JP2019119833A - Thermosetting resin composition and cured article thereof - Google Patents
Thermosetting resin composition and cured article thereof Download PDFInfo
- Publication number
- JP2019119833A JP2019119833A JP2018002418A JP2018002418A JP2019119833A JP 2019119833 A JP2019119833 A JP 2019119833A JP 2018002418 A JP2018002418 A JP 2018002418A JP 2018002418 A JP2018002418 A JP 2018002418A JP 2019119833 A JP2019119833 A JP 2019119833A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- group
- thermosetting resin
- resin
- indene
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 69
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 56
- 239000003822 epoxy resin Substances 0.000 claims abstract description 48
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 48
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000005011 phenolic resin Substances 0.000 claims abstract description 26
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 229920003986 novolac Polymers 0.000 claims abstract description 21
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 46
- 238000001723 curing Methods 0.000 claims description 22
- 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 claims description 16
- 238000013007 heat curing Methods 0.000 claims description 8
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 abstract description 26
- 150000002469 indenes Chemical class 0.000 abstract description 15
- 239000000047 product Substances 0.000 description 68
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000011156 evaluation Methods 0.000 description 23
- -1 pentadiene modified phenol Chemical class 0.000 description 20
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 150000002989 phenols Chemical class 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 14
- 239000003377 acid catalyst Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- SPFZKMMPGXBEPX-UHFFFAOYSA-N 1-propyl-1h-indene Chemical compound C1=CC=C2C(CCC)C=CC2=C1 SPFZKMMPGXBEPX-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 235000019256 formaldehyde Nutrition 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 238000011088 calibration curve Methods 0.000 description 5
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical group C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- LYRSLMWAHYTKIG-UHFFFAOYSA-N 3-(1h-inden-1-yl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C2C3=CC=CC=C3C=C2)=C1 LYRSLMWAHYTKIG-UHFFFAOYSA-N 0.000 description 4
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 3
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 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 2
- AMNBEEFDKXPOCA-UHFFFAOYSA-N 2,3-dimethylphenol;2,6-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C.CC1=CC=CC(C)=C1O AMNBEEFDKXPOCA-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WLOHKZPZHBMVBK-UHFFFAOYSA-N 2-(chloromethyl)oxirane Chemical compound ClCC1CO1.ClCC1CO1 WLOHKZPZHBMVBK-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- VSSZKXRAUHZJFV-UHFFFAOYSA-N 3,5-dimethylphenol Chemical group CC1=CC(C)=CC(O)=C1.CC1=CC(C)=CC(O)=C1 VSSZKXRAUHZJFV-UHFFFAOYSA-N 0.000 description 2
- IRAWLGHJHQBREM-UHFFFAOYSA-N 4-methyl-1h-indene Chemical compound CC1=CC=CC2=C1C=CC2 IRAWLGHJHQBREM-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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002460 imidazoles Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- CGUISEQGDJSNFM-UHFFFAOYSA-N 1-(1h-inden-1-yl)naphthalene Chemical class C1=CC=C2C(C3C4=CC=CC=C4C=C3)=CC=CC2=C1 CGUISEQGDJSNFM-UHFFFAOYSA-N 0.000 description 1
- KQTUDLZJWGRUNH-UHFFFAOYSA-N 1-(1h-inden-4-yl)naphthalene Chemical class C1=CC=C2C(C3=CC=CC4=C3C=CC4)=CC=CC2=C1 KQTUDLZJWGRUNH-UHFFFAOYSA-N 0.000 description 1
- BZXCTOUQHHTLCO-UHFFFAOYSA-N 1-(1h-inden-5-yl)naphthalene Chemical class C1=CC=C2C(C=3C=C4C=CCC4=CC=3)=CC=CC2=C1 BZXCTOUQHHTLCO-UHFFFAOYSA-N 0.000 description 1
- HXFBWURKBSHKGH-UHFFFAOYSA-N 1-(3h-inden-1-yl)naphthalene Chemical class C1=CC=C2C(C3=CCC4=CC=CC=C43)=CC=CC2=C1 HXFBWURKBSHKGH-UHFFFAOYSA-N 0.000 description 1
- YXMOIKVSXKGFFD-UHFFFAOYSA-N 1-(3h-inden-4-yl)naphthalene Chemical class C1=CC=C2C(C=3C=CC=C4C=CCC=34)=CC=CC2=C1 YXMOIKVSXKGFFD-UHFFFAOYSA-N 0.000 description 1
- DPHLCNUTUWZQCX-UHFFFAOYSA-N 1-(3h-inden-5-yl)naphthalene Chemical class C1=CC=C2C(C3=CC=C4C=CCC4=C3)=CC=CC2=C1 DPHLCNUTUWZQCX-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- IEKPDJDYFASRFB-UHFFFAOYSA-N 1-ethyl-1h-indene Chemical compound C1=CC=C2C(CC)C=CC2=C1 IEKPDJDYFASRFB-UHFFFAOYSA-N 0.000 description 1
- PXORBAGTGTXORO-UHFFFAOYSA-N 1-phenyl-1h-indene Chemical class C1=CC2=CC=CC=C2C1C1=CC=CC=C1 PXORBAGTGTXORO-UHFFFAOYSA-N 0.000 description 1
- VTACPFVLSHWTGG-UHFFFAOYSA-N 1-propan-2-yl-1h-indene Chemical compound C1=CC=C2C(C(C)C)C=CC2=C1 VTACPFVLSHWTGG-UHFFFAOYSA-N 0.000 description 1
- IHHBPJRQKRVWAY-UHFFFAOYSA-N 1-tert-butyl-1h-indene Chemical compound C1=CC=C2C(C(C)(C)C)C=CC2=C1 IHHBPJRQKRVWAY-UHFFFAOYSA-N 0.000 description 1
- VRLWYYZVFNNMET-UHFFFAOYSA-N 16327-42-7 Chemical compound C1C2C3C(C)C=CC3C1C=C2 VRLWYYZVFNNMET-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- LMFSGXGLXDXFHH-UHFFFAOYSA-N 2-(1h-inden-1-yl)naphthalene Chemical class C1=CC=CC2=CC(C3C4=CC=CC=C4C=C3)=CC=C21 LMFSGXGLXDXFHH-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical class CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- BSHJHVHMLRKHBZ-UHFFFAOYSA-N 2-ethyl-1h-indene Chemical compound C1=CC=C2CC(CC)=CC2=C1 BSHJHVHMLRKHBZ-UHFFFAOYSA-N 0.000 description 1
- ABLCFODXAYBNID-UHFFFAOYSA-N 2-heptyl-1h-imidazole Chemical compound CCCCCCCC1=NC=CN1 ABLCFODXAYBNID-UHFFFAOYSA-N 0.000 description 1
- YSAXEHWHSLANOM-UHFFFAOYSA-N 2-methyl-1h-indene Chemical compound C1=CC=C2CC(C)=CC2=C1 YSAXEHWHSLANOM-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
- BSBXLZYWGGAVHD-UHFFFAOYSA-N 2-phenyl-1h-indene Chemical class C=1C2=CC=CC=C2CC=1C1=CC=CC=C1 BSBXLZYWGGAVHD-UHFFFAOYSA-N 0.000 description 1
- NIZLMLNEWVSBGD-UHFFFAOYSA-N 2-propan-2-yl-1h-indene Chemical compound C1=CC=C2CC(C(C)C)=CC2=C1 NIZLMLNEWVSBGD-UHFFFAOYSA-N 0.000 description 1
- ZYFRKOCXVOSMQM-UHFFFAOYSA-N 2-tert-butyl-1h-indene Chemical compound C1=CC=C2CC(C(C)(C)C)=CC2=C1 ZYFRKOCXVOSMQM-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、熱硬化性樹脂組成物およびその硬化物に関する。 The present invention relates to a thermosetting resin composition and a cured product thereof.
エポキシ樹脂をフェノール性水酸基、アミノ基または酸無水物基等を持つ化合物によって硬化して得られる硬化物は、強度、耐熱性および難燃性が優れることから、プリント配線基板および半導体封止材等の原料として用いられている。 A cured product obtained by curing an epoxy resin with a compound having a phenolic hydroxyl group, an amino group, an acid anhydride group or the like is excellent in strength, heat resistance and flame retardancy, and thus a printed wiring board, a semiconductor sealing material, etc. It is used as a raw material for
近年、電子機器、特に、情報通信機器の分野においては、通信速度の高速化およびデータ処理の大容量化が進んでいることから、高速大容量の処理が求められる高周波回路では、伝送損失が少ない、誘電特性に優れた材料に対する需要が高まってきている。 In recent years, in the field of electronic devices, in particular, information communication devices, transmission speed has been increased and data processing has been increased in capacity, so high frequency circuits requiring high speed and large capacity processing have less transmission loss. There is an increasing demand for materials with excellent dielectric properties.
また、従来、電子回路などの基板に電子部品を搭載するためには鉛と錫の合金であるはんだ（含鉛はんだ）が大量に使用されていた。しかし、鉛は人体に有害であり、環境負荷も高いことから、欧州連合ではパソコンおよびテレビ受像機など電気・電子機器への含鉛はんだの使用が原則として禁止され（ＲｏＨＳ）、さらに日本をはじめとする各国でも規制が進んでいる（Ｊ−ＭＯＳＳなど）。そのため、含鉛はんだから、鉛を含まない鉛フリーはんだ（無鉛はんだ）への切り替えが進められているが、鉛フリーはんだは、合金の溶融温度がこれまでの含鉛はんだよりも高いため、はんだが接触する部材には、より高い耐熱性が要求されるようになった。 Also, conventionally, in order to mount electronic components on a substrate such as an electronic circuit, a large amount of solder (lead-containing solder), which is an alloy of lead and tin, has been used. However, since lead is harmful to human body and environmental load is high, the use of lead-containing solder in electrical and electronic devices such as personal computers and TV sets is prohibited in principle in the European Union (RoHS), and also in Japan. Regulations are also in progress in each of the countries where it is used (J-MOSS etc.). Therefore, the switch from lead-containing solder to lead-free lead-free solder (lead-free solder) has been promoted, but lead-free solder has a higher melting temperature than conventional lead-containing solders. Higher heat resistance has come to be required for members in contact with.
しかし、従来、この分野で用いられてきた、クレゾールボラック型エポキシ樹脂またはフェノールノボラック型エポキシ樹脂をフェノールノボラック型硬化剤で硬化させた硬化物は、耐熱性は十分であるものの、要求に応えるだけの誘電特性を備えてはいなかった。
また、特許文献１には、ジシクロペンタジエン型フェノール樹脂をノボラック型フェノール樹脂で硬化した硬化物が開示されている（実施例）が、特許文献１に記載された硬化物は、従来の硬化物に比べて誘電特性が優れるが、耐熱性は高いものではなかった。
However, cured products obtained by curing cresolvolac epoxy resin or phenol novolac epoxy resin with phenol novolac curing agent, which have been conventionally used in this field, have sufficient heat resistance, but only meet the requirements. Not have the dielectric properties of
Further, Patent Document 1 discloses a cured product obtained by curing a dicyclopentadiene type phenolic resin with a novolac type phenolic resin (Example), but the cured product described in Patent Document 1 is a conventional cured product. The dielectric properties are superior to those of the above, but the heat resistance is not high.
そこで、本発明は、耐熱性と誘電特性の両方に優れた硬化物を得ることができる熱硬化性樹脂組成物ならびにその硬化物を提供することを課題とする。 Then, this invention makes it a subject to provide the thermosetting resin composition which can obtain the hardened | cured material excellent in both heat resistance and a dielectric characteristic, and its hardened | cured material.
本発明者は、上記課題を解決すべく鋭意検討を重ねた結果、ジシクロペンタジエン型エポキシ樹脂の硬化剤として、ノボラック型フェノール樹脂およびインデン類と無水マレイン酸類の共重合体を特定量用いると、耐熱性と誘電特性の両方に優れた硬化物を得ることができる熱硬化性樹脂組成物ならびにその硬化物を提供することができることを知得し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have used specific amounts of novolac type phenol resin and copolymer of indene and maleic anhydride as a curing agent of dicyclopentadiene type epoxy resin. The inventors have found that a thermosetting resin composition capable of obtaining a cured product excellent in both heat resistance and dielectric properties and a cured product thereof can be provided, and the present invention has been completed.
すなわち、本発明は以下の［１］および［２］を提供する。
［１］ ジシクロペンタジエン型エポキシ樹脂（Ａ）、ノボラック型フェノール樹脂（Ｂ）、インデン類と無水マレイン酸類との共重合体（Ｃ）および硬化触媒（Ｄ）を含有する熱硬化性樹脂組成物であって、
前記ジシクロペンタジエン型エポキシ樹脂（Ａ）中のエポキシ基のモル数ａと、前記ノボラック型フェノール樹脂（Ｂ）中のフェノール性水酸基のモル数ｂと、前記インデン類と無水マレイン酸類との共重合体（Ｄ）中の酸無水物基のモル数ｃが下記の関係を満たす、熱硬化性樹脂組成物。
ａ：ｂ＋ｃ＝１．００：１．１０〜１．００：０．４５、かつ
ｂ：ｃ＝９６：４〜６５：３５
［２］ 上記［１］に記載の熱硬化性樹脂組成物を加熱硬化して得られる硬化物。
That is, the present invention provides the following [1] and [2].
[1] A thermosetting resin composition comprising a dicyclopentadiene type epoxy resin (A), a novolac type phenolic resin (B), a copolymer of indene and maleic anhydride (C) and a curing catalyst (D) And
The number of moles a of epoxy groups in the dicyclopentadiene type epoxy resin (A), the number b of moles of phenolic hydroxyl groups in the novolac type phenolic resin (B), and the co-weight of the indens and the maleic anhydrides The thermosetting resin composition in which the number of moles c of the acid anhydride group in the united body (D) satisfies the following relationship.
a: b + c = 1.00: 1.10 to 1.00: 0.45, and b: c = 96: 4 to 65: 35
[2] A cured product obtained by heat curing the thermosetting resin composition according to the above [1].
本発明によれば、耐熱性と誘電特性の両方に優れた硬化物を得ることができる熱硬化性樹脂組成物ならびにその硬化物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition which can obtain the hardened | cured material excellent in both heat resistance and a dielectric characteristic, and its hardened | cured material can be provided.
本発明において、数量範囲を「〜」を用いて表現したときは、その数量範囲には「〜」の両側を含むものとする。
また、本発明において、数量範囲を「以下」または「以上」を用いて表現したときは、その数量範囲には基準となる数量を含むものとする。
また、本発明において、数量範囲を「未満」または「超」もしくは「超える」を用いて表現したときは、その数量範囲には基準となる数量を含まないものとする。
In the present invention, when the numerical range is expressed using “to”, the numerical range includes both sides of “to”.
Further, in the present invention, when the numerical range is expressed using “below” or “above”, the numerical range includes the standard quantity.
Further, in the present invention, when the numerical range is expressed using “less than”, “over” or “over”, the numerical range does not include the standard quantity.
以下、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail.
［熱硬化性樹脂組成物］
本発明の熱硬化性樹脂組成物は、ジシクロペンタジエン型エポキシ樹脂（Ａ）、ノボラック型フェノール樹脂（Ｂ）、インデン類と無水マレイン酸類との共重合体（Ｃ）および硬化触媒（Ｄ）を含有する熱硬化性樹脂組成物である。
ここで、ジシクロペンタジエン型エポキシ樹脂（Ａ）中のエポキシ基のモル数ａと、ノボラック型フェノール樹脂（Ｂ）中のフェノール性水酸基のモル数ｂと、インデン類と無水マレイン酸類との共重合体（Ｃ）中の酸無水物基のモル数ｃは、下記の関係を満たす。
ａ：ｂ＋ｃ＝１．００：１．１０〜１．００：０．４５、かつ
ｂ：ｃ＝９６：４〜６５：３５
[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises a dicyclopentadiene type epoxy resin (A), a novolac type phenol resin (B), a copolymer (C) of indens and maleic anhydrides and a curing catalyst (D). It is a thermosetting resin composition to contain.
Here, the number of moles a of epoxy groups in the dicyclopentadiene type epoxy resin (A), the number of moles b of phenolic hydroxyl groups in the novolac type phenol resin (B), and the co-weight of indene and maleic anhydride The number of moles c of the acid anhydride group in the united body (C) satisfies the following relationship.
a: b + c = 1.00: 1.10 to 1.00: 0.45, and b: c = 96: 4 to 65: 35
〈ジシクロペンタジエン型エポキシ樹脂（Ａ）〉
上記ジシクロペンタジエン型エポキシ樹脂（Ａ）（以下、単に「エポキシ樹脂（Ａ）」という場合がある）は、ジシクロペンタジエン類とフェノール類とを酸触媒の存在下で縮合させて得られるジシクロペンタジエン変性フェノール樹脂をエポキシ化して得られるエポキシ樹脂である。
<Dicyclopentadiene type epoxy resin (A)>
The above dicyclopentadiene type epoxy resin (A) (hereinafter sometimes simply referred to as “epoxy resin (A)”) is a dicyclo obtained by condensation of dicyclopentadienes and phenols in the presence of an acid catalyst. It is an epoxy resin obtained by epoxidizing a pentadiene modified phenol resin.
《ジシクロペンタジエン類》
エポキシ樹脂（Ａ）を製造する際の原料として用いることができるジシクロペンタジエン類は、ジシクロペンタジエン骨格を有する有機化合物であれば特に限定されない。
<< Dicyclopentadienes >>
Dicyclopentadienes which can be used as a raw material at the time of manufacturing an epoxy resin (A) will not be specifically limited if it is an organic compound which has dicyclopentadiene frame | skeleton.
上記ジシクロペンタジエン類として、例えば、ジシクロペンタジエン、１−メチルジシクロペンタジエン、２−メチルジシクロペンタジエン、２，３−ジメチルジシクロペンタジエン、２，３−ジヒドロキシジシクロペンタジエン、ジシクロペンタジエンモノエポキシド、ビニルノルボルネンおよび５−エチリデンノルボルネンを挙げることができる。
これらのジシクロペンタジエン類は、１種類を単独で、または２種類以上を組み合わせて、エポキシ樹脂（Ａ）の製造に用いることができる。ジシクロペンタジエン類を２種類以上組み合わせて用いるときは、２種類以上を混合物として用いてもよい。
Examples of the above dicyclopentadienes include dicyclopentadiene, 1-methyldicyclopentadiene, 2-methyldicyclopentadiene, 2,3-dimethyldicyclopentadiene, 2,3-dihydroxydicyclopentadiene, dicyclopentadiene monoepoxide And vinyl norbornene and 5-ethylidene norbornene.
These dicyclopentadienes can be used for manufacture of an epoxy resin (A) individually by 1 type or in combination of 2 or more types. When two or more dicyclopentadienes are used in combination, two or more may be used as a mixture.
上記ジシクロペンタジエン類の中では、入手が容易であり、かつ、最終的に得られる硬化物の誘電特性がより優れたものとなることから、ジシクロペンタジエンが好ましい。 Among the above dicyclopentadienes, dicyclopentadiene is preferable because it is easily available and the dielectric properties of the finally obtained cured product become more excellent.
《フェノール類》
エポキシ樹脂（Ａ）を製造する際の原料として用いることができるフェノール類は、フェノールまたはその誘導体であれば特に限定されない。
"Phenols"
The phenol which can be used as a raw material at the time of manufacturing an epoxy resin (A) will not be specifically limited if it is a phenol or its derivative (s).
上記フェノール類として、例えば、オルトクレゾール（２−メチルフェノール）、メタクレゾール（３−メチルフェノール）、パラクレゾール（４−メチルフェノール）、フェノール、２，６−キシレノール（２，３−ジメチルフェノール）、３，５−キシレノール（３，５−ジメチルフェノール）その他のアルキル置換フェノール類、αナフトール、βナフトールその他のアルキル置換ナフトール類およびフェノールを挙げることができる。
これらのフェノール類は、１種類を単独で、または２種類以上を組み合わせて、エポキシ樹脂（Ａ）の製造に用いることができる。フェノール類を２種類以上組み合わせて用いるときは、２種類以上を混合物として用いてもよい。
Examples of the above-mentioned phenols include ortho-cresol (2-methylphenol), meta-cresol (3-methylphenol), para-cresol (4-methylphenol), phenol, 2,6-xylenol (2,3-dimethylphenol), Mention may be made of 3,5-xylenol (3,5-dimethylphenol) and other alkyl substituted phenols, alpha naphthol, beta naphthol and other alkyl substituted naphthols and phenol.
These phenols can be used for manufacture of an epoxy resin (A) individually by 1 type or in combination of 2 or more types. When two or more types of phenols are used in combination, two or more types may be used as a mixture.
上記フェノール類の中では、入手が容易であり、かつ、安価であることから、フェノール、オルトクレゾール、メタクレゾールおよびパラクレゾールからなる群から選択される１種類以上が好ましく、フェノールがより好ましい。 Among the above-mentioned phenols, at least one selected from the group consisting of phenol, ortho-cresol, meta-cresol and para-cresol is preferable, and phenol is more preferable, because it is easily available and inexpensive.
《エポキシ樹脂（Ａ）の製造方法》
（ジシクロペンタジエン変性フェノール樹脂の製造）
ジシクロペンタジエン変性フェノール樹脂の製造方法は、特に制限されないが、一例として次の方法で製造することができる。
ジシクロペンタジエン類に対し、過剰モル量のフェノール類を反応容器に仕込み、これに酸触媒を加えて、５０℃から１５０℃の範囲に加熱する。加熱後、反応容器内の混合物にジシクロペンタジエン類を少量ずつ滴下して反応させる。反応後、反応混合物から過剰のフェノール類を減圧蒸留等により除去し、得られた樹脂を、加熱溶融した状態で回収する。
<< Method for producing epoxy resin (A) >>
(Production of dicyclopentadiene modified phenolic resin)
Although the manufacturing method in particular of a dicyclopentadiene modified phenolic resin is not restrict | limited, It can manufacture by the following method as an example.
With respect to the dicyclopentadienes, an excess molar amount of phenols is charged into a reaction vessel, to which an acid catalyst is added and heated to a range of 50 ° C to 150 ° C. After heating, dicyclopentadienes are added dropwise little by little to the mixture in the reaction vessel and reacted. After the reaction, excess phenols are removed from the reaction mixture by distillation or the like under reduced pressure, and the obtained resin is recovered in a heat-melted state.
上記酸触媒は、特に限定されないが、例えば、三フッ化ホウ素フェノール錯体、三フッ化ホウ素エーテル錯体その他のルイス酸、または硫酸、塩酸、パラトルエンスルホンその他のプロトン酸である。上記酸触媒の中では、生成物の着色が少なく、かつ、副生成物が生じにくいことから、三フッ化ホウ素フェノール錯体または三フッ化ホウ素エーテル錯体が好ましい。 The acid catalyst is not particularly limited, and is, for example, boron trifluoride phenol complex, boron trifluoride ether complex or other Lewis acid, or sulfuric acid, hydrochloric acid, paratoluene sulfone or other protonic acid. Among the above acid catalysts, a boron trifluoride phenol complex or a boron trifluoride ether complex is preferable because the coloration of the product is small and by-products are hard to occur.
反応終了後には、反応混合物に中和剤を添加し、酸触媒を中和して失活させることが好ましい。また、中和後の生成物中の酸触媒残渣は、濾過または水洗によって生成物から除去することが好ましい。 After completion of the reaction, a neutralizing agent is preferably added to the reaction mixture to neutralize and deactivate the acid catalyst. Also, the acid catalyst residue in the product after neutralization is preferably removed from the product by filtration or water washing.
上記中和剤は、使用する酸触媒に応じて適宜選択することができるが、例えば、酸触媒として三フッ化ホウ素フェノール錯体を用いた場合は、ハイドロタルサイトその他の層状無機物を用いることができ、酸触媒としてパラトルエンスルホン酸を用いた場合は、水酸化ナトリウム、炭酸水素ナトリウムその他のアルカリ金属またはアルカリ土類金属の水酸化物または塩を用いることできる。ハイドロタルサイトは、酸触媒を中和することができるだけでなく、吸着することもできるので好ましく、水酸化ナトリウムおよび炭酸カルシウムは安価であるので好ましい。 Although the said neutralizing agent can be suitably selected according to the acid catalyst to be used, for example, when using a boron trifluoride phenol complex as an acid catalyst, hydrotalcite other layered inorganic substances can be used When p-toluenesulfonic acid is used as an acid catalyst, hydroxides or salts of sodium hydroxide, sodium hydrogencarbonate and other alkali metals or alkaline earth metals can be used. Hydrotalcite is preferable because it can not only neutralize the acid catalyst but also adsorb it, and sodium hydroxide and calcium carbonate are preferable because they are inexpensive.
（ジシクロペンタジエン変性フェノール樹脂のエポキシ化）
ジシクロペンタジエン変性フェノール樹脂のエポキシ化方法は、特に限定されないが、一例として次の方法でエポキシ化することができる。
ジメチルスルホキシド等の極性溶媒中で、ジシクロペンタジエン変性フェノール樹脂、エピクロロヒドリンおよび水酸化ナトリウムを反応させてエポキシ化反応を行う。反応後、溶媒および過剰のエピクロロヒドリンを蒸留除去し、残渣にメチルエチルケトン等の抽出溶媒を加え、さらに、イオン交換水で数回洗浄し、生成した塩化ナトリウムを除去した後、溶媒のメチルエチルケトンを蒸留除去することにより、ジシクロペンタジエン変性フェノール樹脂のエポキシ化物、すなわち、エポキシ樹脂（Ａ）を得ることができる。
(Epoxidation of dicyclopentadiene modified phenolic resin)
The epoxidation method of the dicyclopentadiene modified phenolic resin is not particularly limited, but can be epoxidized by the following method as an example.
The epoxidation reaction is carried out by reacting a dicyclopentadiene modified phenolic resin, epichlorohydrin and sodium hydroxide in a polar solvent such as dimethyl sulfoxide. After the reaction, the solvent and excess epichlorohydrin are distilled off, an extraction solvent such as methyl ethyl ketone is added to the residue, and the product is further washed several times with ion exchanged water to remove sodium chloride formed, and then methyl ethyl ketone as a solvent is used. By distillative removal, it is possible to obtain an epoxy compound of dicyclopentadiene modified phenolic resin, that is, an epoxy resin (A).
《エポキシ樹脂（Ａ）の平均分子量》
エポキシ樹脂（Ａ）の平均分子量は、特に限定されないが、重量平均分子量（ポリスチレン換算）で、好ましくは１００〜１００００であり、より好ましくは３００〜５０００である。重量平均分子量がこの範囲内であると、耐熱性がより優れたものとなり、かつ、加熱時に粘度が高くなり過ぎず成形性がより優れたものとなる。
なお、上記エポキシ樹脂（Ａ）の重量平均分子量は、以下の条件でＧＰＣ（ゲル浸透クロマトグラフィー）により測定したものである。
ＧＰＣ条件：
カラム Ｓｈｏｄｅｘ（登録商標） ＫＦ−８０１、ＫＦ−８０２．５、ＫＦ−８０２．５、ＫＦ−８０３（昭和電工社製）
ガードカラム Ｓｈｏｄｅｘ ＫＦ−８０１（昭和電工社製）
連結溶離液 テトラヒドロフラン
流速 ０．８Ｌ／ｍｉｎ．
カラム温度 ４０℃
検出 示差屈折（ＲＩ）検出器（Refractive Index Detector）
標準物質 ポリスチレン
<< Average Molecular Weight of Epoxy Resin (A) >>
The average molecular weight of the epoxy resin (A) is not particularly limited, but is preferably 100 to 10,000, more preferably 300 to 5,000, in terms of weight average molecular weight (in terms of polystyrene). When the weight average molecular weight is in this range, the heat resistance is further improved, and the viscosity is not excessively increased during heating, and the formability is further improved.
In addition, the weight average molecular weight of the said epoxy resin (A) is measured by GPC (gel permeation chromatography) on condition of the following.
GPC conditions:
Column Shodex (registered trademark) KF-801, KF-802.5, KF-802.5, KF-803 (manufactured by Showa Denko KK)
Guard column Shodex KF-801 (made by Showa Denko)
Connected eluent tetrahydrofuran Flow rate 0.8 L / min.
Column temperature 40 ° C
Detection Differential Refraction (RI) Detector (Refractive Index Detector)
Reference material polystyrene
〈ノボラック型フェノール樹脂（Ｂ）〉
上記ノボラック型フェノール樹脂（Ｂ）（以下、単に「フェノール樹脂（Ｂ）」という場合がある）は、フェノール類とホルムアルデヒド類とを酸触媒の存在下で縮合させて得られるフェノール樹脂である。
<Novolak-type phenolic resin (B)>
The novolac type phenol resin (B) (hereinafter sometimes simply referred to as "phenol resin (B)") is a phenol resin obtained by condensing phenols and formaldehyde in the presence of an acid catalyst.
《フェノール類》
フェノール樹脂（Ｂ）を製造する際の原料として用いることができるフェノール類は、フェノールまたはその誘導体であれば特に限定されない。
"Phenols"
The phenols which can be used as a raw material at the time of manufacturing a phenol resin (B) will not be specifically limited if it is phenol or its derivative (s).
上記フェノール類として、例えば、オルトクレゾール（２−メチルフェノール）、メタクレゾール（３−メチルフェノール）、パラクレゾール（４−メチルフェノール）、フェノール、２，６−キシレノール（２，３−ジメチルフェノール）、３，５−キシレノール（３，５−ジメチルフェノール）その他のアルキル置換フェノール類、αナフトール、βナフトールその他のアルキル置換ナフトール類およびフェノールを挙げることができる。
これらのフェノール類は、１種類を単独で、または２種類以上を組み合わせて、フェノール樹脂（Ｂ）の製造に用いることができる。フェノール類を２種類以上組み合わせて用いるときは、２種類以上を混合物として用いてもよい。
Examples of the above-mentioned phenols include ortho-cresol (2-methylphenol), meta-cresol (3-methylphenol), para-cresol (4-methylphenol), phenol, 2,6-xylenol (2,3-dimethylphenol), Mention may be made of 3,5-xylenol (3,5-dimethylphenol) and other alkyl substituted phenols, alpha naphthol, beta naphthol and other alkyl substituted naphthols and phenol.
These phenols can be used for manufacture of a phenol resin (B) individually by 1 type or in combination of 2 or more types. When two or more types of phenols are used in combination, two or more types may be used as a mixture.
上記フェノール類の中では、入手が容易であり、かつ、安価であることから、フェノール、オルトクレゾール、メタクレゾールおよびパラクレゾールからなる群から選択される１種類以上が好ましく、フェノールがより好ましい。 Among the above-mentioned phenols, at least one selected from the group consisting of phenol, ortho-cresol, meta-cresol and para-cresol is preferable, and phenol is more preferable, because it is easily available and inexpensive.
《ホルムアルデヒド類》
フェノール樹脂（Ｂ）を製造する際の原料として用いることができるホルムアルデヒド類は、例えば、ホルムアルデヒド、ホルマリン（ホルムアルデヒドの水溶液）およびパラホルムアルデヒド（ホルムアルデヒドの重合体（固体））が挙げられる。
これらのホルムアルデヒド類は、１種類を単独で、または２種類以上を組み合わせてフェノール樹脂（Ｂ）の製造に用いることができる。ホルムアルデヒド類を２種類以上組み合わせて用いるときは、２種類以上を混合物として用いてもよい。
<< Formaldehydes >>
Examples of formaldehydes that can be used as a raw material for producing the phenolic resin (B) include formaldehyde, formalin (an aqueous solution of formaldehyde) and paraformaldehyde (a polymer of formaldehyde (solid)).
These formaldehydes can be used for manufacture of a phenol resin (B) individually by 1 type or in combination of 2 or more types. When two or more types of formaldehyde are used in combination, two or more types may be used as a mixture.
《酸触媒》
フェノール樹脂（Ｂ）を製造する際の原料として用いることができる酸触媒は、特に限定されないが、入手が容易であり、かつ、安価であることから、パラトルエンスルホン酸、硫酸およびシュウ酸からなる群から選択される少なくとも１種類が好ましい。
Acid Catalyst
The acid catalyst that can be used as a raw material for producing the phenolic resin (B) is not particularly limited, but is easy to obtain and is inexpensive, and therefore is composed of p-toluenesulfonic acid, sulfuric acid and oxalic acid At least one selected from the group is preferred.
《市販のフェノール樹脂（Ｂ）》
フェノール樹脂（Ｂ）は、合成してもよいが、市販品を購入することもできる。
このような市販品として、例えば、ＰＨＥＮＯＬＩＴＥ（登録商標） ＴＤ−２１３１（１０４ｇ／当量）、ＴＤ−２１０６（１０４ｇ／当量）、ＴＤ−２０９３（１０４ｇ／当量）およびＴＤ−２０９０（１０５ｇ／当量）等のフェノールノボラック樹脂、ならびにＰＨＥＮＯＬＩＴＥ ＫＡ−１１６０（１１７ｇ／当量）、ＫＡ−１１６３（１１８ｇ／当量）およびＫＡ−１１６５（１１９ｇ／当量）等のクレゾールノボラック樹脂を挙げることができる（いずれもＤＩＣ社製；括弧内にはフェノール水酸基当量を記載した）。
Commercially available phenolic resin (B)
The phenol resin (B) may be synthesized or commercially available.
As such commercial products, for example, PHENOLITE (registered trademark) TD-2131 (104 g / equivalent), TD-2106 (104 g / equivalent), TD-2093 (104 g / equivalent), TD-2090 (105 g / equivalent), etc. And phenolic cresol novolak resins such as PHENOLITE KA-1160 (117 g / eq), KA-1163 (118 g / eq) and KA-1165 (119 g / eq) (all from DIC; The phenol hydroxyl equivalent was described in parentheses).
〈インデン類と無水マレイン酸類との共重合体（Ｃ）〉
インデン類と無水マレイン酸の共重合体（Ｃ）（以下、単に「共重合体（Ｃ）」という場合がある）は、溶媒を用いて（溶媒中で）、または溶媒を用いないで、触媒またはラジカル開始剤の存在下、インデン類と無水マレイン酸類とを加熱し、重合させて得られる共重合体である。
Copolymer of Indenes and Maleic Anhydrides (C)
The copolymer (C) of indene and maleic anhydride (hereinafter sometimes simply referred to as "copolymer (C)") is a catalyst using a solvent (in a solvent) or without a solvent Or a copolymer obtained by heating and polymerizing indenes and maleic anhydride in the presence of a radical initiator.
《インデン類》
上記インデン類は、二重結合を有し、インデン骨格を有する化合物であれば、特に限定されず、例えば、インデン、インデンの１つ以上の水素原子にメチル基、エチル基、ｔ−ブチル基その他のアルキル基が置換したアルキル置換インデン、インデンの１つ以上の水素原子にフェニル基、ナフチル基その他のアリール基が置換したアリール置換インデン、インデンの２つ以上の水素原子にアルキル基およびアリール基が置換したアルキル／アリール置換インデンが挙げられる。
«Indenes»
The above indene is not particularly limited as long as it is a compound having a double bond and having an indene skeleton, for example, indene, one or more hydrogen atoms of indene, methyl group, ethyl group, t-butyl group, etc. Alkyl-substituted indene substituted with an alkyl group, aryl-substituted indene wherein one or more hydrogen atoms of indene are substituted with a phenyl group, a naphthyl group or another aryl group, an alkyl group and an aryl group exist as two or more hydrogen atoms of indene Substituted alkyl / aryl substituted indene may be mentioned.
上記アルキル置換インデンの具体例として、１−メチルインデン、２−メチルインデン、３−メチルインデン、４−メチルインデン、５−メチルインデン、６−メチルインデン、７−メチルインデン、１−エチルインデン、２−エチルインデン、３−エチルインデン、４−エチルインデン、５−エチルインデン、６−エチルインデン、７−エチルインデン、１−ｎプロピルインデン、２−ｎプロピルインデン、３−ｎプロピルインデン、４−ｎプロピルインデン、５−ｎプロピルインデン、６−ｎプロピルインデン、７−ｎプロピルインデン、１−イソプロピルインデン、２−イソプロピルインデン、３−イソプロピルインデン、４−イソプロピルインデン、５−イソプロピルインデン、６−イソプロピルインデン、７−イソプロピルインデン、１−ｔ−ブチルインデン、２−ｔ−ブチルインデン、３−ｔ−ブチルインデン、４−ｔ−ブチルインデン、５−ｔ−ブチルインデン、６−ｔ−ブチルインデンおよび７−ｔ−ブチルインデンが挙げられる。 Specific examples of the above alkyl-substituted indene include 1-methylindene, 2-methylindene, 3-methylindene, 4-methylindene, 5-methylindene, 6-methylindene, 7-methylindene, 1-ethylindene, 2 -Ethyl indene, 3-ethyl indene, 4-ethyl indene, 5-ethyl indene, 6-ethyl indene, 7-ethyl indene, 1-n propyl indene, 2-n propyl indene, 3-n propyl indene, 4-n Propyl indene, 5-n propyl indene, 6-n propyl indene, 7-n propyl indene, 1-isopropyl indene, 2-isopropyl indene, 3-isopropyl indene, 4-isopropyl indene, 5-isopropyl indene, 6-isopropyl indene , 7- isopropyl ind 1-t-butylindene, 2-t-butylindene, 3-t-butylindene, 4-t-butylindene, 5-t-butylindene, 6-t-butylindene and 7-t-butylindene It can be mentioned.
また、上記アリール置換インデンの具体例として、１−フェニルインデン、２−フェニルインデン、３−フェニルインデン、４−フェニルインデン、５−フェニルインデン、６−フェニルインデン、１−ナフチルインデン、２−ナフチルインデン、３−ナフチルインデン、４−ナフチルインデン、５−ナフチルインデン、６−ナフチルインデンおよび７−ナフチルインデンが挙げられる。 Also, as specific examples of the above aryl-substituted indene, 1-phenylindene, 2-phenylindene, 3-phenylindene, 4-phenylindene, 5-phenylindene, 6-phenylindene, 1-naphthylindene, 2-naphthylindene And 3-naphthylindene, 4-naphthylindene, 5-naphthylindene, 6-naphthylindene and 7-naphthylindene.
上記インデン類の中でも、入手が容易であることから、インデンおよびメチルインデン（インデンの水素原子の１つにメチル基が置換したアルキル置換インデン）が好ましく、さらに、得られる硬化物の誘電特性がより優れたものとなることから、メチルインデン類がより好ましい。 Among the above indens, indene and methyl indene (alkyl-substituted indene in which one of hydrogen atoms of indene is substituted with methyl group) are preferable because of easy availability, and further, the dielectric property of the obtained cured product is more Methyl indenes are more preferable because they are excellent.
《無水マレイン酸類》
上記無水マレイン酸類は、下記式（１）で表される、酸無水物基を含む五員環に重合性の炭素−炭素二重結合を含む構造を分子構造中に有する酸無水物であれば特に限定されないが、好ましくは下記式（２）で表される化合物である。
Maleic anhydrides
The above-mentioned maleic anhydride is an acid anhydride represented by the following formula (1) which has a structure containing a polymerizable carbon-carbon double bond in a five-membered ring containing an acid anhydride group in its molecular structure Although it does not specifically limit, Preferably it is a compound represented by following formula (2).
上記式（２）中、Ｒ１およびＲ２は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基およびアリール基からなる群から選択される基である。また、上記Ｒ１およびＲ２は、結合して、５〜８員の炭素環を形成してもよい。さらに、上記アルキル基、アルケニル基、アルキニル基およびアリール基は、水素原子の１つ以上にアルキル基および／またはアリール基が置換してもよい。 In the above formula (2), R 1 and R 2 are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group and an aryl group. Moreover, said R < 1 > and R < 2 > may combine and form a 5- to 8-membered carbocyclic ring. Furthermore, in the above-mentioned alkyl group, alkenyl group, alkynyl group and aryl group, one or more of hydrogen atoms may be substituted by an alkyl group and / or an aryl group.
上記Ｒ１およびＲ２は、好ましくは、それぞれ独立に、水素原子、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基およびｔｅｒｔ−ブチル基からなる群から選択される基であり、より好ましくは、それぞれ独立に、水素原子、メチル基およびエチル基からなる群から選択される基である。 Each of R 1 and R 2 is preferably independently selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. And more preferably each independently a group selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.
上記無水マレイン酸類の具体例として、無水マレイン酸、無水マレイン酸の水素原子の１つ以上にアルキル基および／またはアリール基が置換した置換無水マレイン酸、１−シクロヘキセン−１，２−ジカルボン酸無水物、ならびに１−シクロヘキセン−１，２−ジカルボン酸無水物の水素原子の１つ以上にアルキル基および／またはアリール基が置換した置換１−シクロヘキセン−１，２−ジカルボン酸無水物を挙げることができる。 Specific examples of the above-mentioned maleic anhydrides include maleic anhydride, substituted maleic anhydride in which one or more hydrogen atoms of maleic anhydride are substituted with an alkyl group and / or aryl group, 1-cyclohexene-1,2-dicarboxylic acid anhydride And substituted 1-cyclohexene-1,2-dicarboxylic acid anhydrides in which one or more of the hydrogen atoms of 1-cyclohexene-1,2-dicarboxylic acid anhydride are substituted with an alkyl group and / or an aryl group. it can.
上記無水マレイン酸類は、より好ましくは、無水マレイン酸または１−シクロヘキセン−１，２−ジカルボン酸無水物であり、さらに好ましくは、無水マレイン酸である。 The above-mentioned maleic anhydride is more preferably maleic anhydride or 1-cyclohexene-1,2-dicarboxylic acid anhydride, still more preferably maleic anhydride.
《インデン類と無水マレイン酸類との重合反応》
重合反応の形態は、ラジカル重合、カチオン重合およびアニオン重合のいずれを用いてもよいが、反応速度が早く、かつ、副生物の生成が少ない点で、ラジカル重合を用いることが好ましい。ラジカル重合では、ラジカル開始剤を用いなければ重合反応が進行しないわけではないが、反応速度が速くなることから、ラジカル開始剤を用いることが好ましい。
<< Polymerization Reaction of Indenes and Maleic Anhydrides >>
As the form of the polymerization reaction, any of radical polymerization, cationic polymerization and anionic polymerization may be used, but it is preferable to use radical polymerization in that the reaction rate is fast and generation of by-products is small. In radical polymerization, the polymerization reaction does not proceed unless a radical initiator is used, but it is preferable to use a radical initiator because the reaction rate is increased.
上記ラジカル開始剤は特に限定されないが、例えば、各種アゾ化合物、各種過酸化物、各種酸化剤と還元剤の組み合わせ（レドックス開始剤）からなる混合物およびジハロゲンを挙げることができる。
上記ラジカル開始剤の中では、常温で比較的安定で取扱い容易であり、かつ、反応性が高いことから、アゾビスイソブチルニトリルまたはベンゾイルパーオキサイドが好ましい。
Although the said radical initiator is not specifically limited, For example, the mixture which consists of various azo compounds, various peroxides, the combination of various oxidizing agents and a reducing agent (redox initiator), and dihalogen can be mentioned.
Among the above radical initiators, azobisisobutyronitrile or benzoyl peroxide is preferable because it is relatively stable at room temperature, easy to handle, and highly reactive.
共重合体（Ｂ）の製造時のインデン類と無水マレイン酸の重合反応の際の加熱温度は、特に限定されないが、好ましくは０℃〜２００℃であり、より好ましくは２０℃〜１８０℃であり、さらに好ましくは４０℃〜１６０℃である。上記加熱温度がこの範囲内であると、反応速度が速いことから生産性がより良好なものとなり、かつ、重合度が高くなり過ぎないことから反応容器から生成物を回収することがより容易なものとなる。 The heating temperature in the polymerization reaction of the indene and maleic anhydride during the production of the copolymer (B) is not particularly limited, but is preferably 0 ° C. to 200 ° C., more preferably 20 ° C. to 180 ° C. C., and more preferably 40.degree. C. to 160.degree. When the heating temperature is within this range, the reaction rate is fast, the productivity is better, and the degree of polymerization does not become too high, so that it is easier to recover the product from the reaction vessel It becomes a thing.
共重合体（Ｂ）の製造時のインデン類と無水マレイン酸の重合反応の際に溶媒を用いる場合の溶媒は、特に限定されないが、入手が容易であることから、ベンゼン、トルエン、メチルエチルケトンおよびメチルイソブチルケトンからなる群から選択される少なくとも１種類が好ましい。 The solvent in the case of using a solvent in the polymerization reaction of indene and maleic anhydride at the time of production of the copolymer (B) is not particularly limited, but benzene, toluene, methyl ethyl ketone and methyl are easy to obtain. At least one selected from the group consisting of isobutyl ketones is preferred.
《共重合体（Ｃ）の平均分子量》
共重合体（Ｃ）の平均分子量は、特に限定されないが、重量平均分子量（ポリスチレン換算）で、好ましくは１００〜１０００００であり、より好ましくは３００〜５００００である。重量平均分子量がこの範囲内であると、耐熱性がより優れたものとなり、かつ、加熱時に粘度が高くなり過ぎず成形性がより優れたものとなる。
なお、上記共重合体（Ｃ）の重量平均分子量は、以下の条件でＧＰＣ（ゲル浸透クロマトグラフィー）により測定したものである。
ＧＰＣ条件：
カラム Ｓｈｏｄｅｘ ＫＦ−８０１、ＫＦ−８０２．５、ＫＦ−８０２．５、ＫＦ−８０３
ガードカラム Ｓｈｏｄｅｘ ＫＦ−８０１
連結溶離液 テトラヒドロフラン
流速 ０．８Ｌ／ｍｉｎ．
カラム温度 ４０℃
検出 示差屈折（ＲＩ）検出器（Refractive Index Detector）
標準物質 ポリスチレン
<< Average Molecular Weight of Copolymer (C) >>
The average molecular weight of the copolymer (C) is not particularly limited, but is preferably 100 to 1000000, more preferably 300 to 50000 in terms of weight average molecular weight (in terms of polystyrene). When the weight average molecular weight is in this range, the heat resistance is further improved, and the viscosity is not excessively increased during heating, and the formability is further improved.
In addition, the weight average molecular weight of the said copolymer (C) is measured by GPC (gel permeation chromatography) on condition of the following.
GPC conditions:
Column Shodex KF-801, KF-802.5, KF-802.5, KF-803
Guard column Shodex KF-801
Connected eluent tetrahydrofuran Flow rate 0.8 L / min.
Column temperature 40 ° C
Detection Differential Refraction (RI) Detector (Refractive Index Detector)
Reference material polystyrene
〈硬化触媒（Ｄ）〉
硬化触媒（Ｄ）は、エポキシ樹脂（Ａ）と、硬化剤であるフェノール樹脂（Ｂ）および共重合体（Ｃ）との硬化反応を触媒する化合物である。
<Curing catalyst (D)>
The curing catalyst (D) is a compound that catalyzes the curing reaction of the epoxy resin (A) and the curing agent, the phenol resin (B) and the copolymer (C).
上記硬化触媒（Ｄ）として、例えば、有機リン系化合物、４級ホスホニウム塩類、イミダゾール類、有機金属化合物、無機金属化合物、３級アミン類、ジアザビシクロアルケン類、４級アンモニウム類、ホウ素化合物および金属ハロゲン化物を挙げることができる。 As the curing catalyst (D), for example, organic phosphorus compounds, quaternary phosphonium salts, imidazoles, organic metal compounds, inorganic metal compounds, tertiary amines, diazabicycloalkenes, quaternary ammoniums, boron compounds and Metal halides can be mentioned.
上記有機リン系化合物の具体例としては、トリフェニルホスフィン、トリパラトリルホスフィン、ジフェニルシクロヘキシルホスフィン、トリシクロヘキシルホスフィン、エチルトリフェニルホスヒホニウムブロマイド、ベンジルトリフェニルホスホニウムクロライド、１，４−ビスジフェニルホスフィノブタンおよびテトラフェニルホスホニウムテトラ−ｐ−トリルボレートが挙げられる。 Specific examples of the above organic phosphorus compounds include triphenylphosphine, triparatylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride and 1,4-bisdiphenylphosphinobutane. And tetraphenylphosphonium tetra-p-tolylborate.
上記４級ホスホニウム塩類の具体例としては、ベンジルトリフェニルホスホニウムクロライド、テトラ−ｎ−ブチルホスホニウムブロマイド、メチルトリフェニルホスホニウムブロマイド、エチルトリフェニルホスホニウムブロマイド、ｎ−ブチルトリフェニルホスホニウムブロマイド、テトラフェニルホスホニウムブロマイド、エチルトリフェニルホスホニウムヨーダイド、エチルトリフェニルホスホニウムアセテート、メチルトリブチルホスホニウムジメチルホスフェート、テトラブチルホスホニウムジエチルホスホジチオネート、テトラ−ｎ−ブチルホスホニウムベンゾトリアゾレート、テトラ−ｎ−ブチルホスホニウムテトラフルオロボレート、テトラ−ｎ−ブチルホスホニウムテトラフェニルボレートおよびテトラフェニルホスホニウムテトラフェニルボレートが挙げられる。 Specific examples of the quaternary phosphonium salts include benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide and tetraphenylphosphonium bromide. Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, methyltributylphosphonium dimethyl phosphate, tetrabutylphosphonium diethylphosphodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra- n-Butylphosphonium tetraphenylborate and tetraphenylphosphorous Um tetraphenylborate and the like.
上記イミダゾール類の具体例としては、２−メチルイミダゾール、２−ｎ−ヘプチルイミダゾール、２−ｎ−ウンデシルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１，２−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、１−（２−シアノエチル）−２−メチルイミダゾール、１−（２−シアノエチル）−２−ｎ−ウンデシルイミダゾール、１−（２−シアノエチル）−２−フェニルイミダゾール、１−（２−シアノエチル）−２−エチル−４−メチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニル−４，５−ジ（ヒドロキシメチル）イミダゾール、１−（２−シアノエチル）−２−フェニル−４，５−ジ〔（２’−シアノエトキシ）メチル〕イミダゾール、１−（２−シアノエチル）−２−ｎ−ウンデシルイミダゾリウムトリメリテート、１−（２−シアノエチル）−２−フェニルイミダゾリウムトリメリテート、１−（２−シアノエチル）−２−エチル−４−メチルイミダゾリウムトリメリテート、２，４−ジアミノ−６−〔２’−メチルイミダゾリル−（１’）〕エチル−ｓ−トリアジン、２，４−ジアミノ−６−（２’−ｎ−ウンデシルイミダゾリル）エチル−ｓ−トリアジン、２，４−ジアミノ−６−〔２’−エチル−４’−メチルイミダゾリル−（１’）〕エチル−ｓ−トリアジン、２−メチルイミダゾールのイソシアヌル酸付加物、２−フェニルイミダゾールのイソシアヌル酸付加物、および２，４−ジアミノ−６−〔２’−メチルイミダゾリル−（１’）〕エチル−ｓ−トリアジンのイソシアヌル酸付加物が挙げられる。 Specific examples of the above imidazoles include 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2- 2 n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazo 1- (2-cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2′- Methylimidazolyl- (1 ′)! Ethyl-s-triazine, 2,4-diamino-6- (2′-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2′- Ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanato of 2-phenylimidazole Le acid adduct, and 2,4-diamino-6- [2'-methylimidazolyl- - (1 ')] isocyanuric acid adduct of ethyl -s- triazine.
上記ジアザビシクロアルケン類の具体例としては、１，８−ジアザビシクロ［５．４．０］ウンデセン−７およびその有機酸塩が挙げられる。 Specific examples of the diazabicycloalkenes include 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof.
上記４級アンモニウム塩類の具体例としては、テトラエチルアンモニウムブロマイドおよびテトラ−ｎ−ブチルアンモニウムブロマイドが挙げられる。 Specific examples of the quaternary ammonium salts include tetraethylammonium bromide and tetra-n-butylammonium bromide.
上記ホウ素化合物の具体例としては、三フッ化ホウ素およびホウ酸トリフェニルが挙げられる。 Specific examples of the boron compound include boron trifluoride and triphenyl borate.
上記金属ハロゲン化合物の具体例としては、塩化亜鉛および塩化第二錫が挙げられる。 Specific examples of the above metal halide compounds include zinc chloride and stannic chloride.
硬化反応の際の硬化触媒（Ｄ）の使用量（質量）は、本発明の効果を損なわない範囲であれば適宜設定することができるが、エポキシ樹脂（Ａ）、フェノール樹脂（Ｂ）および共重合体（Ｃ）の合計量（質量）に対して、好ましくは０．００１質量％〜２０質量％であり、より好ましくは０．０１質量％〜１０質量％であり、さらに好ましくは０．０５質量％〜５質量％である。酸化触媒（Ｄ）の使用量がこの範囲内であると、硬化速度が速く、生産性がより良好であり、かつ、耐熱性および誘電特性に優れた硬化物を得ることができる。 The use amount (mass) of the curing catalyst (D) in the curing reaction can be appropriately set as long as the effect of the present invention is not impaired. However, the epoxy resin (A), the phenol resin (B) and the cocatalyst Preferably it is 0.001 mass%-20 mass% with respect to the total amount (mass) of a polymer (C), More preferably, it is 0.01 mass%-10 mass%, More preferably, it is 0.05 It is mass%-5 mass%. When the amount of the oxidation catalyst (D) used is in this range, a cured product having a high curing rate, better productivity, and excellent heat resistance and dielectric properties can be obtained.
〈ａ，ｂ，ｃ〉
本発明の熱硬化性樹脂組成物においては、エポキシ樹脂（Ａ）中のエポキシ基のモル数ａと、フェノール樹脂（Ｂ）中のフェノール性水酸基のモル数ｂと、共重合体（Ｃ）中の酸無水物基のモル数ｃが、以下の関係（１）および関係（２）を満たすように、各成分を配合する。
<A, b, c>
In the thermosetting resin composition of the present invention, in the copolymer (C), the number a of moles of epoxy groups in the epoxy resin (A), the number b of moles of phenolic hydroxyl groups in the phenol resin (B), and Each component is mix | blended so that the number-of-moles c of the acid anhydride group of these satisfy | fills the following relationship (1) and relationship (2).
・関係（１）
ａ：ｂ＋ｃ＝１．００：１．１０〜１．００：０．４５、好ましくはａ：ｂ＋ｃ＝１．００：１．００〜１．００：０．５０
ａ：ｂ＋ｃが上記範囲内であると、得られる硬化物の強度が十分に高くなる。
ａと（ｂ＋ｃ）の比の値〔ａ／（ｂ＋ｃ）〕が０．４５／１．００未満であると、得られる硬化物の耐熱性が不十分となり、１．００／１．１０超であると、得られる硬化物の誘電性能が不十分となる。
・ Relationship (1)
a: b + c = 1.00: 1.10 to 1.00: 0.45, preferably a: b + c = 1.00: 1.00 to 1.00: 0.50
When the a: b + c is in the above range, the strength of the resulting cured product is sufficiently high.
If the value of the ratio of a to (b + c) [a / (b + c)] is less than 0.45 / 1.00, the heat resistance of the resulting cured product becomes insufficient, and if it exceeds 1.00 / 1.10 If so, the dielectric performance of the resulting cured product is insufficient.
・関係（２）
ｂ：ｃ＝９６：４〜６５：３５、好ましくはｂ：ｃ＝９５：５〜７０：３０
ｂ：ｃが上記範囲内であると、得られる硬化物の誘電特性および耐熱性を両立することができる。
ｂとｃの比の値〔ｂ／ｃ〕が９６／４超であると、得られる硬化物の誘電性能が不十分となり、６５／３５未満であると、得られる硬化物の成形性が不十分となる。
・ Relationship (2)
b: c = 96: 4 to 65:35, preferably b: c = 95: 5 to 70:30
When the b: c is in the above range, both the dielectric properties and the heat resistance of the resulting cured product can be achieved.
When the ratio of b to c [b / c] is more than 96/4, the dielectric performance of the resulting cured product is insufficient, and when it is less than 65/35, the formability of the resulting cured product is not good. It will be enough.
《エポキシ基のモル数・エポキシ当量》
エポキシ樹脂（Ａ）中のエポキシ基のモル数は、例えば、ＪＩＳ Ｋ ７２３６：２００９「エポキシ樹脂のエポキシ当量の求め方」に従って、エポキシ当量を求め測定することができる。すなわち、エポキシ樹脂（Ａ）のエポキシ当量は、１当量のエポキシ基を含む質量であり、この値から、単位質量に含まれるエポキシ基のモル数を求めることができる。
<< mole number of epoxy group, epoxy equivalent >>
The number of moles of the epoxy group in the epoxy resin (A) can be determined by measuring the epoxy equivalent according to, for example, JIS K 7236: 2009 “How to determine the epoxy equivalent of the epoxy resin”. That is, the epoxy equivalent of the epoxy resin (A) is a mass containing one equivalent of an epoxy group, and from this value, the number of moles of the epoxy group contained in the unit mass can be determined.
《フェノール性水酸基のモル数・フェノール性水酸基当量》
フェノール性水酸基当量：ビスフェノールＦ（本州化学工業株式会社製、商品名：ＢＰＦ−Ｄ）を５ｍｇ／Ｌ、２０ｍｇ／Ｌ又は５０ｍｇ／Ｌ含有するテトラヒドロフラン溶液を５０ｍＬ作成し、テトラブチルアンモニウムヒドロキサイド１０％水溶液を２０μＬ添加混合した後、ＵＶスペクトルを測定し、３０５ｎｍの吸光度により検量線を作成した。実施例及び比較例のサンプルを０．１ｇ秤量し、テトラヒドロフラン５０ｍＬに溶解（希釈倍率：５００倍）させて、テトラブチルアンモニウムヒドロキサイド１０％水溶液を２０μＬ添加混合した後、ＵＶスペクトルを測定し、３０５ｎｍの吸光度からビスフェノールＦに由来するフェノール性水酸基当量（ＰＯＨＥ）を下記の数式にて算出した。
ＰＯＨＥ＝｛（ｍ×ｋ）／（ｃ×ｄ）｝×１０６
ただし、式中、ｍ、ｋ、ｃおよびｄは以下に示すものである。
ｍ：試料採取量（ｇ）
ｋ：ビスフェノールＦのグラム当量、１００（ｇ／当量）
ｃ：検量線濃度（ｍｇ／Ｌ）
ｄ：試料溶液の希釈倍率、５００（ｍＬ）
<< mole number of phenolic hydroxyl group / equivalent of phenolic hydroxyl group >>
Phenolic hydroxyl group equivalent: 50 mL of a tetrahydrofuran solution containing 5 mg / L, 20 mg / L or 50 mg / L of bisphenol F (product of Honshu Chemical Industry Co., Ltd., trade name: BPF-D) is prepared, and 10% of tetrabutylammonium hydroxide is prepared. After adding and mixing 20 microliters of aqueous solution, UV spectrum was measured and the calibration curve was created by the light absorbency of 305 nm. 0.1 g of the sample of Example and Comparative Example is weighed, dissolved in 50 mL of tetrahydrofuran (dilution ratio: 500 times), and 20 μL of 10% aqueous solution of tetrabutylammonium hydroxide is added and mixed, and then the UV spectrum is measured. The phenolic hydroxyl group equivalent (POHE) derived from bisphenol F was calculated by the following formula from the absorbance of.
POHE = {(m × k) / (c × d)} × 10 6
However, in the formula, m, k, c and d are as follows.
m: Sampling amount (g)
k: gram equivalent of bisphenol F, 100 (g / equivalent)
c: Standard curve concentration (mg / L)
d: dilution ratio of sample solution, 500 (mL)
《酸無水物基のモル数・酸無水物基当量》
共重合体（Ｃ）中の酸無水物基のモル数は、例えば、ＩＲスペクトルの吸光度を測定し、単位質量に含まれる酸無水物基のモル数を求めることができる。すなわち、予め、種々の配合割合でインデン類と無水マレイン酸類の混合物を作成し、各配合のＩＲスペクトルの吸光度を測定する。これらのＩＲスペクトルについて、無水マレイン酸類に含まれるＣ＝Ｏ結合に起因する１７８５ｃｍ−１のピーク強度とインデン類および無水マレイン酸類に含まれるＣ−Ｈ結合に起因する２８００〜３０００ｃｍ−１のピーク強度との比Ｒ〔Ｒ＝１７８５ｃｍ−１のピーク強度／２８００〜３０００ｃｍ−１のピーク強度〕を求め、無水マレイン酸類の物質量（モル）とインデン類および無水マレイン酸類の合計物質量（モル）の比Ｌ〔Ｌ＝無水マレイン酸類の物質量（モル）／インデン類および無水マレイン酸類の合計物質量（モル）〕に関する検量線を作成する。次に、共重合体（Ｃ）のＩＲスペクトルを測定し、Ｒを求め、検量線からＬを算出することで、単位質量あたりの酸無水物基のモル数を求めることができる。
<< mole number of acid anhydride group / acid anhydride group equivalent >>
The number of moles of the acid anhydride group in the copolymer (C) can be determined, for example, by measuring the absorbance of the IR spectrum to determine the number of moles of the acid anhydride group contained in the unit mass. That is, a mixture of indene and maleic anhydride is prepared in various proportions in advance, and the absorbance of IR spectrum of each combination is measured. For these IR spectra, the peak intensity at 1785 cm −1 due to the C = O bond contained in maleic anhydrides and the peak intensity at 2800 to 3000 cm −1 due to the C—H bonds contained in indenes and maleic anhydrides The ratio R (R = 1785 cm -1 peak intensity / 2800 to 3000 cm -1 peak intensity) to the ratio of the product mass (moles) of maleic anhydrides and the total mass (moles) of indenes and maleic anhydrides A calibration curve is prepared for the ratio L [L = the mass of the maleic anhydrides (moles) / total mass of the indenes and maleic anhydrides (moles)]. Next, the IR spectrum of the copolymer (C) is measured, R is determined, and L is calculated from the calibration curve, whereby the number of moles of acid anhydride group per unit mass can be determined.
〈その他含有してもよい成分〉
本発明の熱硬化性樹脂組成物には、本発明の目的を損なわない範囲で様々な無機充填剤および／または各種添加剤を配合することができる。
使用できる無機充填剤としては、例えば、カーボンブラック、シリカ、アルミナ、窒化ケイ素、炭化ケイ素、タルク、マイカ、ガラス繊維および炭素繊維が挙げられる。無機充填剤を配合する場合、熱膨張が低く熱伝導性に優れることから、シリカが好ましい。
使用できる各種添加剤としては、例えば、脂肪酸およびワックス等の離形剤、ならびに臭素系難燃剤、りん系難燃剤およびアンチモン系難燃助剤等の難燃剤・難燃助剤が挙げられる。
<Other ingredients that may be contained>
Various inorganic fillers and / or various additives can be blended into the thermosetting resin composition of the present invention as long as the object of the present invention is not impaired.
Inorganic fillers which can be used include, for example, carbon black, silica, alumina, silicon nitride, silicon carbide, talc, mica, glass fibers and carbon fibers. In the case of blending an inorganic filler, silica is preferable because of its low thermal expansion and excellent thermal conductivity.
Examples of various additives that can be used include mold release agents such as fatty acids and waxes, and flame retardants and flame retardant aids such as bromine flame retardants, phosphorus flame retardants and antimony flame retardant aids.
［硬化物］
本発明の硬化物は、上述した本発明の熱硬化性樹脂組成物を加熱硬化して得られる硬化物である。
より具体的には、本発明の熱硬化性樹脂組成物を加圧または非加圧下で、常圧または減圧下に加熱硬化することで、本発明の硬化物を得ることができる。
本発明の熱硬化性樹脂組成物を加熱硬化する方法は、特に限定されないが、例えば、以下のようにすることができる。
１５０℃〜２００℃の温度で、エポキシ樹脂（Ａ）、フェノール樹脂（Ｂ）および共重合体（Ｃ）を溶融混練して均一にした後、混合物の温度を１４０℃に下げ、硬化触媒（Ｄ）を加えてさらに溶融混練する。その後、１５０℃で２時間加熱し、１７０℃で２時間加熱し、さらに１８０℃で２時間加熱する。この一連の加熱操作により、本発明の熱硬化性樹脂組成物を加熱硬化させ、本発明の硬化物を得ることができる。
また、変法として、エポキシ樹脂（Ａ）、フェノール樹脂（Ｂ）、共重合体（Ｃ）および硬化触媒（Ｄ）を予めメチルエチルケトン等の溶媒に溶解し、８０℃〜１００℃に加熱して溶媒を蒸発させ、さらに、上記温度および上記時間で加熱して、本発明の熱硬化性樹脂組成物を加熱硬化させる方法も用いることができる。
[Cured product]
The cured product of the present invention is a cured product obtained by heat curing the above-mentioned thermosetting resin composition of the present invention.
More specifically, the cured product of the present invention can be obtained by heat curing the thermosetting resin composition of the present invention under normal pressure or reduced pressure under pressure or no pressure.
Although the method to heat-cure the thermosetting resin composition of this invention is not specifically limited, For example, it can be carried out as follows.
After the epoxy resin (A), the phenol resin (B) and the copolymer (C) are melt-kneaded at a temperature of 150 ° C. to 200 ° C. to make them uniform, the temperature of the mixture is lowered to 140 ° C., and a curing catalyst (D ) And further melt and knead. Then, it heats at 150 degreeC for 2 hours, heats at 170 degreeC for 2 hours, and also heats at 180 degreeC for 2 hours. By the series of heating operations, the thermosetting resin composition of the present invention can be heat-cured to obtain the cured product of the present invention.
As a modification, epoxy resin (A), phenol resin (B), copolymer (C) and curing catalyst (D) are dissolved in advance in a solvent such as methyl ethyl ketone and heated to 80 ° C. to 100 ° C. It is also possible to use a method of heating and curing the thermosetting resin composition of the present invention by evaporating and heating at the above temperature and the above time.
以下に、本発明を実施例により詳細に説明するが、本発明は、本実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples.
［ジシクロペンタジエン型エポキシ樹脂の合成］
容量１Ｌのガラス製セパラブルフラスコに、フェノール１０６ｇを入れ、オイルバスで１０５℃に加熱した。加熱後、三フッ化ホウ素フェノール錯体４ｇ（触媒）を、加熱したフェノールに加えた。次いで、上記セパラブルフラスコに、ジシクロペンタジエン８８ｇを、１時間かけて滴下した。滴下終了後、反応液を１４５℃に昇温し、さらに５時間反応させた。反応終了後、反応液にハイドロタルサイト１６．０ｇ（触媒中和剤）を添加し、撹拌しながら３０分かけて触媒を触媒中和剤に吸着させた。吸着後、反応液を濾過し、触媒を吸着した触媒中和剤を濾別した。濾別後、減圧下で、反応液を２２０℃まで昇温してフェノールを蒸留除去し、赤褐色のジシクロペンタジエン変性フェノール樹脂を得た。
[Synthesis of dicyclopentadiene type epoxy resin]
106 g of phenol was placed in a 1 L glass separable flask and heated to 105 ° C. in an oil bath. After heating, 4 g of boron trifluoride phenol complex (catalyst) was added to the heated phenol. Next, 88 g of dicyclopentadiene was dropped to the separable flask over 1 hour. After completion of the dropwise addition, the reaction solution was heated to 145 ° C. and allowed to react for 5 hours. After completion of the reaction, 16.0 g of hydrotalcite (catalyst neutralizer) was added to the reaction solution, and the catalyst was adsorbed on the catalyst neutralizer over 30 minutes with stirring. After adsorption, the reaction solution was filtered, and the catalyst neutralizer which adsorbed the catalyst was separated by filtration. After filtration, the reaction solution was heated to 220 ° C. under reduced pressure to distill off the phenol to obtain a reddish brown dicyclopentadiene modified phenolic resin.
容量５００ｍＬの４つ口フラスコに、得られたジシクロペンタジエン変性フェノール樹脂２５ｇ、クロロメチルオキシラン（エピクロロヒドリン）５１．４ｇおよびジメチルスルホキシド３０ｇを入れ、４０℃に加熱した。加熱後、上記４つ口フラスコに、水酸化ナトリウムを１．０ｇずつ、１０分間隔で６回、合計６．０ｇを添加した。次いで、反応液を５０℃で１時間反応させた後、７０℃に昇温し、さらに１時間反応させた。反応終了後、反応液を１３０℃に加熱し、減圧下で、過剰のクロロメチルオキシラン（エピクロロヒドリン）を１時間かけて蒸留除去した。除去後、反応液にメチルイソブチルケトンを４００ｇ加え、７０℃で１時間反応させた。反応液を分液ロートに移し、蒸留水２００ｍＬを加えて良く振り混ぜ、静置した。分液ロート内容物が有機層と水層に分離してから、水層を除去した。分液ロートに再び蒸留水２００ｍＬを加え、良く振り混ぜ、静置して有機層と水層に分離させ、水槽を除去する操作を、水層が中性になるまで繰り返し行った。水層が中性になった後、有機層をナスフラスコに移し、エバポレーターを用いて、バス温７０℃でメチルエチルケトンを蒸留除去し、ジシクロペンタジエン変性フェノール樹脂のエポキシ化物を得た。 In a 500 mL four-necked flask, 25 g of the obtained dicyclopentadiene modified phenolic resin, 51.4 g of chloromethyl oxirane (epichlorohydrin) and 30 g of dimethyl sulfoxide were placed and heated to 40 ° C. After heating, 1.0 g of sodium hydroxide was added to the four-necked flask six times at 10-minute intervals, for a total of 6.0 g. Then, the reaction solution was reacted at 50 ° C. for 1 hour, and then heated to 70 ° C., and further reacted for 1 hour. After completion of the reaction, the reaction solution was heated to 130 ° C., and excess chloromethyloxirane (epichlorohydrin) was distilled off under reduced pressure for 1 hour. After removal, 400 g of methyl isobutyl ketone was added to the reaction solution, and reacted at 70 ° C. for 1 hour. The reaction solution was transferred to a separatory funnel, 200 mL of distilled water was added, the mixture was shaken well, and allowed to stand. The aqueous layer was removed after the contents of the separating funnel separated into organic and aqueous layers. 200 mL of distilled water was again added to the separating funnel, shaken well, allowed to stand, and separated into an organic layer and an aqueous layer, and the operation of removing the water tank was repeated until the aqueous layer became neutral. After the aqueous layer became neutral, the organic layer was transferred to an eggplant flask, and methyl ethyl ketone was distilled off using an evaporator at a bath temperature of 70 ° C. to obtain an epoxidized dicyclopentadiene modified phenolic resin.
得られたジシクロペンタジエン変性フェノール樹脂のエポキシ化物のエポキシ当量を、ＪＩＳ Ｋ ７２３６：２００９「エポキシ樹脂のエポキシ当量の求め方」に従って測定した結果、２６０ｇ／当量であった。 As a result of measuring the epoxy equivalent of the epoxy compound of the obtained dicyclopentadiene modified phenolic resin according to JIS K 7236: 2009 "method of determining the epoxy equivalent of an epoxy resin", it was 260 g / equivalent.
以下、得られたジシクロペンタジエン変性フェノール樹脂のエポキシ化物を「ＤＣＰＤエポキシ樹脂１」という場合がある。 Hereinafter, the epoxy compound of the obtained dicyclopentadiene modified phenol resin may be called "DCPD epoxy resin 1".
［インデン無水マレイン酸共重合樹脂の合成］
容量１リットルのガラス製セパラブルフラスコに、インデン６０ｇ、無水マレイン酸３５．９ｇおよびトルエン４００ｇを加え、セパラブルフラスコ内容物を１００℃に昇温した。次いで、上記セパラブルフラスコに、アゾビスイソブチロニトロル１．２ｇをトルエン３０ｇに溶解した溶液を、３０分かけて滴下した。滴下終了後、反応液を４時間反応させ、１晩放置して冷却した。冷却後、２Ｌのメタノール中に反応液を徐々に滴下して、再沈殿させた。沈殿物を濾別して、インデン無水マレイン酸共重合樹脂を得た。
得られたインデン無水マレイン酸共重合樹脂の酸無水物当量を、以下の測定方法に従って測定したところ、１３１ｇ／当量であった。
[Synthesis of Indene and Maleic Anhydride Copolymer Resin]
60 g of indene, 35.9 g of maleic anhydride and 400 g of toluene were added to a 1-liter glass separable flask, and the contents of the separable flask were heated to 100 ° C. Next, a solution of 1.2 g of azobisisobutyronitrol in 30 g of toluene was added dropwise to the separable flask over 30 minutes. After completion of the dropwise addition, the reaction solution was allowed to react for 4 hours and left to stand overnight for cooling. After cooling, the reaction solution was gradually dropped in 2 L of methanol to cause reprecipitation. The precipitate was separated by filtration to obtain an indene maleic anhydride copolymer resin.
It was 131 g / equivalent when the acid anhydride equivalent of the obtained indene maleic anhydride copolymer resin was measured according to the following measuring methods.
予め、種々の配合割合でインデンと無水マレイン酸の混合物を作成し、各配合のＩＲスペクトルの吸光度を測定した。これらのＩＲスペクトルについて、無水マレイン酸に含まれるＣ＝Ｏ結合に起因する１７８５ｃｍ−１のピーク強度とインデンおよび無水マレイン酸に含まれるＣ−Ｈ結合に起因する２８００〜３０００ｃｍ−１のピーク強度の比の値Ｒ〔Ｒ＝１７８５ｃｍ−１のピーク強／２８００〜３０００ｃｍ−１のピーク強度〕と無水マレイン酸の物質量（モル）とインデンおよび無水マレイン酸の合計物質量（モル）の比の値Ｌ〔Ｌ＝無水マレイン酸の物質量（モル）／インデンおよび無水マレイン酸の合計物質量（モル）〕に関する検量線を作成した。次に、インデン無水マレイン酸共重合樹脂のＩＲスペクトルを測定し、Ｒを求め、検量線からＬを算出し、１当量の酸無水物基を含む樹脂の質量を求めた。 In advance, mixtures of indene and maleic anhydride were prepared at various compounding proportions, and the absorbance of the IR spectrum of each compound was measured. Regarding these IR spectra, the peak intensity of 1785 cm −1 due to the C = O bond contained in maleic anhydride and the peak intensity of 2800 to 3000 cm −1 due to the C—H bond contained in indene and maleic anhydride the ratio of the values of R substance amount of maleic acid [R = 1785 cm peak intensity of the peak strength / 2800 to 3000 cm -1 -1] (mol) and indene and total amount of substance of maleic anhydride ratio (mol) A calibration curve was prepared for L [L = quantity of substance of the maleic anhydride (moles) / total mass of the indene and maleic anhydride (moles)]. Next, the IR spectrum of the indene maleic anhydride copolymer resin was measured, R was determined, L was calculated from the calibration curve, and the mass of the resin containing one equivalent of an acid anhydride group was determined.
以下、得られたインデン無水マレイン酸共重合樹脂を「ＩＭＡ樹脂１」という場合がある。 Hereinafter, the obtained indene maleic anhydride copolymer resin may be called "IMA resin 1".
［実施例１］
〈硬化物の製造〉
上記のとおり合成したＤＣＰＤエポキシ樹脂１ ３．０ｇ（エポキシ基のモル数＝ａ１［モル］）、ノボラック型フェノール樹脂（ＰＨＥＮＯＬＩＴＥ ＴＤ−２０９０，ＤＩＣ社製；フェノール性水酸基当量１０５ｇ／当量；以下「フェノールノボラック樹脂１」という場合がある）０．８５ｇ（フェノール性水酸基のモル数＝ｂ１［モル］）、上記のとおり合成したＩＭＡ樹脂１ １．５３ｇ（酸無水物基のモル数＝ｃ１［モル］）を混合して、熱硬化性樹脂組成物（以下「熱硬化性樹脂組成物１」という場合がある）を製造した〔ａ１：（ｂ１＋ｃ１）＝１．００：１．００，ｂ１：ｃ１＝７０：３０〕。
熱硬化性樹脂組成物１をアルミ製カップに入れ、ホットプレートを用いて１８０℃に加熱し、ステンレス製スプーンを用いて均一に撹拌した。温度を１４０℃に下げて、２−メチルイミダゾール０．０４ｇ（硬化触媒）を加え、均一にした。その後、１５０℃で２時間、１７０℃で２時間、１８０℃で２時間加熱して、熱硬化性樹脂組成物１を硬化させ、硬化物（以下「熱硬化物１」という場合がある）を得た。
Example 1
<Manufacture of hardened material>
3.0 g of DCPD epoxy resin 1 synthesized as described above (mole number of epoxy group = a 1 [mole]), novolac type phenol resin (PHENOLITE TD-2090, manufactured by DIC; phenolic hydroxyl equivalent 105 g / equivalent; 0.85 g (mole number of phenolic hydroxyl group = b 1 [mole]), sometimes referred to as “phenol novolac resin 1”, 1.53 g of IMA resin 1 synthesized as described above (mole number of acid anhydride group = c 1 [Mol] was mixed to produce a thermosetting resin composition (hereinafter sometimes referred to as “thermosetting resin composition 1”) [a 1 : (b 1 + c 1 ) = 1.00: 1 .00, b 1: c 1 = 70: 30 ].
The thermosetting resin composition 1 was placed in an aluminum cup, heated to 180 ° C. using a hot plate, and uniformly stirred using a stainless steel spoon. The temperature was lowered to 140 ° C. and 0.04 g of 2-methylimidazole (curing catalyst) was added and homogenized. Thereafter, the thermosetting resin composition 1 is cured by heating at 150 ° C. for 2 hours, at 170 ° C. for 2 hours, and at 180 ° C. for 2 hours, and a cured product (hereinafter sometimes referred to as “thermally cured product 1”) Obtained.
〈硬化物の耐熱性および誘電特性の評価〉
《耐熱性の評価方法》
耐熱性は、熱硬化性樹脂組成物１を上記加熱条件で加熱硬化して製造した測定用試料のガラス転移温度（Ｔｇ；単位℃）を測定することで評価した。評価結果を表１の該当欄に示す。
測定用試料は、厚み０．３ｍｍに成形した硬化成形体を１０ｍｍ×１０ｍｍ角に切断した後、表面を紙やすりで研磨して、平滑にして製造した。
測定用試料のＴｇは、熱機械分析装置（ＴＭＡ−５０，島津製作所社製）を用いて、針入法（プローブ径＝０．５ｍｍ）により、荷重１．０ｇの条件で、窒素雰囲気下、室温から２５０℃まで、１０℃／分で昇温した時のＴＭＡ曲線を測定し、変曲点近傍の接線の交点として測定した。
<Evaluation of heat resistance and dielectric properties of cured product>
Evaluation method of heat resistance
The heat resistance was evaluated by measuring the glass transition temperature (Tg; unit ° C.) of a measurement sample produced by heat curing the thermosetting resin composition 1 under the above heating conditions. The evaluation results are shown in the corresponding columns of Table 1.
The measurement sample was manufactured by cutting a cured molded product molded to a thickness of 0.3 mm into 10 mm × 10 mm square and then polishing the surface with a sandpaper to make it smooth.
The Tg of the sample for measurement is a nitrogen atmosphere under a condition of a load of 1.0 g by a penetration method (probe diameter = 0.5 mm) using a thermomechanical analyzer (TMA-50, manufactured by Shimadzu Corporation). The TMA curve was measured when the temperature was raised from room temperature to 250 ° C. at 10 ° C./min, and was measured as the intersection of tangents near the inflection point.
《誘電特性の評価方法》
誘電特性は、熱硬化性樹脂組成物１を上記加熱条件で加熱硬化し、加工して製造した測定用試料の比誘電率（εｒ；単位なし）を測定することで評価した。誘電率は評価結果を表１の該当欄に示す。
測定用試料は、厚み０．３ｍｍに成形した硬化成形体を４０ｍｍ×４０ｍｍ角に切断した後、表面を紙やすりで研磨して、平滑にして製造した。
測定用試料のεｒは、誘電率測定装置（ＡＥＴ社製）を用いて、同軸共振法により１ＧＨｚの共振周波数の条件で測定した。
<< Evaluation method of dielectric characteristics >>
The dielectric properties were evaluated by measuring the relative dielectric constant (ε r ; no unit) of the measurement sample produced by heat curing the thermosetting resin composition 1 under the above heating conditions and processing it. The dielectric constant is shown in the corresponding column of Table 1 for the evaluation results.
The measurement sample was manufactured by cutting a cured molded product molded to a thickness of 0.3 mm into a 40 mm × 40 mm square and then polishing the surface with a sandpaper to make it smooth.
The ε r of the measurement sample was measured by a coaxial resonance method under the condition of a resonance frequency of 1 GHz using a dielectric constant measurement device (manufactured by AET).
〈硬化物の成形性の評価方法〉
表１には以下の形式で示した。
１８０℃において、エポキシ樹脂と硬化剤が均一に混ざり、その後の触媒添加と加熱処理によって硬化物が得られ、得られた硬化物を誘電特性の測定用試料に加工することができた、・・・・・・Ａ
１８０℃において、エポキシ樹脂と硬化剤が不均一で混ざりにくく、その後の触媒添加と加熱処理によって硬化物が得られず、誘電特性の測定用試料への加工ができなかった・・・・・・Ｘ
<Method of evaluating moldability of cured product>
Table 1 shows the following format.
At 180 ° C., the epoxy resin and the curing agent were uniformly mixed, and a cured product was obtained by the subsequent addition of a catalyst and heat treatment, and the obtained cured product could be processed into a sample for measurement of dielectric properties, ... A
At 180 ° C., the epoxy resin and the curing agent are uneven and difficult to mix, and no cured product was obtained by the subsequent addition of catalyst and heat treatment, and processing into a sample for measurement of dielectric characteristics could not be performed. X
［実施例２］
ＤＣＰＤエポキシ樹脂１ ３．０ｇ（エポキシ基のモル数＝ａ２［モル］）、フェノールノボラック樹脂１ １．０３ｇ（フェノール性水酸基のモル数＝ｂ２［モル］）およびＩＭＡ樹脂１ ０．７９ｇ（酸無水物基のモル数＝ｃ２［モル］）を混合して、熱硬化性樹脂組成物（以下「熱硬化性樹脂組成物２」という場合がある）を製造した〔ａ２：（ｂ２＋ｃ２）＝１．００：１．００，ｂ２：ｃ２＝８５：１５〕。
Example 2
DCPD epoxy resin 1 3.0 g (mole number of epoxy group = a 2 [mole]), phenol novolak resin 1 1.03 g (mole number of phenolic hydroxyl group = b 2 [mole]) and IMA resin 1 0.79 g (mole) The number of moles of acid anhydride group = c 2 [moles] was mixed to produce a thermosetting resin composition (hereinafter sometimes referred to as “thermosetting resin composition 2”) [a 2 : (b 2 + c 2 ) = 1.00: 1.00, b 2 : c 2 = 85: 15].
熱硬化性樹脂組成物２を実施例１に記載した加熱条件で熱硬化させて、硬化物（以下「硬化物２」という場合がある）を得た。 The thermosetting resin composition 2 was thermally cured under the heating conditions described in Example 1 to obtain a cured product (hereinafter sometimes referred to as “cured product 2”).
実施例１に記載した評価方法により、熱硬化性樹脂組成物２の硬化物の耐熱性、誘電特性および成形性を評価した。評価結果を表１の該当欄にそれぞれ示す。 The heat resistance, dielectric properties and moldability of the cured product of the thermosetting resin composition 2 were evaluated by the evaluation method described in Example 1. The evaluation results are shown in the corresponding columns of Table 1, respectively.
［実施例３］
ＤＣＰＤエポキシ樹脂１ ３．０ｇ（エポキシ基のモル数＝ａ３［モル］）、フェノールノボラック樹脂１ １．０９ｇ（フェノール性水酸基のモル数＝ｂ３［モル］）およびＩＭＡ樹脂１ ０．５１ｇ（酸無水物基のモル数＝ｃ３［モル］）を混合して、熱硬化性樹脂組成物（以下「熱硬化性樹脂組成物３」という場合がある）を製造した〔ａ３：（ｂ３＋ｃ３）＝１．００：１．００，ｂ３：ｃ３＝９０：１０〕。
[Example 3]
DCPD epoxy resin 1 3.0 g (mole number of epoxy group = a 3 [mole]), phenol novolak resin 1 1.09 g (mole number of phenolic hydroxyl group = b 3 [mole]), IMA resin 1 0.51 g (mole) The number of moles of acid anhydride group = c 3 [mole] was mixed to produce a thermosetting resin composition (hereinafter sometimes referred to as "thermosetting resin composition 3") [a 3 : (b 3 + c 3 ) = 1.00: 1.00, b 3 : c 3 = 90: 10].
熱硬化性樹脂組成物３を実施例１に記載した加熱条件で熱硬化させて、硬化物（以下「硬化物３」という場合がある）を得た。 The thermosetting resin composition 3 was thermally cured under the heating conditions described in Example 1 to obtain a cured product (hereinafter sometimes referred to as “cured product 3”).
実施例１に記載した評価方法により、熱硬化性樹脂組成物３の硬化物の耐熱性、誘電特性および成形性を評価した。評価結果を表１の該当欄にそれぞれ示す。 The heat resistance, dielectric properties and moldability of the cured product of the thermosetting resin composition 3 were evaluated by the evaluation method described in Example 1. The evaluation results are shown in the corresponding columns of Table 1, respectively.
［実施例４］
ＤＣＰＤエポキシ樹脂１ ３．０ｇ（エポキシ基のモル数＝ａ４［モル］）、フェノールノボラック樹脂１ １．１５ｇ（フェノール性水酸基のモル数＝ｂ４［モル］）およびＩＭＡ樹脂１ ０．２５ｇ（酸無水物基のモル数＝ｃ４［モル］）を混合して、熱硬化性樹脂組成物（以下「熱硬化性樹脂組成物４」という場合がある）を製造した〔ａ４：（ｂ４＋ｃ４）＝１．００：１．００，ｂ４：ｃ４＝９５：５〕。
Example 4
DCPD epoxy resin 1 3.0 g (mole number of epoxy group = a 4 [mole]), phenol novolak resin 1 1.15 g (mole number of phenolic hydroxyl group = b 4 [mole]) and IMA resin 1 0.25 g (mole) The number of moles of acid anhydride group = c 4 [mole] was mixed to produce a thermosetting resin composition (hereinafter sometimes referred to as "thermosetting resin composition 4") [a 4 : (b 4 + c 4 ) = 1.00: 1.00, b 4 : c 4 = 95: 5].
熱硬化性樹脂組成物４を実施例１に記載した加熱条件で熱硬化させて、硬化物（以下「硬化物４」という場合がある）を得た。 The thermosetting resin composition 4 was thermally cured under the heating conditions described in Example 1 to obtain a cured product (hereinafter sometimes referred to as “cured product 4”).
実施例１に記載した評価方法により、熱硬化性樹脂組成物４の硬化物の耐熱性、誘電特性および成形性を評価した。評価結果を表１の該当欄にそれぞれ示す。 The heat resistance, dielectric properties and moldability of the cured product of the thermosetting resin composition 4 were evaluated by the evaluation method described in Example 1. The evaluation results are shown in the corresponding columns of Table 1, respectively.
［実施例５］
ＤＣＰＤエポキシ樹脂１ ３．０ｇ（エポキシ基のモル数＝ａ５［モル］）、フェノールノボラック樹脂１ ０．４３ｇ（フェノール性水酸基のモル数＝ｂ５［モル］）およびＩＭＡ樹脂１ ０．７７ｇ（酸無水物基のモル数＝ｃ５［モル］）を混合して、熱硬化性樹脂組成物（以下「熱硬化性樹脂組成物５」という場合がある）を製造した〔ａ５：（ｂ５＋ｃ５）＝１．００：０．５０，ｂ５：ｃ５＝７０：３０〕。
[Example 5]
DCPD epoxy resin 1 3.0 g (mole number of epoxy group = a 5 [mole]), phenol novolac resin 1 0.43 g (mole number of phenolic hydroxyl group = b 5 [mole]) and IMA resin 1 0.77 g (mole) The number of moles of acid anhydride group = c 5 [mole]) was mixed to produce a thermosetting resin composition (hereinafter sometimes referred to as “thermosetting resin composition 5”) [a 5 : (b 5 + c 5 ) = 1.00: 0.50, b 5 : c 5 = 70:30].
熱硬化性樹脂組成物５を実施例１に記載した加熱条件で熱硬化させて、硬化物（以下「硬化物５」という場合がある）を得た。 The thermosetting resin composition 5 was thermally cured under the heating conditions described in Example 1 to obtain a cured product (hereinafter sometimes referred to as “cured product 5”).
実施例１に記載した評価方法により、熱硬化性樹脂組成物５の硬化物の耐熱性、誘電特性および成形性を評価した。評価結果を表１の該当欄にそれぞれ示す。 The heat resistance, dielectric properties and moldability of the cured product of the thermosetting resin composition 5 were evaluated by the evaluation method described in Example 1. The evaluation results are shown in the corresponding columns of Table 1, respectively.
［比較例１］
ＤＣＰＤエポキシ樹脂１ ３．０ｇ（エポキシ基のモル数＝ａ６［モル］）およびＩＭＡ樹脂１ ５．１１ｇ（酸無水物基のモル数＝ｃ６［モル］）を混合して、フェノールノボラック樹脂１は使用せず（フェノール性水酸基のモル数＝ｂ５［モル］）、樹脂組成物（以下「樹脂組成物６」という場合がある）を製造した〔ａ６：（ｂ６＋ｃ６）＝１．００：１．００，ｂ６：ｃ６＝０：１００〕。
樹脂組成物６を実施例１に記載した加熱条件で熱硬化させようとしたが、硬化物を得ることができなかった。
硬化物の耐熱性および誘電特性の評価を行っていない。評価結果として「Ｎ．Ｄ．」（データなし）を表１の該当欄に示す。
成形性は、樹脂組成物６を用いて評価を行った。評価結果を表１の該当欄に示す。
Comparative Example 1
DCPD epoxy resin 1 3.0 g (mole number of epoxy group = a 6 [mole]) and IMA resin 15 5.11 g (mole number of acid anhydride group = c 6 [mole]) are mixed to obtain a phenol novolac resin 1 was not used (mole number of phenolic hydroxyl group = b 5 [mole]), and a resin composition (hereinafter sometimes referred to as “resin composition 6”) was produced [a 6 : (b 6 + c 6 ) = 1.00: 1.00, b 6 : c 6 = 0: 100].
Although it was tried to thermally cure the resin composition 6 under the heating conditions described in Example 1, a cured product could not be obtained.
The heat resistance and dielectric properties of the cured product were not evaluated. As an evaluation result, "ND" (no data) is shown in the corresponding column of Table 1.
The moldability was evaluated using resin composition 6. The evaluation results are shown in the corresponding columns of Table 1.
［比較例２］
ＤＣＰＤエポキシ樹脂１ ３．０ｇ（エポキシ基のモル数＝ａ７［モル］）、フェノールノボラック樹脂１ ０．６１ｇ（フェノール性水酸基のモル数＝ｂ７［モル］）およびＩＭＡ樹脂１ ２．５６ｇ（酸無水物基のモル数＝ｃ７［モル］）を混合して、樹脂組成物（以下「樹脂組成物７」という場合がある）を製造した〔ａ７：（ｂ７＋ｃ７）＝１．００：１．００，ｂ７：ｃ７＝５０：５０〕。
樹脂組成物６を実施例１に記載した加熱条件で熱硬化させようとしたが、硬化物を得ることができなかった。
硬化物の耐熱性および誘電特性の評価を行っていない。評価結果として「Ｎ．Ｄ．」（データなし）を表１の該当欄に示す。
成形性は、樹脂組成物７を用いて評価を行った。評価結果を表１の該当欄に示す。
Comparative Example 2
DCPD epoxy resin 1 3.0 g (mole number of epoxy group = a 7 [mole]), phenol novolak resin 1 0.61 g (mole number of phenolic hydroxyl group = b 7 [mole]), and IMA resin 1 2.56 g (mole) The number of moles of acid anhydride group = c 7 (mole) was mixed to produce a resin composition (hereinafter sometimes referred to as “resin composition 7”) [a 7 : (b 7 + c 7 ) = 1 .00: 1.00, b 7 : c 7 = 50: 50].
Although it was tried to thermally cure the resin composition 6 under the heating conditions described in Example 1, a cured product could not be obtained.
The heat resistance and dielectric properties of the cured product were not evaluated. As an evaluation result, "ND" (no data) is shown in the corresponding column of Table 1.
The moldability was evaluated using resin composition 7. The evaluation results are shown in the corresponding columns of Table 1.
［比較例３］
ＤＣＰＤエポキシ樹脂１ ３．０ｇ（エポキシ基のモル数＝ａ８［モル］）およびフェノールノボラック樹脂１ １．５４ｇ（フェノール性水酸基のモル数＝ｂ８［モル］）を混合して、ＩＭＡ樹脂１を使用せず（酸無水物基のモル数＝ｃ８［モル］）、熱硬化性樹脂組成物（以下「熱硬化性樹脂組成物８」という場合がある）を製造した〔ａ８：（ｂ８＋ｃ８）＝１．００：１．２７，ｂ８：ｃ８＝１００：０〕。
Comparative Example 3
DCPD epoxy resin 1 3.0 g (mole number of epoxy group = a 8 [mole]) and phenol novolac resin 1 1.54 g (mole number of phenolic hydroxyl group = b 8 [mole]) are mixed to obtain IMA resin 1 Were used (number of moles of acid anhydride group = c 8 [mole]) to produce a thermosetting resin composition (hereinafter sometimes referred to as "thermosetting resin composition 8") [a 8 : ( b 8 + c 8) = 1.00 : 1.27, b 8: c 8 = 100: 0 ].
熱硬化性樹脂組成物８を実施例１に記載した加熱条件で熱硬化させて、硬化物（以下「硬化物８」という場合がある）を得た。 The thermosetting resin composition 8 was thermally cured under the heating conditions described in Example 1 to obtain a cured product (hereinafter sometimes referred to as “cured product 8”).
実施例１に記載した評価方法により、熱硬化性樹脂組成物８の硬化物の耐熱性、誘電特性および成形性を評価した。評価結果を表１の該当欄にそれぞれ示す。 The heat resistance, dielectric properties and moldability of the cured product of the thermosetting resin composition 8 were evaluated by the evaluation method described in Example 1. The evaluation results are shown in the corresponding columns of Table 1, respectively.
［比較例４］
オルトクレゾールノボラック型エポキシ樹脂（ＥＰＩＣＬＯＮ（登録商標） Ｎ−６７３，ＤＩＣ社製；エポキシ基当量２０５〜２１５ｇ／当量；以下「ＯＣＮエポキシ樹脂１」という場合がある） ３．０ｇ（エポキシ基のモル数＝ａ９［モル］）およびフェノールノボラック樹脂１ １．５４ｇ（フェノール性水酸基のモル数＝ｂ９［モル］）を混合して、ＩＭＡ樹脂１を使用せず（酸無水物基のモル数＝ｃ９［モル］）、熱硬化性樹脂組成物（以下「熱硬化性樹脂組成物９」という場合がある）を製造した〔ａ９：（ｂ９＋ｃ９）＝１．００：１．００，ｂ９：ｃ９＝１００：０〕。
Comparative Example 4
Ortho cresol novolac type epoxy resin (EPICLON (registered trademark) N-673, manufactured by DIC; epoxy group equivalent 205 to 215 g / equivalent; hereinafter sometimes referred to as "OCN epoxy resin 1") 3.0 g (the number of moles of epoxy group) = A 9 [mol]) and 1.54 g of phenol novolak resin 1 (mol of phenolic hydroxyl group = b 9 [mol]) are mixed without using IMA resin 1 (mol of acid anhydride group = c 9 [mol]), a thermosetting resin composition (hereinafter sometimes referred to as “thermosetting resin composition 9”) was produced [a 9 : (b 9 + c 9 ) = 1.00: 1.00 , B 9 : c 9 = 100: 0].
熱硬化性樹脂組成物９を実施例１に記載した加熱条件で熱硬化させて、硬化物（以下「硬化物９」という場合がある）を得た。 The thermosetting resin composition 9 was thermally cured under the heating conditions described in Example 1 to obtain a cured product (hereinafter sometimes referred to as “cured product 9”).
実施例１に記載した評価方法により、熱硬化性樹脂組成物９の硬化物の耐熱性、誘電特性および成形性を評価した。評価結果を表１の該当欄にそれぞれ示す。 The heat resistance, dielectric properties and moldability of the cured product of the thermosetting resin composition 9 were evaluated by the evaluation method described in Example 1. The evaluation results are shown in the corresponding columns of Table 1, respectively.
［比較例５］
ＯＣＮエポキシ樹脂１ ３．０ｇ（エポキシ基のモル数＝ａ１０［モル］）、フェノールノボラック樹脂１ １．２３ｇ（フェノール性水酸基のモル数＝ｂ１０［モル］）およびＩＭＡ樹脂１ １．２９ｇ（酸無水物基のモル数＝ｃ１０［モル］）を混合して、樹脂組成物（以下「樹脂組成物１０」という場合がある）を製造した〔ａ１０：（ｂ１０＋ｃ１０）＝１．００：１．００，ｂ１０：ｃ１０＝８０：２０〕。
樹脂組成物１０を実施例１に記載した加熱条件で熱硬化させようとしたが、硬化物を得ることができなかった。
硬化物の耐熱性および誘電特性の評価を行っていない。評価結果として「Ｎ．Ｄ．」（データなし）を表１の該当欄に示す。
成形性は、樹脂組成物１０を用いて評価を行った。評価結果を表１の該当欄に示す。
Comparative Example 5
3.0 g of OCN epoxy resin 1 (mole number of epoxy group = a 10 [mole]), 1.23 g of phenol novolac resin 1 (mole number of phenolic hydroxyl group = b 10 [mole]) and 1.29 g of IMA resin 1 the number of moles of the acid anhydride group = c 10 [mol]) were mixed, the resin composition (prepared following may be referred to as "resin composition 10") [a 10: (b 10 + c 10) = 1 .00: 1.00, b 10: c 10 = 80: 20 ].
Although the resin composition 10 was to be thermally cured under the heating conditions described in Example 1, a cured product could not be obtained.
The heat resistance and dielectric properties of the cured product were not evaluated. As an evaluation result, "ND" (no data) is shown in the corresponding column of Table 1.
The moldability was evaluated using the resin composition 10. The evaluation results are shown in the corresponding columns of Table 1.
実施例１〜５の熱硬化性樹脂組成物は、高いガラス転移温度と低い誘電率を合わせもつ硬化物が得られた。これに対し、比較例３の組成物は、ガラス転移温度が低く、比較例４の組成物は、比誘電率の高い硬化物であった。
比較例１、２および５の樹脂組成物は、硬化物が得られなかったことから、ガラス転移温度、誘電特性を評価できなかった。
本発明の熱硬化性樹脂組成物を加熱硬化して得られる硬化物は、耐熱性が高く、比誘電率が低く、伝送損失が少ないことから、高速大容量の通信機器向けの回路基板や半導体封止材等に用いることができる。
The thermosetting resin compositions of Examples 1 to 5 gave cured products having a high glass transition temperature and a low dielectric constant. On the other hand, the composition of Comparative Example 3 had a low glass transition temperature, and the composition of Comparative Example 4 had a cured product with a high relative dielectric constant.
The resin compositions of Comparative Examples 1, 2 and 5 could not evaluate the glass transition temperature and the dielectric characteristics because no cured product was obtained.
The cured product obtained by heat curing the thermosetting resin composition of the present invention has high heat resistance, low relative dielectric constant, and low transmission loss, so it can be used as a circuit board or semiconductor for high-speed large-capacity communication devices. It can be used as a sealing material or the like.
Claims (2)
前記ジシクロペンタジエン型エポキシ樹脂（Ａ）中のエポキシ基のモル数ａと、前記ノボラック型フェノール樹脂（Ｂ）中のフェノール性水酸基のモル数ｂと、前記インデン類と無水マレイン酸類との共重合体（Ｃ）中の酸無水物基のモル数ｃが下記の関係を満たす、熱硬化性樹脂組成物。
ａ：ｂ＋ｃ＝１．００：１．１０〜１．００：０．４５、かつ
ｂ：ｃ＝９６：４〜６５：３５ A thermosetting resin composition comprising a dicyclopentadiene type epoxy resin (A), a novolac type phenol resin (B), a copolymer (C) of indene and maleic anhydrides, and a curing catalyst (D) ,
The number of moles a of epoxy groups in the dicyclopentadiene type epoxy resin (A), the number b of moles of phenolic hydroxyl groups in the novolac type phenolic resin (B), and the co-weight of the indens and the maleic anhydrides Thermosetting resin composition in which the number of moles c of acid anhydride groups in united (C) satisfies the following relationship.
a: b + c = 1.00: 1.10 to 1.00: 0.45, and b: c = 96: 4 to 65: 35
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114423799A (en) * | 2019-08-08 | 2022-04-29 | 阿迪塔亚博拉化学品(泰国)有限公司(环氧树脂事业部) | Modified epoxy resins |
| JP7132385B1 (en) | 2021-03-30 | 2022-09-06 | 日本化薬株式会社 | Epoxy resin, curable resin composition, and cured product thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09249794A (en) * | 1996-03-15 | 1997-09-22 | Nippon Steel Chem Co Ltd | Liquid epoxy resin composition for sealing electronic component and cured product thereof |
| JPH10330461A (en) * | 1997-03-31 | 1998-12-15 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing electronic part and electronic part |
| JPH11124427A (en) * | 1997-10-24 | 1999-05-11 | Osaka Organic Chem Ind Ltd | Thermosetting resin composition |
| JP2012153896A (en) * | 2006-12-05 | 2012-08-16 | Hitachi Chemical Co Ltd | Flame retardant resin compound, thermosetting resin composition using the same, prepreg, and laminate |
| JP2015166431A (en) * | 2014-03-04 | 2015-09-24 | 日立化成株式会社 | Thermosetting resin composition, prepreg and laminated plate |
| JP2017039909A (en) * | 2015-08-21 | 2017-02-23 | 住友ベークライト株式会社 | Resin composition, photosensitive resin composition, resin film and electronic device |
-
2018
- 2018-01-11 JP JP2018002418A patent/JP6764885B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09249794A (en) * | 1996-03-15 | 1997-09-22 | Nippon Steel Chem Co Ltd | Liquid epoxy resin composition for sealing electronic component and cured product thereof |
| JPH10330461A (en) * | 1997-03-31 | 1998-12-15 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing electronic part and electronic part |
| JPH11124427A (en) * | 1997-10-24 | 1999-05-11 | Osaka Organic Chem Ind Ltd | Thermosetting resin composition |
| JP2012153896A (en) * | 2006-12-05 | 2012-08-16 | Hitachi Chemical Co Ltd | Flame retardant resin compound, thermosetting resin composition using the same, prepreg, and laminate |
| JP2015166431A (en) * | 2014-03-04 | 2015-09-24 | 日立化成株式会社 | Thermosetting resin composition, prepreg and laminated plate |
| JP2017039909A (en) * | 2015-08-21 | 2017-02-23 | 住友ベークライト株式会社 | Resin composition, photosensitive resin composition, resin film and electronic device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114423799A (en) * | 2019-08-08 | 2022-04-29 | 阿迪塔亚博拉化学品(泰国)有限公司(环氧树脂事业部) | Modified epoxy resins |
| JP7132385B1 (en) | 2021-03-30 | 2022-09-06 | 日本化薬株式会社 | Epoxy resin, curable resin composition, and cured product thereof |
| WO2022209642A1 (en) * | 2021-03-30 | 2022-10-06 | 日本化薬株式会社 | Epoxy resin and production method therefor, curable resin composition, and cured product thereof |
| JP2022154013A (en) * | 2021-03-30 | 2022-10-13 | 日本化薬株式会社 | Epoxy resin, curable resin composition, and cured product of the same |
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