group, an alkoxy group, a halogen atom, an aryl group, an aralkyl group, or the like, having one or more substituents. Each of these may be used alone, or two or more of them may be used in combination.
前記分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)は、例えば、各種の芳香族ポリヒドロキシ化合物や、下記構造式(1)で表される化合物、下記構造式(3)で表される化合物等が挙げられる。分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)はそれぞれ単独で用いても良いし、2種類以上を併用しても良い。また、前記分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)は The compound (a2) having two or more phenolic hydroxyl groups in the molecular structure includes, for example, various aromatic polyhydroxy compounds, compounds represented by the following structural formula (1), and represented by the following structural formula (3). and the like. The compound (a2) having two or more phenolic hydroxyl groups in its molecular structure may be used alone or in combination of two or more. Further, the compound (a2) having two or more phenolic hydroxyl groups in the molecular structure is
前記各種の芳香族ポリヒドロキシ化合物は、例えば、ジヒドロキシベンゼン、トリヒドロキシベンゼン、テトラヒドロキシベンゼン、ジヒドロキシナフタレン、トリヒドロキシナフタレン、テトラヒドロキシナフタレン、ジヒドロキシアントラセン、トリヒドロキシアントラセン、テトラヒドロキシアントラセン、ビフェノール、テトラヒドロキシビフェニル等の他、これらの芳香核上に一つ乃至複数の置換基を有する化合物等が挙げられる。芳香核上の置換基は前記重合性不飽和結合含有基(P)、アルキル基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基等が挙げられ、其々の具体例は前述の通りである。 The various aromatic polyhydroxy compounds include, for example, dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, and tetrahydroxybiphenyl. and the like, compounds having one or more substituents on these aromatic nuclei. Substituents on the aromatic nucleus include the aforementioned polymerizable unsaturated bond-containing group (P), alkyl groups, alkoxy groups, halogen atoms, aryl groups, aralkyl groups, etc. Specific examples are as described above.
前記構造式(1)~(4)中のR1、R2について、重合性不飽和結合含有基(P)、アルキル基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の具体例は前述の通りである。また、nは1以上の整数であるが、硬化物における耐熱性や誘電特性の他、汎用溶剤への溶解性や低溶融粘度性に優れるポリエステル樹脂となることから、1~4程度であることが好ましい。 Specific examples of the polymerizable unsaturated bond-containing group (P), the alkyl group, the alkoxy group, the halogen atom, the aryl group, and the aralkyl group for R 1 and R 2 in the structural formulas (1) to (4) are described above. Street. In addition, n is an integer of 1 or more, but in addition to heat resistance and dielectric properties in the cured product, the polyester resin is excellent in solubility in general-purpose solvents and low melt viscosity, so it should be about 1 to 4. is preferred.
前記構造式(1)~(4)中のXは炭素原子数1~4のアルキレン基、アリールメチレン基、アルキレンアリーレンアルキレン基、アルキレンビフェニレンアルキレン基、シクロアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。前記アリールメチレン基、アルキレンアリーレンアルキレン基、アルキレンビフェニレンアルキレン基、シクロアルキレン基は、具体的には、其々、下記構造式で表されるもの等が挙げられる。 X in the structural formulas (1) to (4) is an alkylene group having 1 to 4 carbon atoms, an arylmethylene group, an alkylenearylenealkylene group, an alkylenebiphenylenealkylene group, a cycloalkylene group, an oxygen atom, a sulfur atom, and a carbonyl group. is either Specific examples of the arylmethylene group, alkylenearylenealkylene group, alkylenebiphenylenealkylene group, and cycloalkylene group include those represented by the following structural formulas.
これら分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)の中でも、硬化物における耐熱性や誘電特性の他、汎用溶剤への溶解性や低溶融粘度性に優れるポリエステル樹脂となることから、前記構造式(1)で表される化合物が好ましく、構造式(1)及び(2)中のnの値の合計が1~4の範囲であるものがより好ましい。前記分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)がn数の異なる成分を複数含有する樹脂である場合には、nの値の合計の平均が1~4の範囲であるものが好ましい。 Among these compounds (a2) having two or more phenolic hydroxyl groups in the molecular structure, in addition to heat resistance and dielectric properties in the cured product, it is a polyester resin that is excellent in solubility in general-purpose solvents and low melt viscosity. , the compound represented by the above structural formula (1) is preferable, and those in which the sum of the values of n in the structural formulas (1) and (2) is in the range of 1 to 4 are more preferable. When the compound (a2) having two or more phenolic hydroxyl groups in the molecular structure is a resin containing a plurality of components with n different numbers, the average total value of n is in the range of 1 to 4. is preferred.
更に、前記分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)は、分子中に前記重合性不飽和結合含有炭化水素基(P)を少なくとも1つ有するものが好ましく、1~10個の範囲で有するものがより好ましく、1~4個の範囲で有するものが特に好ましい。前記分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)がn数の異なる成分を複数含有する樹脂である場合には、一分子あたりの重合性不飽和結合含有炭化水素基(P)含有数の平均が1~4の範囲であるものが好ましい。 Furthermore, the compound (a2) having two or more phenolic hydroxyl groups in the molecular structure preferably has at least one polymerizable unsaturated bond-containing hydrocarbon group (P) in the molecule, and preferably has 1 to 10 groups. more preferably in the range of 1 to 4, particularly preferably in the range of 1 to 4. When the compound (a2) having two or more phenolic hydroxyl groups in the molecular structure is a resin containing a plurality of components with n different numbers, the polymerizable unsaturated bond-containing hydrocarbon group (P) per molecule The average content number is preferably in the range of 1-4.
前記芳香族ポリカルボン酸又はその酸ハロゲン化物(a3)は、例えば、イソフタル酸、テレフタル酸等のベンゼンジカルボン酸;トリメリット酸等のベンゼントリカルボン酸;ナフタレン-1,4-ジカルボン酸、ナフタレン-2,3-ジカルボン酸、ナフタレン-2,6-ジカルボン酸、ナフタレン-2,7-ジカルボン酸等のナフタレンジカルボン酸;これらの酸ハロゲン化物;これらの芳香核上に一つ乃至複数の置換基を有する化合物等が挙げられる。前記酸ハロゲン化物は、酸塩化物、酸臭化物、酸フッ化物、酸ヨウ化物等が挙げられる。また、芳香核上の置換基は前記重合性不飽和結合含有基(P)、アルキル基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基等が挙げられ、其々の具体例は前述の通りである。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。中でも、硬化物における耐熱性や誘電特性に一層優れるポリエステル樹脂となることから、イソフタル酸やテレフタル酸等のベンゼンジカルボン酸又はその酸ハロゲン化物が好ましい。 The aromatic polycarboxylic acid or its acid halide (a3) includes, for example, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid; benzenetricarboxylic acids such as trimellitic acid; naphthalene-1,4-dicarboxylic acid and naphthalene-2. ,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid; acid halides thereof; having one or more substituents on the aromatic nucleus thereof compounds and the like. Examples of the acid halides include acid chlorides, acid bromides, acid fluorides, acid iodides, and the like. Further, substituents on the aromatic nucleus include the aforementioned polymerizable unsaturated bond-containing group (P), alkyl groups, alkoxy groups, halogen atoms, aryl groups, aralkyl groups, etc. Specific examples are as described above. be. Each of these may be used alone, or two or more of them may be used in combination. Among these, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid or acid halides thereof are preferred because they provide polyester resins with even more excellent heat resistance and dielectric properties in cured products.
本発明のポリエステル樹脂は、例えば、アルカリ触媒の存在下、40~65℃程度の温度条件下で各反応原料を混合撹拌する方法により製造することができる。反応は必要に応じて有機溶媒中で行っても良い。また、反応終了後は水洗や再沈殿等により反応生成物を精製しても良い。 The polyester resin of the present invention can be produced, for example, by a method of mixing and stirring each reaction raw material under a temperature condition of about 40 to 65° C. in the presence of an alkali catalyst. You may perform reaction in an organic solvent as needed. Further, after the reaction is completed, the reaction product may be purified by washing with water, reprecipitation, or the like.
前記アルカリ触媒は、例えば、水酸化ナトリウム、水酸化カリウム、トリエチルアミン、ピリジン等が挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。また、3.0~30%程度の水溶液として用いても良い。中でも、触媒能の高い水酸化ナトリウム又は水酸化カリウムが好ましい。 Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. Each of these may be used alone, or two or more of them may be used in combination. Also, it may be used as an aqueous solution of about 3.0 to 30%. Among them, sodium hydroxide or potassium hydroxide with high catalytic ability is preferable.
前記有機溶媒は、例えば、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン溶媒、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル溶媒、セロソルブ、ブチルカルビトール等のカルビトール溶媒、トルエン、キシレン等の芳香族炭化水素溶媒、ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン等が挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上の混合溶媒としても良い。 Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetic ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; and carbitols such as cellosolve and butyl carbitol. Solvents include aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Each of these may be used alone, or two or more of them may be used as a mixed solvent.
各反応原料の反応割合は得られるポリエステル樹脂の所望の物性等に応じて適宜調整されるが、特に好ましくは以下の通りである。 The reaction ratio of each reaction raw material is appropriately adjusted according to the desired physical properties of the polyester resin to be obtained, and is particularly preferably as follows.
前記ポリエステル樹脂が芳香族モノカルボン酸又はその酸ハロゲン化物(a1)と分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)とのエステル化物である場合、前記分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)が有するフェノール性水酸基の合計1モルに対し、前記芳香族モノカルボン酸又はその酸ハロゲン化物(a1)が0.95~1.05モルとなる割合であることが好ましい。この場合、ポリエステル樹脂の150℃における溶融粘度は0.01~5dPa・sの範囲であることが好ましい。なお、本発明において150℃における溶融粘度はASTM D4287に準拠し、ICI粘度計にて測定した値である。また、その官能基当量は150~450g/当量の範囲であることが好ましい。なお、本発明においてポリエステル樹脂中の官能基とは、ポリエステル樹脂中のエステル結合部位とフェノール性水酸基とのことを言う。また、ポリエステル樹脂の官能基当量は、反応原料の仕込み量から算出される値である。 When the polyester resin is an ester of an aromatic monocarboxylic acid or an acid halide thereof (a1) and a compound (a2) having two or more phenolic hydroxyl groups in the molecular structure, the phenolic hydroxyl group in the molecular structure A ratio of 0.95 to 1.05 moles of the aromatic monocarboxylic acid or its acid halide (a1) with respect to a total of 1 mole of phenolic hydroxyl groups possessed by the compound (a2) having two or more is preferred. In this case, the melt viscosity of the polyester resin at 150° C. is preferably in the range of 0.01 to 5 dPa·s. In the present invention, the melt viscosity at 150° C. is a value measured with an ICI viscometer according to ASTM D4287. Also, the functional group equivalent is preferably in the range of 150 to 450 g/equivalent. In the present invention, the functional group in the polyester resin means the ester bond site and the phenolic hydroxyl group in the polyester resin. Further, the functional group equivalent weight of the polyester resin is a value calculated from the charged amount of the reaction raw materials.
前記ポリエステル樹脂が芳香族モノカルボン酸又はその酸ハロゲン化物(a1)、分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)、及び芳香族ポリカルボン酸又はその酸ハロゲン化物(a3)のエステル化物である場合、前記芳香族モノカルボン酸又はその酸ハロゲン化物(a1)が有するカルボキシル基又は酸ハライド基の合計1モルに対し、前記芳香族ポリカルボン酸又はその酸ハロゲン化物(a3)が有するカルボキシル基又は酸ハライド基の合計との割合が0.5~5モルの範囲であることが好ましく、0.8~3モルの範囲であることがより好ましい。また、前記分子構造中にフェノール性水酸基を2つ以上有する化合物(a2)が有する水酸基1モルに対し、前記芳香族モノカルボン酸又はその酸ハロゲン化物(a1)と前記芳香族ポリカルボン酸又はその酸ハロゲン化物(a3)とが有するカルボキシル基又は酸ハライド基の合計が0.9~1.1の範囲であることが好ましい。この場合、ポリエステル樹脂の軟化点はJIS K7234に基づいて測定される値で60~200℃の範囲であることが好ましく、80~180℃の範囲であることがより好ましい。また、その官能基当量は150~450g/当量の範囲であることが好ましい。 The polyester resin comprises an aromatic monocarboxylic acid or an acid halide thereof (a1), a compound having two or more phenolic hydroxyl groups in the molecular structure (a2), and an aromatic polycarboxylic acid or an acid halide thereof (a3). When it is an esterified product, the aromatic polycarboxylic acid or its acid halide (a3) is added to a total of 1 mol of the carboxyl groups or acid halide groups possessed by the aromatic monocarboxylic acid or its acid halide (a1). The ratio to the total number of carboxyl groups or acid halide groups possessed is preferably in the range of 0.5 to 5 mol, more preferably in the range of 0.8 to 3 mol. Further, the aromatic monocarboxylic acid or its acid halide (a1) and the aromatic polycarboxylic acid or its The total number of carboxyl groups or acid halide groups possessed by the acid halide (a3) is preferably in the range of 0.9 to 1.1. In this case, the softening point of the polyester resin is preferably in the range of 60 to 200°C, more preferably in the range of 80 to 180°C, as measured according to JIS K7234. Also, the functional group equivalent is preferably in the range of 150 to 450 g/equivalent.
本発明のポリエステル樹脂は、分子構造中に重合性不飽和結合含有基(P)を有することから、それ単独で硬化性の樹脂材料として用いることができる。また、各種添加剤や、前記ポリエステル樹脂のエステル結合部位或いは重合性不飽和結合含有基(P)と反応し得る硬化剤と配合して硬化性樹脂組成物として用いてもよい。前記硬化剤は本発明のポリエステル樹脂と反応し得る化合物であれば良く、特に限定なく様々な化合物が利用できる。硬化剤の一例としては、例えば、エステル結合部位と硬化反応を生じる得るものとしてエポキシ樹脂、重合性不飽和結合含有基(P)と硬化反応を生じ得るものとしてビスマレイミド樹脂、スチレン-無水マレイン酸樹脂、ジアリルビスフェノールやトリアリルイソシアヌレート等に代表されるアリル基含有樹脂等が挙げられる。
が挙げられる。
Since the polyester resin of the present invention has a polymerizable unsaturated bond-containing group (P) in its molecular structure, it can be used alone as a curable resin material. It may also be used as a curable resin composition by blending with various additives and a curing agent capable of reacting with the ester bond site or polymerizable unsaturated bond-containing group (P) of the polyester resin. The curing agent may be any compound that can react with the polyester resin of the present invention, and various compounds can be used without particular limitation. Examples of curing agents include epoxy resins that can cause a curing reaction with an ester bond site, bismaleimide resins that can cause a curing reaction with a polymerizable unsaturated bond-containing group (P), and styrene-maleic anhydride. Examples include resins, allyl group-containing resins represented by diallyl bisphenol, triallyl isocyanurate, and the like.
is mentioned.
前記エポキシ樹脂は、例えば、ビスフェノール型エポキシ樹脂;ビフェニル型エポキシ樹脂;フェノールやクレゾール、ナフトール、ビフェノール、ビスフェノール等を原料とする各種のノボラック型エポキシ樹脂;トリフェノールメタン型エポキシ樹脂;ジシクロペンタジエン-フェノール付加反応型エポキシ樹脂;ポリアリーレンエーテル型エポキシ樹脂;フェノールやクレゾール、ナフトール、ビフェノール、ビスフェノール等がアリーレンジアルキレン基で連結された樹脂構造を有するフェノール樹脂のポリグリシジルエーテル等が挙げられる。 The epoxy resins include, for example, bisphenol-type epoxy resins; biphenyl-type epoxy resins; various novolac-type epoxy resins made from phenol, cresol, naphthol, biphenol, bisphenol, etc.; triphenolmethane-type epoxy resins; dicyclopentadiene-phenol addition reaction type epoxy resins; polyarylene ether type epoxy resins; and polyglycidyl ethers of phenol resins having a resin structure in which phenol, cresol, naphthol, biphenol, bisphenol, etc. are linked by arylene dialkylene groups.
前記硬化剤としてエポキシ樹脂を用いる場合、更に、一般的なエポキシ樹脂用硬化剤として用いられている各種の化合物を併用してもよい。その具体例としては、本発明のポリエステル樹脂以外の活性エステル樹脂、フェノール樹脂、アミン化合物、アミド化合物、酸無水物等が挙げられる。これらを用いる場合、本発明の効果が十分に発揮されることから、本発明のポリエステル樹脂を含むエポキシ樹脂硬化剤の総質量に対し、本発明のポリエステル樹脂の割合が30質量%以上であることが好ましく、50質量%以上であることがより好ましい。 When an epoxy resin is used as the curing agent, various compounds commonly used as curing agents for epoxy resins may be used in combination. Specific examples thereof include active ester resins other than the polyester resin of the present invention, phenol resins, amine compounds, amide compounds, acid anhydrides, and the like. When these are used, the effects of the present invention are sufficiently exhibited, so the ratio of the polyester resin of the present invention to the total mass of the epoxy resin curing agent containing the polyester resin of the present invention is 30% by mass or more. is preferred, and it is more preferably 50% by mass or more.
前記エポキシ樹脂用硬化剤は、エポキシ樹脂と硬化反応を生じるものであれば特に限定なく、多種多様のものを用いることができる。その具体例としては、アミン化合物、アミド化合物、酸無水物、フェノ-ル樹脂、活性エステル樹脂等が挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。前記アミン化合物は、例えば、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、BF3-アミン錯体、グアニジン誘導体等が挙げられる。前記アミド系化合物は、例えば、ジシアンジアミド、脂肪族二塩基酸やダイマー酸、脂肪酸のカルボン酸化合物とエチレンジアミン等のアミンとより合成されるポリアミド樹脂等が挙げられる。前記酸無水物は、例えば、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。前記フェノール樹脂は、例えば、フェノールやクレゾール、ナフトール、ビフェノール、ビスフェノール等を原料とする各種のノボラック樹脂、トリフェノールメタン型樹脂、ジシクロペンタジエン付加型フェノール樹脂、ポリアリーレンエーテル型フェノール樹脂、フェノールやクレゾール、ナフトール、ビフェノール、ビスフェノール等がアリーレンジアルキレン基で連結された樹脂構造を有するフェノール樹脂等が挙げられる。前記活性エステル樹脂は、例えば、前記フェノール樹脂と芳香族ジカルボン酸、フェノール性水酸基含有化合物とのエステル化物、芳香族ジカルボン酸とフェノール性水酸基含有化合物とのエステル化物等が挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。 The epoxy resin curing agent is not particularly limited as long as it causes a curing reaction with the epoxy resin, and a wide variety of agents can be used. Specific examples thereof include amine compounds, amide compounds, acid anhydrides, phenol resins and active ester resins. Each of these may be used alone, or two or more of them may be used in combination. Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, BF 3 -amine complexes, and guanidine derivatives. Examples of the amide compounds include dicyandiamide, aliphatic dibasic acids, dimer acids, and polyamide resins synthesized from carboxylic acid compounds of fatty acids and amines such as ethylenediamine. The acid anhydrides are, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydro Examples include phthalic anhydride and the like. Examples of the phenolic resin include various novolac resins, triphenolmethane type resins, dicyclopentadiene addition type phenolic resins, polyarylene ether type phenolic resins, phenol and cresol, which are made from phenol, cresol, naphthol, biphenol, bisphenol, and the like. , naphthol, biphenol, bisphenol, etc., having a resin structure linked by an arylene dialkylene group, and the like. Examples of the active ester resin include esterified products of the phenolic resin and aromatic dicarboxylic acid, phenolic hydroxyl group-containing compounds, and esterified compounds of aromatic dicarboxylic acid and phenolic hydroxyl group-containing compounds. Each of these may be used alone, or two or more of them may be used in combination.
本発明のポリエステル樹脂、エポキシ樹脂、及びその他のエポキシ樹脂用硬化剤の配合割合は、エポキシ樹脂中のエポキシ基の合計1モルに対して、前記ポリエステル樹脂及びその他のエポキシ樹脂用硬化剤中の官能基の合計が0.7~1.5モルとなる割合であることが好ましい。 The blending ratio of the polyester resin, epoxy resin, and other curing agent for epoxy resins of the present invention is such that, with respect to a total of 1 mol of epoxy groups in the epoxy resin, The ratio is preferably such that the total number of groups is 0.7 to 1.5 mol.
本発明の硬化性樹脂組成物は、この他、シアン酸エステル樹脂、ベンゾオキサジン樹脂、ポリフェニレンエーテル樹脂、アクリル樹脂、ポリリン酸エステルやリン酸エステル-カーボネート共重合体等を含有しても良い。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。 The curable resin composition of the present invention may also contain cyanate ester resins, benzoxazine resins, polyphenylene ether resins, acrylic resins, polyphosphate esters, phosphate ester-carbonate copolymers, and the like. Each of these may be used alone, or two or more of them may be used in combination.
本発明の硬化性樹脂組成物は必要に応じて硬化促進剤、難燃剤、無機質充填材、シランカップリング剤、離型剤、顔料、乳化剤等の各種添加剤を含有しても良い。 The curable resin composition of the present invention may optionally contain various additives such as curing accelerators, flame retardants, inorganic fillers, silane coupling agents, release agents, pigments and emulsifiers.
前記硬化促進剤は、例えば、リン系化合物、第3級アミン、イミダゾール化合物、ピリジン化合物、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。中でも、硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、リン系化合物ではトリフェニルホスフィン、第3級アミンでは1,8-ジアザビシクロ-[5.4.0]-ウンデセン(DBU)、イミダゾール化合物では2-エチル-4-メチルイミダゾール、ピリジン化合物では4-ジメチルアミノピリジンが好ましい。 Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, and amine complex salts. Among them, triphenylphosphine is a phosphorus compound and 1,8-diazabicyclo-[5.4.0]-undecene (DBU ), the imidazole compound is preferably 2-ethyl-4-methylimidazole, and the pyridine compound is preferably 4-dimethylaminopyridine.
前記難燃剤は、例えば、赤リン、リン酸一アンモニウム、リン酸二アンモニウム、リン酸三アンモニウム、ポリリン酸アンモニウム等のリン酸アンモニウム、リン酸アミド等の無機リン化合物;リン酸エステル化合物、ホスホン酸化合物、ホスフィン酸化合物、ホスフィンオキシド化合物、ホスホラン化合物、有機系含窒素リン化合物、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキシド、10-(2,5―ジヒドロオキシフェニル)―10H-9-オキサ-10-ホスファフェナントレン-10-オキシド、10―(2,7-ジヒドロオキシナフチル)-10H-9-オキサ-10-ホスファフェナントレン-10-オキシド等の環状有機リン化合物、及びそれをエポキシ樹脂やフェノール樹脂等の化合物と反応させた誘導体等の有機リン化合物;トリアジン化合物、シアヌル酸化合物、イソシアヌル酸化合物、フェノチアジン等の窒素系難燃剤;シリコーンオイル、シリコーンゴム、シリコーン樹脂等のシリコーン系難燃剤;金属水酸化物、金属酸化物、金属炭酸塩化合物、金属粉、ホウ素化合物、低融点ガラス等の無機難燃剤等が挙げられる。これら難燃剤を用いる場合は、硬化性樹脂組成物中0.1~20質量%の範囲であることが好ましい。 The flame retardant is, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphoric acid amide; compound, phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl )-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus organic phosphorus compounds such as compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, nitrogen-based flame retardants such as phenothiazine; silicone oils, silicone rubbers, silicones silicone-based flame retardants such as resins; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When using these flame retardants, it is preferably in the range of 0.1 to 20% by mass in the curable resin composition.
前記無機質充填材は、例えば、本発明の硬化性樹脂組成物を半導体封止材料用途に用いる場合などに配合される。前記無機質充填材は、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ等が挙げられる。中でも、無機質充填材をより多く配合することが可能となることから、前記溶融シリカが好ましい。前記溶融シリカは破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め、且つ、硬化性組成物の溶融粘度の上昇を抑制するためには、球状のものを主に用いることが好ましい。更に、球状シリカの配合量を高めるためには、球状シリカの粒度分布を適当に調整することが好ましい。その充填率は硬化性樹脂組成物100質量部中、0.5~95質量部の範囲で配合することが好ましい。 The inorganic filler is added, for example, when the curable resin composition of the present invention is used as a semiconductor sealing material. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among them, the fused silica is preferable because it allows a larger amount of inorganic filler to be blended. The fused silica may be crushed or spherical, but spherical fused silica is mainly used in order to increase the amount of fused silica and to suppress the increase in the melt viscosity of the curable composition. is preferred. Furthermore, in order to increase the compounding amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass per 100 parts by mass of the curable resin composition.
この他、本発明の硬化性樹脂組成物を導電ペーストなどの用途に使用する場合は、銀粉や銅粉等の導電性充填剤を用いることができる。 In addition, when the curable resin composition of the present invention is used as a conductive paste, a conductive filler such as silver powder or copper powder can be used.
以上詳述した通り、本発明のポリエステル樹脂は、硬化物における耐熱性や誘電特性に優れる特徴を有する。この他、汎用有機溶剤への溶解性や、エポキシ樹脂との硬化性、耐吸湿性、保存安定性、基剤密着性等、樹脂材料に求められる一般的な要求性能も十分に高いものであり、プリント配線基板や半導体封止材料、レジスト材料等の電子材料用途の他、塗料や接着剤、成型品等の用途にも広く利用することができる。 As described in detail above, the polyester resin of the present invention is characterized by excellent heat resistance and dielectric properties when cured. In addition, general performance requirements for resin materials, such as solubility in general-purpose organic solvents, curability with epoxy resins, moisture absorption resistance, storage stability, and adhesion to base materials, are sufficiently high. , electronic materials such as printed wiring boards, semiconductor sealing materials, and resist materials, as well as coatings, adhesives, molded products, and the like.
本発明の硬化性樹脂組成物をプリント配線基板用途やビルドアップ接着フィルム用途に用いる場合、一般には有機溶剤を配合して希釈して用いることが好ましい。前記有機溶剤は、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。有機溶剤の種類や配合量は硬化性樹脂組成物の使用環境に応じて適宜調整できるが、例えば、プリント配線板用途では、メチルエチルケトン、アセトン、ジメチルホルムアミド等の沸点が160℃以下の極性溶剤であることが好ましく、不揮発分が40~80質量%となる割合で使用することが好ましい。ビルドアップ接着フィルム用途では、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン溶剤、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル溶剤、セロソルブ、ブチルカルビトール等のカルビトール溶剤、トルエン、キシレン等の芳香族炭化水素溶剤、ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン等を用いることが好ましく、不揮発分が30~60質量%となる割合で使用することが好ましい。 When the curable resin composition of the present invention is used for printed wiring boards or build-up adhesive films, it is generally preferable to mix and dilute an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The type and blending amount of the organic solvent can be appropriately adjusted according to the environment in which the curable resin composition is used. It is preferable to use the non-volatile content at a ratio of 40 to 80% by mass. For build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetic ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; and carbitols such as cellosolve and butyl carbitol. It is preferable to use solvents such as aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use such a proportion that the non-volatile content is 30 to 60% by mass.
また、本発明の硬化性樹脂組成物を用いてプリント配線基板を製造する方法は、例えば、硬化性組成物を補強基材に含浸し硬化させてプリプレグを得、これと銅箔とを重ねて加熱圧着させる方法が挙げられる。前記補強基材は、紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布などが挙げられる。硬化性樹脂組成物の含浸量は特に限定されないが、通常、プリプレグ中の樹脂分が20~60質量%となるように調製することが好ましい。 In addition, a method for producing a printed wiring board using the curable resin composition of the present invention includes, for example, impregnating a reinforcing base material with the curable composition and curing it to obtain a prepreg, which is laminated with a copper foil. A method of thermocompression bonding can be used. Examples of the reinforcing base material include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. Although the amount of the curable resin composition to be impregnated is not particularly limited, it is usually preferable to adjust the resin content in the prepreg to 20 to 60% by mass.
本発明の硬化性樹脂組成物を半導体封止材料用途に用いる場合、一般には無機質充填材を配合することが好ましい。本発明のポリエステル樹脂と硬化剤、無機質充填剤、及びその他の任意成分を含有する半導体封止材料は、例えば、押出機、ニーダー、ロール等を用いて配合物を混合して調製することができる。得られた半導体封止材料を用いて半導体パッケージを成型する方法は、例えば、該半導体封止材料を注型或いはトランスファー成形機、射出成型機などを用いて成形し、更に50~200℃の温度条件下で2~10時間加熱する方法が挙げられ、このような方法により、成形物である半導体装置を得ることが出来る。 When the curable resin composition of the present invention is used as a semiconductor encapsulating material, it is generally preferred to incorporate an inorganic filler. The semiconductor encapsulating material containing the polyester resin of the present invention, a curing agent, an inorganic filler, and other optional components can be prepared, for example, by mixing formulations using an extruder, a kneader, a roll, or the like. . A method of molding a semiconductor package using the obtained semiconductor encapsulating material includes, for example, molding the semiconductor encapsulating material using a cast molding machine, a transfer molding machine, an injection molding machine, etc. A method of heating for 2 to 10 hours under certain conditions can be mentioned, and a semiconductor device, which is a molded product, can be obtained by such a method.
次に本発明を実施例、比較例により具体的に説明する。実施例中の「部」及び「%」の記載は、特に断わりのない限り質量基準である。 EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples. Descriptions of "parts" and "%" in the examples are based on mass unless otherwise specified.
本実施例において樹脂のGPCチャートは下記条件にて測定した。 In this example, the GPC chart of the resin was measured under the following conditions.
測定装置 :東ソー株式会社製「HLC-8220 GPC」、
カラム:東ソー株式会社製ガードカラム「HXL-L」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G3000HXL」
+東ソー株式会社製「TSK-GEL G4000HXL」
検出器: RI(示差屈折計)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.10」
測定条件: カラム温度 40℃
展開溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 : 前記「GPC-8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
(使用ポリスチレン)
東ソー株式会社製「A-500」
東ソー株式会社製「A-1000」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of "GPC-8020 Model II Version 4.10".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: 1.0% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)
本実施例において、ポリエステル樹脂中の官能基とは、ポリエステル樹脂中のエステル結合部位とフェノール性水酸基とのことを言う。また、ポリエステル樹脂の官能基当量は、反応原料の仕込み量から算出される値である。 In this embodiment, the functional group in the polyester resin refers to the ester bond site and the phenolic hydroxyl group in the polyester resin. Further, the functional group equivalent weight of the polyester resin is a value calculated from the charged amount of the reaction raw materials.
実施例1 ポリエステル樹脂(1)の製造
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにジアリルビスフェノールA320gとトルエン1500gを仕込み、フラスコ内を減圧窒素置換しながら内容物を溶解させた。次いで、ベンゾイルクロライド281gを仕込み、フラスコ内を減圧窒素置換しながら内容物を溶解させた。更にテトラブチルアンモニウムブロマイド0.8gを加えて溶解させた。窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液412gを3時間かけて滴下した。滴下終了後、同条件下で1.0時間撹拌を続けた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残ったトルエン相に水を投入して約15分間撹拌混合し、静置して水層を取り除いた。水層のpHが7になるまでこの操作を繰り返した。加熱減圧下条件下で乾燥させて活性エステル樹脂(1)505gを得た。活性エステル樹脂(1)の理論構造は下記構造式の通り。活性エステル樹脂(1)の官能基当量は264g/当量、ASTM D4287に準拠しICI粘度計にて測定した150℃での溶融粘度は0.2dPa・sであった。ポリエステル樹脂(1)のGPCチャート図を図1に示す。
Example 1 Production of Polyester Resin (1) A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 320 g of diallyl bisphenol A and 1500 g of toluene. Dissolved. Next, 281 g of benzoyl chloride was charged, and the contents were dissolved while the inside of the flask was replaced with nitrogen under reduced pressure. Further, 0.8 g of tetrabutylammonium bromide was added and dissolved. While purging with nitrogen gas, the inside of the system was controlled at 60° C. or less, and 412 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After the dropwise addition was completed, stirring was continued for 1.0 hour under the same conditions. After completion of the reaction, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Water was added to the remaining toluene phase, stirred and mixed for about 15 minutes, left to stand, and the water layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. It was dried under heating and reduced pressure conditions to obtain 505 g of active ester resin (1). The theoretical structure of the active ester resin (1) is as shown in the following structural formula. The active ester resin (1) had a functional group equivalent weight of 264 g/equivalent and a melt viscosity of 0.2 dPa·s at 150° C. measured with an ICI viscometer according to ASTM D4287. FIG. 1 shows a GPC chart of the polyester resin (1).
実施例2 ポリエステル樹脂(2)の製造
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにジアリルビスフェノールA641gとトルエン2900gを仕込み、フラスコ内を減圧窒素置換しながら内容物を溶解させた。次いで、ベンゾイルクロライド281gとイソフタル酸クロリド203gを仕込み、フラスコ内を減圧窒素置換しながら内容物を溶解させた。更にテトラブチルアンモニウムブロマイド1.5gを加えて溶解させた。窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液824gを3時間かけて滴下した。滴下終了後、同条件下で1.0時間撹拌を続けた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残ったトルエン相に水を投入して約15分間撹拌混合し、静置して水層を取り除いた。水層のpHが7になるまでこの操作を繰り返した。加熱減圧条件下で乾燥させて活性エステル樹脂(2)950gを得た。活性エステル樹脂(2)の理論構造は下記構造式の通り。この活性エステル樹脂(2)の官能基当量は245g/当量、JIS K7234に基づいて測定した軟化点は65℃であった。ポリエステル樹脂(2)のGPCチャート図を図2に示す。
Example 2 Production of polyester resin (2) A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 641 g of diallyl bisphenol A and 2900 g of toluene. Dissolved. Next, 281 g of benzoyl chloride and 203 g of isophthaloyl chloride were charged, and the contents were dissolved while the inside of the flask was replaced with nitrogen under reduced pressure. Further, 1.5 g of tetrabutylammonium bromide was added and dissolved. While purging with nitrogen gas, the inside of the system was controlled at 60° C. or lower, and 824 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After the dropwise addition was completed, stirring was continued for 1.0 hour under the same conditions. After completion of the reaction, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Water was added to the remaining toluene phase, stirred and mixed for about 15 minutes, left to stand, and the water layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. After drying under heating and reduced pressure conditions, 950 g of active ester resin (2) was obtained. The theoretical structure of the active ester resin (2) is as shown in the following structural formula. The active ester resin (2) had a functional group equivalent weight of 245 g/equivalent and a softening point of 65° C. measured according to JIS K7234. FIG. 2 shows a GPC chart of the polyester resin (2).
比較製造例1 ポリエステル樹脂(1’)の製造
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにジシクロペンタジエンとフェノールの重付付加反応樹脂(水酸基当量165g/当量、軟化点85℃)165g、1-ナフトール72g、トルエン630gを仕込み、系内を減圧窒素置換し溶解させた。次いで、イソフタル酸クロライド152g(0.75モル)を仕込み、フラスコ内を減圧窒素置換しながら内容物を溶解させた。次に、テトラブチルアンモニウムブロマイド0.6gを加えて溶解させた。窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液315gを3時間かけて滴下した。滴下終了後、同条件下で1.0時間撹拌を続けた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残ったトルエン層に水を投入して約15分間撹拌混合し、静置して水層を取り除いた。水層のpHが7になるまでこの操作を繰り返した。加熱減圧条件下で乾燥させて活性エステル樹脂(1’)を得た。活性エステル樹脂(1’)の官能基当量は223g/当量、軟化点は150℃であった。
Comparative Production Example 1 Production of polyester resin (1′) A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer was charged with a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/equivalent, 165 g of softening point 85° C.), 72 g of 1-naphthol and 630 g of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Then, 152 g (0.75 mol) of isophthaloyl chloride was charged, and the content was dissolved while the inside of the flask was replaced with nitrogen under reduced pressure. Next, 0.6 g of tetrabutylammonium bromide was added and dissolved. While purging with nitrogen gas, the inside of the system was controlled at 60° C. or lower, and 315 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After the dropwise addition was completed, stirring was continued for 1.0 hour under the same conditions. After completion of the reaction, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Water was added to the remaining toluene layer, stirred and mixed for about 15 minutes, left still, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. It was dried under heating and reduced pressure conditions to obtain an active ester resin (1'). The active ester resin (1') had a functional group equivalent weight of 223 g/equivalent and a softening point of 150°C.
実施例3、4及び比較例1
ポリエステル樹脂、エポキシ樹脂、ジメチルアミノピリジンを下記表1に示す割合で配合して硬化性樹脂組成物を得た。得られた硬化性樹脂組成物について、下記要領で各種評価試験を行った。結果を表1に示す。
エポキシ樹脂(1):ジシクロペンタジエン変性フェノール型エポキシ樹脂(DIC株式会社製「EPICLON HP-7200H」、エポキシ当量277g/当量)
エポキシ樹脂(2):ビスフェノールA型エポキシ樹脂(DIC株式会社製「EPICLON 850-S」、エポキシ当量188g/当量)
Examples 3, 4 and Comparative Example 1
A curable resin composition was obtained by blending a polyester resin, an epoxy resin, and dimethylaminopyridine in the proportions shown in Table 1 below. Various evaluation tests were performed on the obtained curable resin composition in the following manner. Table 1 shows the results.
Epoxy resin (1): dicyclopentadiene-modified phenol-type epoxy resin (manufactured by DIC Corporation "EPICLON HP-7200H", epoxy equivalent 277 g/equivalent)
Epoxy resin (2): Bisphenol A type epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent 188 g/equivalent)
硬化物の作成
先で得た硬化性樹脂組成物を11cm×9cm×2.4mmの型枠に流し込み、プレスで180℃の温度で20分間成型した。型枠から成型物を取り出し、更に、175℃5時間、250℃2時間硬化させて硬化物を得た。
Preparation of Cured Product The curable resin composition obtained above was poured into a mold of 11 cm×9 cm×2.4 mm and molded with a press at a temperature of 180° C. for 20 minutes. The molded product was removed from the mold and further cured at 175° C. for 5 hours and 250° C. for 2 hours to obtain a cured product.
ガラス転移温度の測定
硬化物から5mm×54mm×2.4mmの試験片を切り出した。
粘弾性測定装置(レオメトリック社製「固体粘弾性測定装置RSAII」)を用い、レクタンギュラーテンション法によるDMA(動的粘弾性)測定により弾性率変化点(tanδ変化率が大きい)の温度を測定した。複数の弾性率変化点が測定された場合は、最も高い温度を耐熱性として評価した。測定条件は、周波数1Hz、昇温温度3℃/分とした。
Measurement of Glass Transition Temperature A test piece of 5 mm×54 mm×2.4 mm was cut out from the cured product.
Using a viscoelasticity measuring device (“Solid viscoelasticity measuring device RSA II” manufactured by Rheometric Co., Ltd.), the temperature at the elastic modulus change point (tan δ change rate is large) was measured by DMA (dynamic viscoelasticity) measurement by the rectangular tension method. . When multiple elastic modulus change points were measured, the highest temperature was evaluated as the heat resistance. The measurement conditions were a frequency of 1 Hz and a temperature rise of 3° C./min.
誘電正接の測定
硬化物を加熱真空乾燥後、23℃、湿度50%の室内に24時間保管した後、アジレント・テクノロジー株式会社製ネットワークアナライザ「E8362C」を用い、空洞共振法にて誘電正接を測定した。
Measurement of dielectric loss tangent After heating and vacuum drying the cured product, store it in a room at 23°C and 50% humidity for 24 hours. did.
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