JP2005060649A - Epoxy resin composition, epoxy resin cured product, and novolak resin - Google Patents
Epoxy resin composition, epoxy resin cured product, and novolak resin Download PDFInfo
- Publication number
- JP2005060649A JP2005060649A JP2003349398A JP2003349398A JP2005060649A JP 2005060649 A JP2005060649 A JP 2005060649A JP 2003349398 A JP2003349398 A JP 2003349398A JP 2003349398 A JP2003349398 A JP 2003349398A JP 2005060649 A JP2005060649 A JP 2005060649A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin
- novolak resin
- novolak
- carbon atoms
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 99
- 239000011347 resin Substances 0.000 title claims abstract description 99
- 229920003986 novolac Polymers 0.000 title claims abstract description 88
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 77
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 77
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 125000001424 substituent group Chemical group 0.000 claims abstract description 27
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 43
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 25
- 239000011888 foil Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000012776 electronic material Substances 0.000 abstract description 10
- 125000004093 cyano group Chemical group *C#N 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 150000002989 phenols Chemical class 0.000 description 19
- 239000002904 solvent Substances 0.000 description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000011889 copper foil Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- -1 amine compound Chemical class 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 9
- AYKYOOPFBCOXSL-UHFFFAOYSA-N (4-hydroxyphenyl)acetonitrile Chemical compound OC1=CC=C(CC#N)C=C1 AYKYOOPFBCOXSL-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004373 Pullulan Substances 0.000 description 6
- 229920001218 Pullulan Polymers 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 235000019423 pullulan Nutrition 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Chemical group C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- BTNSSVRIZUUYGM-UHFFFAOYSA-N 2-(4-hydroxyphenyl)propanenitrile Chemical compound N#CC(C)C1=CC=C(O)C=C1 BTNSSVRIZUUYGM-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical group CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical group C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 125000004966 cyanoalkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- ISBHMJZRKAFTGE-ONEGZZNKSA-N (e)-pent-2-enenitrile Chemical group CC\C=C\C#N ISBHMJZRKAFTGE-ONEGZZNKSA-N 0.000 description 1
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical group C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- APGLXTXFTYAQKC-UHFFFAOYSA-N 2,5-dihydroxybenzonitrile Chemical compound OC1=CC=C(O)C(C#N)=C1 APGLXTXFTYAQKC-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- ILGVZPUAKAKBDA-UHFFFAOYSA-N 2-(2-hydroxyphenyl)propanenitrile Chemical compound N#CC(C)C1=CC=CC=C1O ILGVZPUAKAKBDA-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- WBAXCOMEMKANRN-UHFFFAOYSA-N 2-methylbut-3-enenitrile Chemical group C=CC(C)C#N WBAXCOMEMKANRN-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
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 1
- ABHOEQJNEOMTEK-UHFFFAOYSA-N 3,5-dihydroxybenzonitrile Chemical compound OC1=CC(O)=CC(C#N)=C1 ABHOEQJNEOMTEK-UHFFFAOYSA-N 0.000 description 1
- HJZKXUMPVHDEBH-UHFFFAOYSA-N 3-(4-hydroxy-3-methylphenyl)propanenitrile Chemical compound CC1=CC(CCC#N)=CC=C1O HJZKXUMPVHDEBH-UHFFFAOYSA-N 0.000 description 1
- RXPUIKMFNFLESE-UHFFFAOYSA-N 3-(4-hydroxyphenyl)-2-methylpropanenitrile Chemical compound N#CC(C)CC1=CC=C(O)C=C1 RXPUIKMFNFLESE-UHFFFAOYSA-N 0.000 description 1
- KDMJGLYRWRHKJS-UHFFFAOYSA-N 3-(4-hydroxyphenyl)propanenitrile Chemical compound OC1=CC=C(CCC#N)C=C1 KDMJGLYRWRHKJS-UHFFFAOYSA-N 0.000 description 1
- SGHBRHKBCLLVCI-UHFFFAOYSA-N 3-hydroxybenzonitrile Chemical compound OC1=CC=CC(C#N)=C1 SGHBRHKBCLLVCI-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
- KZEJTKHRBQWACL-UHFFFAOYSA-N 4-hydroxy-2,6-dimethylbenzonitrile Chemical compound CC1=CC(O)=CC(C)=C1C#N KZEJTKHRBQWACL-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- DAWMAWYJUCCMHQ-UHFFFAOYSA-N 5-hydroxynaphthalene-1-carbonitrile Chemical compound C1=CC=C2C(O)=CC=CC2=C1C#N DAWMAWYJUCCMHQ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- BSQTUYCOTSTNLF-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carbonitrile Chemical compound N#CC1=CC=CC2=CC(O)=CC=C21 BSQTUYCOTSTNLF-UHFFFAOYSA-N 0.000 description 1
- UDGWTXRLMHXQKB-UHFFFAOYSA-N 7-hydroxynaphthalene-1-carbonitrile Chemical compound C1=CC=C(C#N)C2=CC(O)=CC=C21 UDGWTXRLMHXQKB-UHFFFAOYSA-N 0.000 description 1
- NFBPHZSDBOVNAL-UHFFFAOYSA-N 7-hydroxynaphthalene-2-carbonitrile Chemical compound C1=CC(C#N)=CC2=CC(O)=CC=C21 NFBPHZSDBOVNAL-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- VXBHWFYKVOBYRG-UHFFFAOYSA-N barium(2+);distiborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-][Sb]([O-])([O-])=O.[O-][Sb]([O-])([O-])=O VXBHWFYKVOBYRG-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- NKKMVIVFRUYPLQ-NSCUHMNNSA-N crotononitrile Chemical group C\C=C\C#N NKKMVIVFRUYPLQ-NSCUHMNNSA-N 0.000 description 1
- 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 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- IAJORBGJXHMEOD-UHFFFAOYSA-N naphthalene-2,6-diol;naphthalene-2,7-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21.C1=CC(O)=CC2=CC(O)=CC=C21 IAJORBGJXHMEOD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- FHWAGNWFJRJDBG-UHFFFAOYSA-N trimagnesium distiborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-][Sb]([O-])([O-])=O.[O-][Sb]([O-])([O-])=O FHWAGNWFJRJDBG-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、高誘電率を必要とするフィルム、基板、積層板等の電子部品に用いられる電子材料用樹脂として使用する、高誘電率を有するエポキシ樹脂組成物とその硬化物、及び、エポキシ樹脂組成物の硬化剤として使用するノボラック樹脂に関する。 The present invention relates to an epoxy resin composition having a high dielectric constant, a cured product thereof, and an epoxy resin used as a resin for electronic materials used in electronic parts such as films, substrates, and laminates that require a high dielectric constant. The present invention relates to a novolak resin used as a curing agent for the composition.
従来、誘電率の高い樹脂は、有機エレクトロルミネッセンス用材料やコンデンサ等に有用な樹脂として使用されている。高い比誘電率を有する樹脂としては、シアノエチル化ポリビニルアルコール、シアノエチル化プルラン（例えば、特許文献１参照。）、シアノエチル基を含有する（メタ）アクリル酸エステルモノマー（例えば、特許文献２参照。）シアノエチル基を有するエポキシ化合物（例えば、特許文献３参照）、シアノエチル化アミン化合物を硬化剤とするエポキシ樹脂硬化物（例えば、特許文献４参照。）等の、シアノ基を有する樹脂が知られている。 Conventionally, resins having a high dielectric constant have been used as useful resins for materials for organic electroluminescence, capacitors, and the like. Examples of the resin having a high relative dielectric constant include cyanoethylated polyvinyl alcohol, cyanoethylated pullulan (see, for example, Patent Document 1), and (meth) acrylic acid ester monomers containing a cyanoethyl group (for example, see Patent Document 2). Resins having a cyano group are known, such as epoxy compounds having a group (see, for example, Patent Document 3) and cured epoxy resin (for example, see Patent Document 4) using a cyanoethylated amine compound as a curing agent.
一方、近年、携帯電話やカーナビゲーションシステムを代表とする、可搬性を有する電子機器の需要が進んでいる。それに伴い電子機器の使用環境も大幅に変化しており、それらの使用環境に耐えうるような、耐熱性を有する電子材料が要求されている。 On the other hand, in recent years, demand for portable electronic devices such as mobile phones and car navigation systems has been increasing. Along with this, the usage environment of electronic devices has also changed drastically, and there is a demand for heat-resistant electronic materials that can withstand such usage environments.
しかしながら、上記に挙げた樹脂のうち、例えば、シアノエチル化ポリビニルアルコール、シアノエチル化プルラン、シアノエチル化アクリル系ポリマーは熱可塑性樹脂であり、且つガラス転移点も低いため、ガラス転移点近傍で誘電率が急激に変化してしまうといった問題があった。また、シアノエチル基を有するエポキシ化合物やシアノエチル化アミン化合物を硬化剤に用いたエポキシ樹脂硬化物は、熱硬化性樹脂のため、熱による変形は小さいものの、ガラス転移点が低く、上記要求を満たすまでには至っていない。 However, among the resins listed above, for example, cyanoethylated polyvinyl alcohol, cyanoethylated pullulan, and cyanoethylated acrylic polymer are thermoplastic resins and have a low glass transition point. There was a problem of changing to. In addition, epoxy resin cured products using epoxy compounds having a cyanoethyl group or cyanoethylated amine compounds as curing agents are thermosetting resins, so the deformation due to heat is small, but the glass transition point is low and the above requirements are met. It has not reached.
本発明が解決しようとする課題は、誘電率が高く且つ高い耐熱性を有する樹脂、及びこれを提供する硬化性樹脂組成物を提供することにある。更にこれを用いた電子材料用として有用な基板を提供することにある。 The problem to be solved by the present invention is to provide a resin having a high dielectric constant and high heat resistance, and a curable resin composition providing the same. It is another object of the present invention to provide a substrate useful for an electronic material using the same.
本発明者らは、鋭意検討した結果、芳香環上にシアノ基又はシアノ基を有する置換基を有するノボラック樹脂を硬化剤として用いたエポキシ樹脂が、高誘電率と耐熱性を兼ね備えていることを見出し、本発明に至った。 As a result of intensive studies, the present inventors have found that an epoxy resin using a novolak resin having a cyano group or a substituent having a cyano group on an aromatic ring as a curing agent has both high dielectric constant and heat resistance. The headline, the present invention has been reached.
即ち本発明は、エポキシ樹脂、硬化剤、及び硬化促進剤を含有するエポキシ樹脂組成物において、該硬化剤が、芳香環上に−ＣＮ、−Ｏ−Ｘ１−ＣＮ（但し、Ｘ１は炭素原子数２〜４のアルキレン基を表す）、又は−Ｘ２−ＣＮ（但し、Ｘ２は炭素原子数１〜４のアルキレン基を表す）を置換基として有するノボラック樹脂であるエポキシ樹脂組成物を提供する。 That is, the present invention relates to an epoxy resin composition containing an epoxy resin, a curing agent, and a curing accelerator, wherein the curing agent is —CN, —O—X 1 —CN (where X 1 is carbon represents an alkylene group of atoms 2-4), or -X 2 -CN (where, X 2 is an epoxy resin composition is a novolak resin having as a substituent a represents) an alkylene group having 1 to 4 carbon atoms and provide.
また、本発明は、前記記載のエポキシ樹脂組成物を硬化させることにより得られるエポキシ樹脂硬化物を提供する。 Moreover, this invention provides the epoxy resin hardened | cured material obtained by hardening the epoxy resin composition of the said description.
また、本発明は、前記記載のエポキシ樹脂硬化物の片面又は両面に金属箔を有する基板を提供する。 Moreover, this invention provides the board | substrate which has metal foil on the single side | surface or both surfaces of the said epoxy resin hardened | cured material.
また、本発明は、芳香環上に−Ｏ−Ｘ１−ＣＮ（但し、Ｘ１は炭素原子数２〜４のアルキレン基を表す）、又は−Ｘ２−ＣＮ（但し、Ｘ２は炭素原子数１〜４のアルキレン基を表す）を置換基として有し、重量平均分子量が４００〜８０００の範囲であるノボラック樹脂を提供する。 In the present invention, -O-X 1 -CN (wherein X 1 represents an alkylene group having 2 to 4 carbon atoms) or -X 2 -CN (where X 2 is a carbon atom) on the aromatic ring. And a novolak resin having a weight average molecular weight in the range of 400 to 8000.
本発明のエポキシ樹脂組成物は、芳香環上にシアノ基又はシアノ基を有する置換基を有するノボラック樹脂を硬化剤として用いるので、得られた硬化物は高誘電率と耐熱性とに優れる。従って電子材料として特に有用であり、特に、エポキシ樹脂硬化物の片面又は両面に金属箔を有するものははんだ特性にすぐれ、プリント配線基板等の耐熱性を要求させる電子材料として有用である。 Since the epoxy resin composition of the present invention uses a novolak resin having a cyano group or a substituent having a cyano group on an aromatic ring as a curing agent, the obtained cured product is excellent in high dielectric constant and heat resistance. Therefore, it is particularly useful as an electronic material. In particular, those having a metal foil on one or both sides of a cured epoxy resin have excellent solder characteristics and are useful as electronic materials that require heat resistance of a printed wiring board or the like.
（ノボラック樹脂）
本発明で硬化剤として使用するノボラック樹脂は、芳香環上に−ＣＮ、−Ｏ−Ｘ１−ＣＮ（但し、Ｘ１は炭素原子数２〜４のアルキレン基を表す）、又は−Ｘ２−ＣＮ（但し、Ｘ２は炭素原子数１〜４のアルキレン基を表す）を置換基として有する（以下、ノボラック樹脂（Ａ）と略す）。Ｘ１として、好ましくは、エチレン基、プロピレン基等が挙げられる。また、Ｘ１として、好ましくはメチレン基、ブチレン基等が挙げられる。これらの基は直鎖であっても分岐であってもよい。該置換基は、中でも、−Ｏ−Ｘ１−ＣＮ、又は−Ｘ２−ＣＮが好ましい。
ノボラック樹脂（Ａ）は、前記置換基のうち１種類のみを有していてもよいし、複数の異なる基を有していてもよい。例えば、−Ｘ２−ＣＮのみを有する樹脂であってもよいし、−ＣＮと−Ｏ−Ｘ１−ＣＮの両方の基を有していてもよい。
(Novolac resin)
The novolak resin used as a curing agent in the present invention has —CN, —O—X 1 —CN (wherein X 1 represents an alkylene group having 2 to 4 carbon atoms), or —X 2 — on the aromatic ring. CN (wherein X 2 represents an alkylene group having 1 to 4 carbon atoms) is used as a substituent (hereinafter abbreviated as novolak resin (A)). X 1 is preferably an ethylene group, a propylene group, or the like. X 1 is preferably a methylene group or a butylene group. These groups may be linear or branched. Among these, the substituent is preferably —O—X 1 —CN or —X 2 —CN.
The novolac resin (A) may have only one type of the substituents or may have a plurality of different groups. For example, it may be a resin having a -X 2 -CN, and may have a -CN and -O-X 1 -CN in both groups.
（含有分率Ｍ／Ｎ）
ノボラック樹脂（Ａ）の前記置換基、即ちシアノ基を有する基とフェノール性水酸基とのモル比（官能基モル比）は、前記置換基／フェノール性水酸基が４／６〜９／１の範囲内であることが好ましい。前記モル比が９／１よりも大きい場合、耐熱性が十分ではなく、４／６よりも小さい場合、誘電率が十分ではない。更に、５／５〜８．５／１．５の範囲であることが好ましく、５／５〜８／２の範囲がより好ましい。この範囲とすることで、比誘電率が６以上のフェノール樹脂が得られる。
(Content M / N)
The molar ratio (functional group molar ratio) of the substituent of the novolak resin (A), that is, the group having a cyano group and the phenolic hydroxyl group is within the range of 4/6 to 9/1. It is preferable that When the molar ratio is larger than 9/1, the heat resistance is not sufficient, and when it is smaller than 4/6, the dielectric constant is not sufficient. Furthermore, the range of 5/5 to 8.5 / 1.5 is preferable, and the range of 5/5 to 8/2 is more preferable. By setting it within this range, a phenol resin having a relative dielectric constant of 6 or more can be obtained.
（重量平均分子量）
ノボラック樹脂（Ａ）の重量平均分子量（以下、Ｍｗと略す）は４００〜８０００の範囲が好ましい。この範囲内とすることで、より高い耐熱性が得ることができる。中でも、３０００〜８０００の範囲がより好ましい。
(Weight average molecular weight)
The weight average molecular weight (hereinafter abbreviated as Mw) of the novolak resin (A) is preferably in the range of 400 to 8000. By setting it within this range, higher heat resistance can be obtained. Especially, the range of 3000-8000 is more preferable.
（ノボラック樹脂の製造方法）
ノボラック樹脂（Ａ）は、公知の方法で製造することができる。例えば、芳香環上に−ＣＮ又は−Ｘ２−ＣＮを置換基として有するノボラック樹脂（Ａ）は、−ＣＮ又は−Ｘ２−ＣＮを置換基として有するフェノール類とアルデヒド類とを重縮合させて得ることができる。
(Method for producing novolac resin)
The novolac resin (A) can be produced by a known method. For example, a novolak resin (A) having —CN or —X 2 —CN as a substituent on an aromatic ring is obtained by polycondensing phenols and aldehydes having —CN or —X 2 —CN as a substituent. Can be obtained.
（シアノ基を有するフェノール類）
本発明で使用する、−ＣＮ又は−Ｘ２−ＣＮを置換基として有するフェノール類は、同一の芳香環１個にフェノール性水酸基を１個有する１価フェノール類、同一の芳香環に２〜３個のフェノール性水酸基を有する多価フェノール類、さらには、ビスフェノール類等を使用することが出来る。また、これらのフェノール類を単独又は２種以上を組み合わせて使用することもできる。
１価フェノール類としては、４−ヒドロキシベンゾニトリル、３−ヒドロキシベンゾニトリル、２−ヒドロキシベンゾニトリル、４−ヒドロキシフェニルアセトニトリル、２−ヒドロキシフェニル−α−メチルアセトニトリル、４−ヒドロキシフェニル−α−メチルアセトニトリル、４−ヒドロキシフェニル−α，α−ジメチルアセトニトリル、３−（４−ヒドロキシフェニル）−プロピオニトリル、３−（３−メチル−４−ヒドロキシフェニル）プロピオニトリル、４−ヒドロキシ−２，６−ジメチルベンゾニトリル、３−（４−ヒドロキシフェニル）−２−メチル−プロピオニトリル、５−ヒドロキシ−１−ナフタレンカルボニトリル、６−ヒドロキシ−１−ナフタレンカルボニトリル、７−ヒドロキシ−１−ナフタレンカルボニトリル、６−ヒドロキシ−２−ナフタレンカルボニトリル、７−ヒドロキシ−２−ナフタレンカルボニトリル、等を挙げることができる。
多価フェノールとしては、３，５−ジヒドロキシベンゾニトリル、２，５−ジヒドロキシベンゾニトリル、等を挙げることができる。
(Phenols having a cyano group)
The phenols having —CN or —X 2 —CN as a substituent used in the present invention are monovalent phenols having one phenolic hydroxyl group in the same aromatic ring, and 2 to 3 in the same aromatic ring. Polyhydric phenols having one phenolic hydroxyl group, and bisphenols can be used. Moreover, these phenols can also be used individually or in combination of 2 or more types.
Examples of monohydric phenols include 4-hydroxybenzonitrile, 3-hydroxybenzonitrile, 2-hydroxybenzonitrile, 4-hydroxyphenylacetonitrile, 2-hydroxyphenyl-α-methylacetonitrile, 4-hydroxyphenyl-α-methylacetonitrile. 4-hydroxyphenyl-α, α-dimethylacetonitrile, 3- (4-hydroxyphenyl) -propionitrile, 3- (3-methyl-4-hydroxyphenyl) propionitrile, 4-hydroxy-2,6- Dimethylbenzonitrile, 3- (4-hydroxyphenyl) -2-methyl-propionitrile, 5-hydroxy-1-naphthalenecarbonitrile, 6-hydroxy-1-naphthalenecarbonitrile, 7-hydroxy-1-naphthalenecarbonitrile , - hydroxy-2-naphthalene carbonitrile, 7-hydroxy-2-naphthalene carbonitrile, and the like.
Examples of the polyhydric phenol include 3,5-dihydroxybenzonitrile and 2,5-dihydroxybenzonitrile.
（汎用フェノール類）
また、本発明の効果を損なわない範囲で、即ち、ノボラック樹脂（Ａ）の前記置換基とフェノール性水酸基とのモル比が、前記範囲内となるようにして、シアノ基を置換基として含まない、汎用のフェノール類を共重合させることもできる。汎用フェノール類に特に限定はなく、同一の芳香環１個にフェノール性水酸基を１個有する１価フェノール類、同一の芳香環に２〜３個のフェノール性水酸基を有する多価フェノール類、さらには、ビスフェノール類、トリスフェノール類等を使用することが出来る。また、これらのフェノール類を単独又は２種以上を組み合わせて使用することもできる。
１価フェノール類としては、例えば、フェノール、ｍ−クレゾール、ｐ−クレゾール、ｐ−ｔｅｒｔ−ブチルフェノール、２，３キシレノール、３，４−キシレノール、２，３，５−トリメチルフェノール、３，４，５−トリメチルフェノール、また、α−ナフトール、β−ナフトール等を挙げることができる。
多価フェノール類としては、カテコール、レゾルシノール、ハイドロキノン、また、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン２，７−ジヒドロキシナフタレン等の２価フェノール類、ピロガロール、１，２，４−ベンゼントリオール等の３価フェノール類を挙げることができる。
ビスフェノール類としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ等を、トリスフェノール類としては、トリス（４−ヒドロキシフェニル）メタン、トリス（４−ヒドロキシフェニル）エタン等を挙げることができる。
(General-purpose phenols)
Further, as long as the effect of the present invention is not impaired, that is, the molar ratio of the substituent of the novolak resin (A) to the phenolic hydroxyl group is within the above range, the cyano group is not included as a substituent. General purpose phenols can also be copolymerized. General-purpose phenols are not particularly limited, monohydric phenols having one phenolic hydroxyl group in the same aromatic ring, polyhydric phenols having 2 to 3 phenolic hydroxyl groups in the same aromatic ring, and Bisphenols, trisphenols and the like can be used. Moreover, these phenols can also be used individually or in combination of 2 or more types.
Examples of monohydric phenols include phenol, m-cresol, p-cresol, p-tert-butylphenol, 2,3 xylenol, 3,4-xylenol, 2,3,5-trimethylphenol, 3,4,5. -Trimethylphenol, alpha-naphthol, beta-naphthol, etc. can be mentioned.
Polyhydric phenols include catechol, resorcinol, hydroquinone, dihydric phenols such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene 2,7-dihydroxynaphthalene, pyrogallol, Mention may be made of trihydric phenols such as 1,2,4-benzenetriol.
Examples of bisphenols include bisphenol A, bisphenol F, and bisphenol S, and examples of trisphenols include tris (4-hydroxyphenyl) methane and tris (4-hydroxyphenyl) ethane.
（アルデヒド類）
本発明で使用するアルデヒド類としては、ホルムアルデヒドが好ましいが、ベンズアルデヒド、アセトアルデヒド、パラホルムアルデヒド等を使用することもできる。アルデヒド類の使用量に特に限定はないが、一般的にはフェノール類１モルに対して、０．５〜１．５の範囲で使用するのが好ましい。これらのアルデヒド類も単独又は２種以上を組み合わせて使用することができる。
(Aldehydes)
As the aldehydes used in the present invention, formaldehyde is preferable, but benzaldehyde, acetaldehyde, paraformaldehyde and the like can also be used. Although there is no limitation in the usage-amount of aldehydes, generally it is preferable to use in the range of 0.5-1.5 with respect to 1 mol of phenols. These aldehydes can also be used alone or in combination of two or more.
（製造方法）
前記芳香環上に−ＣＮ又は−Ｘ２−ＣＮを置換基として有するフェノール類と前記アルデヒド類とを重縮合させる際に使用する触媒や溶媒は、公知のものを使用すればよく、例えば、触媒は、塩酸、硝酸、硫酸、ｐ−トルエンスルホン酸等の無機酸又は有機酸が挙げられ、溶媒としては、アルコール類、ケトン類、エーテル類、エステル類の有機溶剤があげられる。合成の常法としては、例えば、触媒下において８０〜１５０℃の液温で、１５分〜５時間程度反応させる方法が一般的である。
(Production method)
A known catalyst or solvent may be used for polycondensation of phenols having —CN or —X 2 —CN as a substituent on the aromatic ring and the aldehydes. For example, a catalyst may be used. Examples include inorganic acids or organic acids such as hydrochloric acid, nitric acid, sulfuric acid, and p-toluenesulfonic acid, and examples of the solvent include organic solvents such as alcohols, ketones, ethers, and esters. As a usual synthesis method, for example, a method of reacting at a liquid temperature of 80 to 150 ° C. for about 15 minutes to 5 hours under a catalyst is common.
以下に、一例として、４−ヒドロキシフェニルアセトニトリルとホルムアルデヒドとを用いてノボラック樹脂を合成した場合の反応式を示す。 As an example, the reaction formula in the case of synthesizing a novolak resin using 4-hydroxyphenylacetonitrile and formaldehyde is shown below.
（式中のｎは、整数を表す。）
(In the formula, n represents an integer.)
また、芳香環上に−Ｏ−Ｘ１−ＣＮを置換基として有するノボラック樹脂（Ａ）は、ノボラック樹脂のフェノール性水酸基の一部に、アルカリ触媒存在下でニトリル化合物を反応させ、フェノール性水酸基をエーテル化させて得ることができる。ノボラック樹脂は、汎用フェノール類とアルデヒド類との重縮合体からなる汎用のノボラック樹脂を使用してもよいし、前記ノボラック樹脂（Ａ）のフェノール性水酸基の一部にニトリル化合物を反応させてもよい。汎用フェノール類及びアルデヒド類は、前記「汎用フェノール類」及び「アルデヒド類」の欄に挙げた化合物を使用することができる。
以下に、一例として、フェノール樹脂の水酸基の一部にニトリル化合物を反応させた場合の反応式を示す。
The novolak resin (A) having —O—X 1 —CN as a substituent on the aromatic ring is obtained by reacting a part of the phenolic hydroxyl group of the novolak resin with a nitrile compound in the presence of an alkali catalyst. Can be obtained by etherification. As the novolak resin, a general-purpose novolak resin composed of a polycondensate of general-purpose phenols and aldehydes may be used, or a nitrile compound may be reacted with a part of the phenolic hydroxyl group of the novolak resin (A). Good. As the general-purpose phenols and aldehydes, the compounds listed in the above-mentioned “general-purpose phenols” and “aldehydes” columns can be used.
As an example, a reaction formula in the case of reacting a nitrile compound with a part of the hydroxyl group of the phenol resin is shown below.
ニトリル化合物としては、アクリロニトリル、メタクリロニトリル、２−ブテンニトリル、３−ブテンニトリル、２−ペンテンニトリル、３−ペンテンニトリル、４−ペンテンニトリル、２−メチル−３−ブテンニトリルなどのシアノ基及び不飽和基を有するモノマーを挙げることができる。
前記ニトリル化合物は、ノボラック樹脂の水酸基１モルに対して１モル以上使用するのが好ましく、１．５モル以上使用するのが好ましい。使用量が１モル未満の場合、反応が上手く進行しないことがある。
Nitrile compounds include cyano groups such as acrylonitrile, methacrylonitrile, 2-butenenitrile, 3-butenenitrile, 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile, 2-methyl-3-butenenitrile and the like. Mention may be made of monomers having a saturated group.
The nitrile compound is preferably used in an amount of 1 mol or more per mol of the hydroxyl group of the novolak resin, and more preferably 1.5 mol or more. When the amount used is less than 1 mol, the reaction may not proceed well.
また、アルカリ触媒としては、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物、ナトリウムメチラート、ナトリウムエチラート等のアルコラート、炭酸ナトリウム、炭酸カリウム等の炭酸塩、ナトリウムオキシド、等が挙げられる。 Examples of the alkali catalyst include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, alcoholates such as sodium methylate and sodium ethylate, carbonates such as sodium carbonate and potassium carbonate, sodium oxide, etc. Is mentioned.
前記反応は、必要に応じて溶剤を使用してもよい。溶剤としては特に制限はなく公知慣用のものを使用できるが、アルカリ触媒存在下でノボラック樹脂を溶解させる溶剤が好ましい。例えば、水、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、等のケトン類、テトラヒドロフラン、ジエチルエーテル、アニソール、等のエーテル類、ジメチルホルムアミド、ジメチルアセトアミド、等のアミド類、アセトニトリル、アクリロニトリル等のニトリル類など、汎用の溶剤が挙げられる。これらの溶剤は、単独、または、２種類以上混合して用いることができる。 In the reaction, a solvent may be used as necessary. There are no particular limitations on the solvent, and known and commonly used solvents can be used, but a solvent that dissolves the novolak resin in the presence of an alkali catalyst is preferred. For example, water, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. ketones, tetrahydrofuran, diethyl ether, anisole, etc. ethers, dimethylformamide, dimethylacetamide, etc. amides, acetonitrile, acrylonitrile etc. nitriles, etc. These solvents are mentioned. These solvents can be used alone or in combination of two or more.
ノボラック樹脂とニトリル化合物との反応は、通常反応温度２００℃以下で行い、室温〜１００℃で行うのが好ましい。反応圧力は、常圧、加圧、いずれでも良い。反応時間は、変性する割合によって異なるが、通常は１〜２４時間である。通常は、前記ニトリル化合物をノボラック樹脂の水酸基１モルに対して１モル以上使用するので、反応終了後、公知の精製方法により未反応のニトリル化合物を取り除くことが好ましい。 The reaction between the novolak resin and the nitrile compound is usually carried out at a reaction temperature of 200 ° C. or lower, preferably from room temperature to 100 ° C. The reaction pressure may be normal pressure or increased pressure. The reaction time varies depending on the rate of modification, but is usually 1 to 24 hours. Usually, since the nitrile compound is used in an amount of 1 mol or more per 1 mol of the hydroxyl group of the novolak resin, it is preferable to remove the unreacted nitrile compound by a known purification method after completion of the reaction.
ノボラック樹脂（Ａ）の好ましい例としては、例えば、４−ヒドロキシフェニル−α−メチルアセトニトリルとホルムアルデヒドとの重縮合体のような、一般式（１）で表される繰り返し単位を有するノボラック樹脂が挙げられる。 Preferable examples of the novolak resin (A) include novolak resins having a repeating unit represented by the general formula (1) such as a polycondensate of 4-hydroxyphenyl-α-methylacetonitrile and formaldehyde. It is done.
式中、Ａはベンゼン環又はナフタレン環を表し、Ｂは−Ｏ−Ｘ１−ＣＮ、又は−Ｘ２−ＣＮを表し、Ｘ１は炭素原子数２〜４のアルキレン基を表し、Ｘ２は炭素原子数１〜４のアルキレン基を表す。 In the formula, A represents a benzene ring or a naphthalene ring, B represents —O—X 1 —CN, or —X 2 —CN, X 1 represents an alkylene group having 2 to 4 carbon atoms, and X 2 represents An alkylene group having 1 to 4 carbon atoms is represented.
あるいは、フェノールホルムアルデヒドノボラック樹脂のフェノール性水酸基にアクリロニトリルを反応させた樹脂のような、一般式（２）及び一般式（３）で表される繰り返し単位を有するノボラック樹脂が挙げられる。 Or the novolak resin which has a repeating unit represented by General formula (2) and General formula (3) like the resin which made acrylonitrile react with the phenolic hydroxyl group of a phenol formaldehyde novolak resin is mentioned.
式中、Ａはベンゼン環又はナフタレン環を表し、Ｄは水素原子、−Ｏ−Ｘ１−ＣＮ、又は−Ｘ２−ＣＮを表し、Ｘ１は炭素原子数２〜４のアルキレン基を表し、Ｘ２は炭素原子数１〜４のアルキレン基を表す。 In the formula, A represents a benzene ring or a naphthalene ring, D represents a hydrogen atom, —O—X 1 —CN, or —X 2 —CN, X 1 represents an alkylene group having 2 to 4 carbon atoms, X 2 represents an alkylene group having 1 to 4 carbon atoms.
（エポキシ樹脂組成物）
本発明のエポキシ樹脂組成物は、エポキシ樹脂、前記ノボラック樹脂（Ａ）、及び硬化促進剤を含有する。また、無機フィラーや、希釈する目的で各種溶剤を含有していてもよい。また、本発明の目的を損なわない範囲で、ＵＶ硬化型樹脂、熱硬化性樹脂、熱可塑性樹脂などの樹脂、充填剤、染料、顔料、その他公知の添加剤等を適量配合してもよい。
(Epoxy resin composition)
The epoxy resin composition of the present invention contains an epoxy resin, the novolak resin (A), and a curing accelerator. Moreover, you may contain various solvents for the purpose of an inorganic filler and dilution. Further, an appropriate amount of a resin such as a UV curable resin, a thermosetting resin, and a thermoplastic resin, a filler, a dye, a pigment, and other known additives may be blended within a range that does not impair the object of the present invention.
（エポキシ樹脂）
本発明に使用するエポキシ樹脂は、分子内に少なくとも２つ以上の反応性エポキシ基を有していれば特に限定はない。具体的には、例えば、ビスフェノールＡ型、ビスフェノールＦ型、ノボラック型、ナフトールアラルキル型、グリシジルアミン型、ナフタレン型、ジシクロペンタジエン型、テトラメチルビフェノール型等が挙げられる。これらのエポキシ樹脂は、１種類で使用しても、２種類以上を混合して用いてもよい。また、これらのエポキシ樹脂は、分子量、その他の物性にも特に制限はない。
(Epoxy resin)
The epoxy resin used in the present invention is not particularly limited as long as it has at least two reactive epoxy groups in the molecule. Specific examples include bisphenol A type, bisphenol F type, novolak type, naphthol aralkyl type, glycidylamine type, naphthalene type, dicyclopentadiene type, and tetramethylbiphenol type. These epoxy resins may be used alone or in combination of two or more. These epoxy resins are not particularly limited in molecular weight and other physical properties.
（硬化促進剤）
本発明に使用する硬化促進剤としては、公知慣用の加熱硬化型触媒を使用できる。例えば、２−メチルイミダゾール、２−エチル−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、２−ヘプタデシルイミダゾール、２−ウンデシルイミダゾールなどのイミダゾール類、トリエチルアミン、トリブチルアミンなどのトリアルキルアミン、４−ジメチルアミノピリジン、ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノール、１，８ジアザビシクロ（５，４，０）−ウンデセン−７（以下ＤＢＵと略称する）などのアミン化合物、トリフェニルホスフィン、トリブチルホスフィンなどの有機ホスフィン化合物、トリメチルホスファイト、トリエチルホスファイトなどの有機ホスファイト化合物などが挙げられる。これらは単独あるいは２種以上の混合物として用いることができる。硬化促進剤は、通常、エポキシ樹脂に対して２質量％未満となるように使用する。中でも、エポキシ樹脂に対して０．１〜１質量％とすることが好ましく、０．２〜０．６質量％とすることがより好ましい。
(Curing accelerator)
As the curing accelerator used in the present invention, a known and commonly used thermosetting catalyst can be used. For example, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole and 2-undecylimidazole, and trialkylamines such as triethylamine and tributylamine , 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8diazabicyclo (5,4,0) -undecene-7 (hereinafter abbreviated as DBU) Examples thereof include organic phosphine compounds such as compounds, triphenylphosphine and tributylphosphine, and organic phosphite compounds such as trimethylphosphite and triethylphosphite. These can be used alone or as a mixture of two or more. A hardening accelerator is normally used so that it may become less than 2 mass% with respect to an epoxy resin. Especially, it is preferable to set it as 0.1-1 mass% with respect to an epoxy resin, and it is more preferable to set it as 0.2-0.6 mass%.
（無機フィラー）
本発明においては、必要に応じて無機フィラーを添加してもよい。無機フィラーとしては特に限定はなく、例えば、炭酸カルシウム、シリカ、ガラスパウダー、ケイ酸カルシウム、タルク、酸化マグネシウム、水酸化マグネシウム、アルミナ、水酸化アルミニウム、酸化ジルコン、硫酸カルシウム、ケイ酸ジルコン、ベンナイト、ゼオライト、カオリン、マイカ、パイロフィライト、セリナイト、ハイドロタルサイト、硫酸バリウム、等を使用することができる。また、特に高誘電率の、チタン酸バリウム、チタン酸亜鉛、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸鉛、チタン酸マグネシウム、酸化チタン、アンチモン酸バリウム、アンチモン酸ストロンチウム、アンチモン酸カルシウム、アンチモン酸マグネシウム、スズ酸バリウムなどの金属酸化物を使用すると、比誘電率の高いエポキシ樹脂硬化物を得ることができ、好ましい。これらの無機フィラーは、複合化合物、固溶体、単なる混合物であってもよい。無機フィラーの含有量は、本発明のエポキシ樹脂硬化物の機械的特性、耐熱性を著しく損なわない限りは特に限定されないが、通常は、体積分率に換算して４０％以下が好ましい。
(Inorganic filler)
In the present invention, an inorganic filler may be added as necessary. The inorganic filler is not particularly limited. For example, calcium carbonate, silica, glass powder, calcium silicate, talc, magnesium oxide, magnesium hydroxide, alumina, aluminum hydroxide, zircon oxide, calcium sulfate, zircon silicate, bennite, Zeolite, kaolin, mica, pyrophyllite, serinite, hydrotalcite, barium sulfate, and the like can be used. Also, especially high dielectric constant barium titanate, zinc titanate, strontium titanate, calcium titanate, lead titanate, magnesium titanate, titanium oxide, barium antimonate, strontium antimonate, calcium antimonate, magnesium antimonate When a metal oxide such as barium stannate is used, an epoxy resin cured product having a high relative dielectric constant can be obtained, which is preferable. These inorganic fillers may be complex compounds, solid solutions, or simple mixtures. The content of the inorganic filler is not particularly limited as long as the mechanical properties and heat resistance of the cured epoxy resin of the present invention are not significantly impaired, but usually 40% or less in terms of volume fraction is preferable.
（溶剤）
本発明のエポキシ樹脂組成物を希釈する目的で使用する溶剤は、フェノール樹脂（Ａ）、エポキシ樹脂、及び、硬化促進剤を溶解しうるものであればよく、例えば、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、テトラヒドロフラン、アニソール等のエーテル系溶剤、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド系溶剤、塩化メチレン、クロロホルム等の塩素系炭化水素系溶媒等を使用することができる。これらは、単独で用いることもできるし、２種類以上混合して用いることもできる。
(solvent)
The solvent used for the purpose of diluting the epoxy resin composition of the present invention may be any solvent that can dissolve the phenol resin (A), the epoxy resin, and the curing accelerator, such as methyl ethyl ketone and methyl isobutyl ketone. It is possible to use ketone solvents, ether solvents such as tetrahydrofuran and anisole, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, and chlorine hydrocarbon solvents such as methylene chloride and chloroform. it can. These can be used alone or in combination of two or more.
（量）
本発明において、エポキシ樹脂とノボラック樹脂（Ａ）との混合比は、エポキシ樹脂のエポキシ当量をＥ、ノボラック樹脂（Ａ）のヒドロキシ基当量をＨ、エポキシ樹脂の質量をｅ、ノボラック樹脂（Ａ）の質量をｈとすると、（ｅ／Ｅ）／（ｈ／Ｈ）が１０／８〜１０／１５となるようにすることが好ましく、１０／９〜１０／１２とすることがより好ましい。（ｅ／Ｅ）／（ｈ／Ｈ）の比、即ちエポキシ基とヒドロキシ基のモル比の該範囲よりエポキシ基が少なくなると高い誘電性が得られにくく、また、ヒドロキシ基が該範囲より多すぎると、架橋密度が低減するため耐熱性が低下する傾向にある。
(amount)
In the present invention, the mixing ratio of the epoxy resin and the novolak resin (A) is as follows: the epoxy equivalent of the epoxy resin is E, the hydroxy group equivalent of the novolac resin (A) is H, the mass of the epoxy resin is e, and the novolac resin (A) When the mass of h is h, (e / E) / (h / H) is preferably 10/8 to 10/15, more preferably 10/9 to 10/12. When the epoxy group is less than the range of the ratio of (e / E) / (h / H), that is, the molar ratio of the epoxy group to the hydroxy group, it is difficult to obtain a high dielectric property, and the hydroxy group is too much above the range. And, since the crosslinking density is reduced, the heat resistance tends to be lowered.
（エポキシ樹脂硬化物）
（製造方法）
本発明のエポキシ樹脂組成物は、一端予備硬化した後、予備硬化物を加熱成形して本硬化させることで、板状、フィルム等の所望の形状を有する本発明のエポキシ樹脂硬化物が得られる。
予備硬化の際には、フェノール樹脂（Ａ）、エポキシ樹脂、及び硬化促進剤が均一に混合していることが好ましい。このため、該組成物は予備硬化の前に、一端溶剤に溶解させ均一としてから再度乾燥させて溶媒を除去するのが好ましい。乾燥は、エポキシ樹脂組成物の硬化を促進させないため、通常室温〜１５０℃付近で行う。得られたエポキシ樹脂組成物を加熱して予備硬化させる。予備硬化の条件は特に限定がないが、得られた予備硬化物が、室温付近では固形物であり、且つ加熱した時には粘調性流動体となることが目安である。具体的には、例えば、加熱温度１３０〜１７０℃、加熱時間５〜３０分で行う。
得られた予備硬化物を必要に応じて粉砕後、圧縮成形法、トランスファー成形法、注型成形法、押出成形法、等の汎用の方法で、加熱成形して本硬化させることで、板状、フィルム等の所望の形状を有する本発明のエポキシ樹脂硬化物を得ることができる。
(Cured epoxy resin)
(Production method)
After the epoxy resin composition of the present invention is preliminarily cured, the cured epoxy resin of the present invention having a desired shape such as a plate shape or a film can be obtained by thermoforming the precured material and performing main curing. .
In the preliminary curing, it is preferable that the phenol resin (A), the epoxy resin, and the curing accelerator are uniformly mixed. For this reason, it is preferable to remove the solvent by preliminarily curing the composition by dissolving it in a solvent and then drying it again. Drying is usually performed at room temperature to around 150 ° C. in order not to accelerate the curing of the epoxy resin composition. The obtained epoxy resin composition is heated and precured. The conditions for preliminary curing are not particularly limited, but it is a standard that the obtained preliminary cured product is a solid at room temperature and becomes a viscous fluid when heated. Specifically, for example, the heating temperature is 130 to 170 ° C. and the heating time is 5 to 30 minutes.
After pre-curing the obtained precured product as necessary, it is plate-shaped by heat-molding and main-curing by a general-purpose method such as compression molding method, transfer molding method, cast molding method, extrusion molding method, etc. The cured epoxy resin product of the present invention having a desired shape such as a film can be obtained.
本発明のエポキシ樹脂硬化物は、５以上の比誘電率を有し、且つ１１０℃以上の耐熱性を有するものが好ましい。これは、使用するエポキシ樹脂とフェノール樹脂（Ａ）との配合比率を変化させることで所望の物性を有する硬化物が得られる。 The epoxy resin cured product of the present invention preferably has a relative dielectric constant of 5 or more and heat resistance of 110 ° C. or more. As for this, the hardened | cured material which has a desired physical property is obtained by changing the compounding ratio of the epoxy resin and phenol resin (A) to be used.
本発明のエポキシ樹脂組成物は、予め金、銅、アルミなどの金属箔、ガラス、アラミドまたはポリエステルなどのクロス材料、不織布、プリント配線基板などの基材上に、塗布し、乾燥させ、本硬化させて、基材付きの基板としてもよい。また、エポキシ樹脂組成物の予備硬化物を加熱成形して本硬化させる際に、必要に応じて前記基材上に載置し、エポキシ樹脂硬化物と基材を積層一体化させてもよいし、加熱成形後、前記基材と積層させてもよい。中でも、金、銅、アルミなどの金属箔を片面又は両面に有する基板は、はんだ特性に優れ、特にプリント配線基板等の耐熱性を要求させる電子材料として特に有用である。 The epoxy resin composition of the present invention is applied in advance to a metal foil such as gold, copper or aluminum, a cloth material such as glass, aramid or polyester, a nonwoven fabric, a substrate such as a printed wiring board, dried, and finally cured. It is good also as a board | substrate with a base material. In addition, when the precured product of the epoxy resin composition is thermoformed and main cured, it may be placed on the base material as necessary, and the cured epoxy resin product and the base material may be laminated and integrated. After heat molding, the substrate may be laminated. Among them, a substrate having a metal foil such as gold, copper, or aluminum on one side or both sides is excellent in solder characteristics and is particularly useful as an electronic material that requires heat resistance such as a printed wiring board.
（金属箔付きエポキシ樹脂）
前記金属箔としては、前記金、銅、アルミ等の金蔵箔があげられる。膜厚は特に限定ないが、１〜１００μｍの範囲が好ましい。
(Epoxy resin with metal foil)
Examples of the metal foil include gold foils such as gold, copper, and aluminum. The film thickness is not particularly limited, but a range of 1 to 100 μm is preferable.
（製造方法）
前記基板は、必要に応じて溶剤で希釈したエポキシ樹脂組成物を金属箔上に塗布乾燥させる。これを前記記載の方法で硬化させ、片面に金属箔を有する基板を得る。あるいは、両面に金属箔を有する基板を得る場合は、前記硬化条件を、予備硬化条件とし、片面に金属箔を有する予備硬化された基板を得る。該基板の樹脂面に、更に金属箔を積層させ、プレス法、ラミネート法、等一般的な方法で加熱して硬化させて得る。
金属箔上に塗布する方法は、ドクターブレードコート法、スピンコート法、ディップコート法、又はスクリーン印刷コート法等の公知の方法を用いることができる。
(Production method)
The said board | substrate applies and drys the epoxy resin composition diluted with the solvent on the metal foil as needed. This is cured by the method described above to obtain a substrate having a metal foil on one side. Or when obtaining the board | substrate which has metal foil on both surfaces, the said hardening conditions are made into the preliminary curing conditions, and the precured board | substrate which has metal foil on one side is obtained. A metal foil is further laminated on the resin surface of the substrate, and is obtained by heating and curing by a general method such as a pressing method or a laminating method.
As a method of coating on the metal foil, a known method such as a doctor blade coating method, a spin coating method, a dip coating method, or a screen printing coating method can be used.
また、本発明の金属箔付き基板は、基板同士を複数積層させて積層板として使用してもよい。基板同士を積層させる場合、金属箔側とエポキシ樹脂側を接触させても、エポキシ樹脂側同士を接触させてもよい。また、プリント配線基板等の電子材料を単数または複数積層させてもよい。さらには、本発明の金属箔付き基板と汎用の金属箔付きエポキシ樹脂とを積層させることもできる。 Further, the substrate with metal foil of the present invention may be used as a laminate by laminating a plurality of substrates. When laminating the substrates, the metal foil side and the epoxy resin side may be brought into contact with each other, or the epoxy resin sides may be brought into contact with each other. Moreover, you may laminate | stack one or more electronic materials, such as a printed wiring board. Furthermore, the board | substrate with metal foil of this invention and the epoxy resin with general purpose metal foil can also be laminated | stacked.
以下、実施例によって本発明を詳細に説明するが、これらによって限定されるものではない。特に断わりのない限り「部」、「％」は質量基準である。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not limited by these. Unless otherwise specified, “part” and “%” are based on mass.
（実施例１）
１００ｍｌの三つ口フラスコに２１．２ｇ（０．２モル）のフェノールノボラック樹脂ＴＤ−２０９０（大日本インキ化学工業（株）社製）、６３．６ｇ（１．２モル）のアクリロニトリル、２ｇの水酸化ナトリウム、そして、４０ｇの水を入れ、６０℃で１．５時間攪拌した。反応後、塩酸を加えてｐＨを７より若干小さくし、そこに水を加えて１００℃で未反応のアクリロニトリルを留去した。その後、塩化ナトリウムが洗い出されるまで熱水で洗いノボラック樹脂（１）を得た。ノボラック樹脂（１）のシアノ基を有する置換基とフェノール性水酸基とのモル比は、５．５／４．５であり、重量平均分子量は、ＧＰＣを用いて測定したところ、スチレン換算で６５００であった。また、ノボラック樹脂（１）を加熱溶融してペレットを作成した。得られたペレットの両側に電極をつけて、比誘電率を測定したところ、６．７であった。
(Example 1)
In a 100 ml three-necked flask, 21.2 g (0.2 mol) of phenol novolac resin TD-2090 (manufactured by Dainippon Ink & Chemicals, Inc.), 63.6 g (1.2 mol) of acrylonitrile, 2 g Sodium hydroxide and 40 g of water were added and stirred at 60 ° C. for 1.5 hours. After the reaction, hydrochloric acid was added to make the pH slightly lower than 7, and water was added thereto to distill off unreacted acrylonitrile at 100 ° C. Then, the novolak resin (1) was obtained by washing with hot water until sodium chloride was washed out. The molar ratio of the cyano group-containing substituent of the novolak resin (1) to the phenolic hydroxyl group is 5.5 / 4.5, and the weight average molecular weight measured by GPC is 6500 in terms of styrene. there were. Moreover, the novolak resin (1) was heated and melted to prepare pellets. An electrode was attached to both sides of the obtained pellet, and the relative dielectric constant was measured and found to be 6.7.
（実施例２）
１００ｍｌの三つ口フラスコに２１．２ｇ（０．２モル）のフェノールノボラック樹脂ＴＤ−２０９０（大日本インキ化学工業（株）社製）、７４．２ｇ（１．４モル）のアクリロニトリル、２ｇの水酸化ナトリウム、そして、４０ｇの水を入れ、６０℃で２時間攪拌した。反応後、塩酸を加えてｐＨを７より若干小さくし、そこに水を加えて１００℃で未反応のアクリロニトリルを留去した。その後、塩化ナトリウムが洗い出されるまで熱水で洗い、ノボラック樹脂（２）を得た。ノボラック樹脂（２）のシアノ基を有する置換基とフェノール性水酸基とのモル比は８．４／１．６であり、重量平均分子量は７０５０であった。実施例１と同様にして比誘電率を測定したところ、７．５であった。
(Example 2)
In a 100 ml three-necked flask, 21.2 g (0.2 mol) of phenol novolac resin TD-2090 (manufactured by Dainippon Ink & Chemicals, Inc.), 74.2 g (1.4 mol) of acrylonitrile, 2 g Sodium hydroxide and 40 g of water were added and stirred at 60 ° C. for 2 hours. After the reaction, hydrochloric acid was added to make the pH slightly lower than 7, and water was added thereto to distill off unreacted acrylonitrile at 100 ° C. Then, it washed with hot water until sodium chloride was washed out, and the novolak resin (2) was obtained. The molar ratio of the substituent having a cyano group of the novolak resin (2) to the phenolic hydroxyl group was 8.4 / 1.6, and the weight average molecular weight was 7050. When the relative dielectric constant was measured in the same manner as in Example 1, it was 7.5.
（実施例３）
１００ｍｌの三つ口フラスコに２１．２ｇ（０．２モル）のフェノールノボラック樹脂ＴＤ−２０９０（大日本インキ化学工業（株）社製）、８０．４ｇ（１．２モル）のメタクリロニトリル、２ｇの水酸化ナトリウム、そして、４０ｇの水を入れ、６０℃で２時間攪拌した。反応後、塩酸を加えてｐＨを７より若干小さくし、そこに水を加えて１００℃で未反応のアクリロニトリルを留去した。その後、塩化ナトリウムが洗い出されるまで熱水で洗い、ノボラック樹脂（３）を得た。ノボラック樹脂（３）のシアノ基を有する置換基とフェノール性水酸基とのモル比は６．１／３．９であり、重量平均分子量は６８００であった。実施例１と同様にして比誘電率を測定したところ、７．０であった。
(Example 3)
In a 100 ml three-necked flask, 21.2 g (0.2 mol) of phenol novolac resin TD-2090 (manufactured by Dainippon Ink & Chemicals, Inc.), 80.4 g (1.2 mol) of methacrylonitrile, 2 g of sodium hydroxide and 40 g of water were added and stirred at 60 ° C. for 2 hours. After the reaction, hydrochloric acid was added to make the pH slightly lower than 7, and water was added thereto to distill off unreacted acrylonitrile at 100 ° C. Then, it washed with hot water until sodium chloride was washed out, and the novolak resin (3) was obtained. The molar ratio of the substituent having a cyano group of the novolak resin (3) to the phenolic hydroxyl group was 6.1 / 3.9, and the weight average molecular weight was 6,800. When the relative dielectric constant was measured in the same manner as in Example 1, it was 7.0.
（実施例４）
１００ｍｌの三つ口フラスコに２４．０ｇ（０．２モル）のビスフェノールＡノボラック樹脂ＫＨ−６０２１（大日本インキ化学工業（株）社製）、６３．６ｇ（１．２モル）のアクリロニトリル、２ｇの水酸化ナトリウム、そして、４０ｇの水を入れ、６０℃で１．５時間攪拌した。反応後、塩酸を加えてｐＨを７より若干小さくし、そこに水を加えて１００℃で未反応のアクリロニトリルを留去した。その後、塩化ナトリウムが洗い出されるまで熱水で洗い、ノボラック樹脂（４）を得た。ノボラック樹脂（４）のシアノ基を有する置換基とフェノール性水酸基とのモル比は６．０／４．０であり、重量平均分子量はスチレン換算で３８００であった。実施例１と同様にして比誘電率を測定したところ、６．９であった。
Example 4
In a 100 ml three-necked flask, 24.0 g (0.2 mol) of bisphenol A novolak resin KH-6021 (manufactured by Dainippon Ink & Chemicals, Inc.), 63.6 g (1.2 mol) of acrylonitrile, 2 g Of sodium hydroxide and 40 g of water were added and stirred at 60 ° C. for 1.5 hours. After the reaction, hydrochloric acid was added to make the pH slightly lower than 7, and water was added thereto to distill off unreacted acrylonitrile at 100 ° C. Then, it washed with hot water until sodium chloride was washed out, and the novolak resin (4) was obtained. The molar ratio of the substituent having a cyano group of the novolak resin (4) to the phenolic hydroxyl group was 6.0 / 4.0, and the weight average molecular weight was 3800 in terms of styrene. The relative dielectric constant was measured in the same manner as in Example 1. As a result, it was 6.9.
（実施例５）
１００ｍｌの三つ口フラスコに１３．３ｇ（０．１モル）の４−ヒドロキシフェニルアセトニトリル、３．０ｇ（０．１モル）のパラホルムアルデヒド、０．４ｇの塩化亜鉛（ＺｎＣｌ２）を入れ、硫酸でｐＨを約１に調製した。７５〜８０℃で５時間攪拌加熱した後、５０ｍｌの蒸留水を加え、８０〜１００℃で３０分間加熱した。その後、樹脂をろ過、４−ヒドロキシフェニルアセトニトリルがなくなり、Ｃｌイオンが検出されなくなるまで湯洗を繰り返し、ノボラック樹脂（５）を得た。ノボラック樹脂（５）のシアノ基を有する置換基とフェノール性水酸基とのモル比は５．０／５．０であり、重量平均分子量はスチレン換算で１８００であった。実施例１と同様にして比誘電率を測定したところ、９．０であった。
(Example 5)
A 100 ml three-necked flask is charged with 13.3 g (0.1 mol) of 4-hydroxyphenylacetonitrile, 3.0 g (0.1 mol) of paraformaldehyde, 0.4 g of zinc chloride (ZnCl 2 ) and sulfuric acid. The pH was adjusted to about 1. After stirring and heating at 75-80 ° C. for 5 hours, 50 ml of distilled water was added and heated at 80-100 ° C. for 30 minutes. Thereafter, the resin was filtered, and washing with hot water was repeated until 4-hydroxyphenylacetonitrile disappeared and no Cl ions were detected to obtain a novolak resin (5). The molar ratio of the substituent having a cyano group of the novolak resin (5) to the phenolic hydroxyl group was 5.0 / 5.0, and the weight average molecular weight was 1800 in terms of styrene. When the relative dielectric constant was measured in the same manner as in Example 1, it was 9.0.
（実施例６）
１００ｍｌの三つ口フラスコに１１．９ｇ（０．１モル）の４−ヒドロキシベンゾニトリル、３．０ｇ（０．１モル）のパラホルムアルデヒド、０．４ｇの塩化亜鉛（ＺｎＣｌ２）を入れ、硫酸でｐＨを約１に調製した。９５℃で６時間攪拌加熱した後、５０ｍｌのアセトニトリルを入れ、樹脂を沈殿させた。これをろ過してアセトニトリルで洗い、１００℃で乾燥させてノボラック樹脂（６）を得た。ノボラック樹脂（６）のシアノ基を有する置換基とフェノール性水酸基とのモル比は５．０／５．０であり、重量平均分子量はスチレン換算で１６００であった。実施例１と同様にして比誘電率を測定したところ、８．０であった。
(Example 6)
A 100 ml three-necked flask is charged with 11.9 g (0.1 mol) of 4-hydroxybenzonitrile, 3.0 g (0.1 mol) of paraformaldehyde, 0.4 g of zinc chloride (ZnCl 2 ), and sulfuric acid. The pH was adjusted to about 1. After stirring and heating at 95 ° C. for 6 hours, 50 ml of acetonitrile was added to precipitate the resin. This was filtered, washed with acetonitrile, and dried at 100 ° C. to obtain a novolak resin (6). The molar ratio of the substituent having a cyano group of the novolak resin (6) to the phenolic hydroxyl group was 5.0 / 5.0, and the weight average molecular weight was 1,600 in terms of styrene. When the relative dielectric constant was measured in the same manner as in Example 1, it was 8.0.
（実施例７）
１００ｍｌの三つ口フラスコに２１．２ｇ（０．２モル）の実施例５で得られたノボラック樹脂（５）、６３．６ｇ（１．２モル）のアクリロニトリル、２ｇの水酸化ナトリウム、そして、４０ｇの水を入れ、６０℃で１．５時間攪拌した。反応後、塩酸を加えてｐＨを７より若干小さくし、そこに水を加えて１００℃で未反応のアクリロニトリルを留去した。その後、塩化ナトリウムが洗い出されるまで熱水で洗いノボラック樹脂（７）を得た。ノボラック樹脂（７）のシアノ基を有する置換基とフェノール性水酸基とのモル比は７．５／２．５であり、重量平均分子量はスチレン換算で４５００であった。実施例１と同様にして比誘電率を測定したところ、１１．２であった。
(Example 7)
In a 100 ml three-necked flask, 21.2 g (0.2 mol) of the novolak resin (5) obtained in Example 5, 63.6 g (1.2 mol) acrylonitrile, 2 g sodium hydroxide, and 40 g of water was added and stirred at 60 ° C. for 1.5 hours. After the reaction, hydrochloric acid was added to make the pH slightly lower than 7, and water was added thereto to distill off unreacted acrylonitrile at 100 ° C. Then, the novolak resin (7) was obtained by washing with hot water until sodium chloride was washed out. The molar ratio of the substituent having a cyano group of the novolak resin (7) to the phenolic hydroxyl group was 7.5 / 2.5, and the weight average molecular weight was 4500 in terms of styrene. When the relative dielectric constant was measured in the same manner as in Example 1, it was 11.2.
（実施例８）
テトラヒドロフラン１００ｇに２−メチル−４−エチル−２−イミダゾール０．０５６ｇ、エポキシ樹脂としてエピクロンＨＰ−７２００Ｈ（大日本インキ化学工業（株）社製）１１．３ｇ、実施例１のノボラック樹脂（１）８．７ｇを加え、攪拌しながら溶解させた。溶解したテトラヒドロフラン溶液５０ｇをアルミカップに入れ、５０℃に設定したホットプレートで、１時間かけて溶剤を除去した。さらに１５０℃に設定したホットプレート上で、エポキシ樹脂組成物をテフロン（テフロンは登録商標である）棒でかき混ぜながら、ゲル化させた。得られたゲル物をハンマーで粉砕し、粉砕物を型枠に詰め、真空下、２ＭＰａの圧力をかけながら、室温から３℃／分で１７０℃まで昇温し、その後１時間プレスすることで、厚みが０．５ｍｍのエポキシ樹脂硬化物を得た。
(Example 8)
100 g of tetrahydrofuran, 0.056 g of 2-methyl-4-ethyl-2-imidazole, 11.3 g of epiclone HP-7200H (manufactured by Dainippon Ink & Chemicals, Inc.) as an epoxy resin, novolak resin (1) of Example 1 8.7 g was added and dissolved with stirring. 50 g of the dissolved tetrahydrofuran solution was put in an aluminum cup, and the solvent was removed with a hot plate set at 50 ° C. over 1 hour. Further, the epoxy resin composition was gelled while stirring with a Teflon (Teflon is a registered trademark) rod on a hot plate set at 150 ° C. By pulverizing the obtained gel material with a hammer, filling the pulverized material into a mold, raising the temperature from room temperature to 170 ° C. at 3 ° C./min while applying a pressure of 2 MPa, and then pressing for 1 hour. An epoxy resin cured product having a thickness of 0.5 mm was obtained.
（実施例９〜１７）
実施例８と同様の方法で、実施例９〜１７のエポキシ樹脂硬化物を得た。表１〜２に詳しい組成を示す。
(Examples 9 to 17)
In the same manner as in Example 8, cured epoxy resins of Examples 9 to 17 were obtained. Detailed compositions are shown in Tables 1-2.
（比較例１）
シアノエチル化プルランを特許文献１の実施例１に従って合成した。得られたシアノエチル化プルランを型枠に入れ、１６０℃、３ＭＰａで５分間プレスすることにより、厚みが０．５ｍｍのシアノエチル化プルラン板を得た。
(Comparative Example 1)
Cyanoethylated pullulan was synthesized according to Example 1 of US Pat. The obtained cyanoethylated pullulan was put into a mold and pressed at 160 ° C. and 3 MPa for 5 minutes to obtain a cyanoethylated pullulan plate having a thickness of 0.5 mm.
（比較例２）
シアノエチル基を含有する（メタ）アクリル酸エステルモノマーを特許文献２の製造例１に従って合成した。次にシアノエチルポリマーを特許文献２の実施例１に従って合成し、これを５０％ＤＭＦ溶液に調製した後、これを離型剤が塗布されたＰＥＴフィルムに塗布、１６０℃で４時間乾燥し、０．１ｍｍのフィルムを得た。さらに得られたフィルムを７枚積層し、厚みが０．５ｍｍになるように型枠に入れ、１７０℃、３ＭＰａで１０分間プレスすることにより、シアノエチル基を含有するアクリル酸エステルポリマー板を得た。
(Comparative Example 2)
A (meth) acrylic acid ester monomer containing a cyanoethyl group was synthesized according to Production Example 1 of Patent Document 2. Next, a cyanoethyl polymer was synthesized according to Example 1 of Patent Document 2 and prepared into a 50% DMF solution, which was then applied to a PET film coated with a release agent and dried at 160 ° C. for 4 hours. A 1 mm film was obtained. Furthermore, 7 sheets of the obtained film were laminated, put into a mold so as to have a thickness of 0.5 mm, and pressed at 170 ° C. and 3 MPa for 10 minutes to obtain an acrylate polymer plate containing a cyanoethyl group. .
（比較例３）
シアノエチル化エポキシ樹脂を特許文献３の実施例１に従って合成した。得られたシアノエチル化エポキシ樹脂１０ｇと硬化剤としてエピクロンＢ−０５３（大日本インキ化学工業（株）社製）４．３ｇを混合、脱泡した後、片面に離型剤を塗布したガラス板２枚をすき間が０．５ｍｍになるように調製したものに流し込み、１５０℃で２時間加熱することによりシアノエチル化されたエポキシ樹脂硬化物を得た。
(Comparative Example 3)
A cyanoethylated epoxy resin was synthesized according to Example 1 of Patent Document 3. 10 g of the obtained cyanoethylated epoxy resin and 4.3 g of Epicron B-053 (manufactured by Dainippon Ink & Chemicals, Inc.) as a curing agent were mixed and degassed, and then a glass plate 2 with a release agent applied on one side The sheet was poured into one prepared to have a gap of 0.5 mm and heated at 150 ° C. for 2 hours to obtain a cured cyanoethylated epoxy resin.
（比較例４）
１００ｍｌの三つ口フラスコに２１．２ｇ（０．２モル）のフェノールノボラック樹脂ＴＤ−２０９０（大日本インキ化学工業（株）社製）、７４．２ｇ（１．４モル）のアクリロニトリル、２ｇの水酸化ナトリウム、そして、４０ｇの水を入れ、６０℃で４時間攪拌した。反応後、塩酸を加えてｐＨを７より若干小さくし、そこに水を加えて１００℃で未反応のアクリロニトリルを留去した。その後、塩化ナトリウムが洗い出されるまで熱水で洗い、９８．３％シアノエチル変性されたノボラック樹脂（比４）を得た。ノボラック樹脂（比４）のシアノ基を有する置換基とフェノール性水酸基とのモル比は、９．８／０．２であり、重量平均分子量は７５００であった。実施例１と同様にして比誘電率を測定したところ、６．９であった。
実施例１のノボラック樹脂（１）の代わりに、ノボラック樹脂（比４）を使用した以外は実施例８と同様にして、エポキシ樹脂硬化物を得た。その詳しい組成を表２に示す。
(Comparative Example 4)
In a 100 ml three-necked flask, 21.2 g (0.2 mol) of phenol novolac resin TD-2090 (manufactured by Dainippon Ink & Chemicals, Inc.), 74.2 g (1.4 mol) of acrylonitrile, 2 g Sodium hydroxide and 40 g of water were added and stirred at 60 ° C. for 4 hours. After the reaction, hydrochloric acid was added to make the pH slightly lower than 7, and water was added thereto to distill off unreacted acrylonitrile at 100 ° C. Thereafter, it was washed with hot water until sodium chloride was washed out to obtain 98.3% cyanoethyl-modified novolak resin (ratio 4). The molar ratio of the substituent having a cyano group and the phenolic hydroxyl group of the novolak resin (ratio 4) was 9.8 / 0.2, and the weight average molecular weight was 7,500. The relative dielectric constant was measured in the same manner as in Example 1. As a result, it was 6.9.
An epoxy resin cured product was obtained in the same manner as in Example 8, except that the novolak resin (ratio 4) was used instead of the novolak resin (1) in Example 1. The detailed composition is shown in Table 2.
（比較例５）
１００ｍｌの三つ口フラスコに２１．２ｇ（０．２モル）のフェノールノボラック樹脂ＴＤ−２０９０（大日本インキ化学工業（株）社製）、２６．５ｇ（０．５モル）のアクリロニトリル、２ｇの水酸化ナトリウム、そして、４０ｇの水を入れ、６０℃で４時間攪拌した。反応後、塩酸を加えてｐＨを７より若干小さくし、そこに水を加えて１００℃で未反応のアクリロニトリルを留去した。その後、塩化ナトリウムが洗い出されるまで熱水で洗い、３０．３％シアノエチル変性されたノボラック樹脂（比５）を得た。ノボラック樹脂（比５）のシアノ基を有する置換基とフェノール性水酸基とのモル比は、３．０／７．０であり、重量平均分子量は５５００であった。実施例１と同様にして比誘電率を測定したところ、５．４であった。
実施例１のノボラック樹脂（１）の代わりに、得られたノボラック樹脂（比５）を使用した以外は実施例８と同様にして、エポキシ樹脂硬化物を得た。その詳しい組成を表２に示す。
(Comparative Example 5)
In a 100 ml three-necked flask, 21.2 g (0.2 mol) of phenol novolac resin TD-2090 (manufactured by Dainippon Ink & Chemicals, Inc.), 26.5 g (0.5 mol) of acrylonitrile, 2 g Sodium hydroxide and 40 g of water were added and stirred at 60 ° C. for 4 hours. After the reaction, hydrochloric acid was added to make the pH slightly lower than 7, and water was added thereto to distill off unreacted acrylonitrile at 100 ° C. Thereafter, it was washed with hot water until sodium chloride was washed out to obtain a 30% cyanoethyl-modified novolak resin (ratio 5). The molar ratio of the substituent having a cyano group of the novolak resin (ratio 5) to the phenolic hydroxyl group was 3.0 / 7.0, and the weight average molecular weight was 5,500. The relative dielectric constant was measured in the same manner as in Example 1. As a result, it was 5.4.
A cured epoxy resin was obtained in the same manner as in Example 8, except that the obtained novolak resin (ratio 5) was used instead of the novolak resin (1) in Example 1. The detailed composition is shown in Table 2.
（比較例６）
実施例１のフェノールノボラック樹脂の代わりに、シアノアルキル変性していないフェノールノボラック樹脂「ＴＤ−２０９０」（大日本インキ化学工業（株）社製）を使用した以外は実施例８と同様にして、エポキシ樹脂硬化物を得た。その詳しい組成を表２に示す。
(Comparative Example 6)
Instead of the phenol novolak resin of Example 1, a phenol novolak resin “TD-2090” (manufactured by Dainippon Ink & Chemicals, Inc.) not modified with cyanoalkyl was used in the same manner as in Example 8, An epoxy resin cured product was obtained. The detailed composition is shown in Table 2.
（表中、単位は質量部である。ＴＤ−２０９０は、シアノアルキル変性していないフェノールノボラック樹脂（大日本インキ化学工業（株）社製）を示し、ＴＨＦはテトラヒドロフランを示す。）
(In the table, the unit is parts by mass. TD-2090 represents a phenol novolak resin (produced by Dainippon Ink & Chemicals, Inc.) not modified with cyanoalkyl, and THF represents tetrahydrofuran.)
（評価結果）
実施例、比較例で得られたエポキシ樹脂硬化物は、比誘電率及び耐熱性により評価した。その結果を表３に示す。評価方法は、次の方法で行った。
(Evaluation results)
The cured epoxy resins obtained in Examples and Comparative Examples were evaluated based on the relative dielectric constant and heat resistance. The results are shown in Table 3. The evaluation method was performed by the following method.
（比誘電率）
得られたエポキシ樹脂硬化物を３ｃｍ×３ｃｍにカットし、両面に金をスパッタすることで比誘電率測定用の試料を作製した。得られた試料はＬＦインピーダンスアナライザ４１９２Ａ（横河ヒューレット・パッカード（株）社製）を用い、１００ｋＨｚの比誘電率を測定した。
(Relative permittivity)
The obtained cured epoxy resin was cut into 3 cm × 3 cm, and gold was sputtered on both sides to prepare a sample for measuring the relative dielectric constant. The obtained sample was measured for a relative dielectric constant of 100 kHz using an LF impedance analyzer 4192A (manufactured by Yokogawa Hewlett-Packard Co.).
（ｔａｎδ）
誘電率の指標としてｔａｎδを測定した。測定は、比誘電率と同様の方法で行った。交流電流で比誘電率を測定する場合、試料に加わる電界のエネルギー損失分が誘電損失として生じる。このエネルギー損失は、通常、熱として発生するので、誘電損失の小さいものほど、優れた材料であると判断できる。ｔａｎδは、誘電損失／比誘電率で定義され、材料の良否を判断する指標とされている。
(Tan δ)
Tan δ was measured as an index of dielectric constant. The measurement was performed by the same method as the relative dielectric constant. When measuring the relative dielectric constant with an alternating current, the energy loss of the electric field applied to the sample occurs as dielectric loss. Since this energy loss is normally generated as heat, it can be determined that the smaller the dielectric loss, the better the material. tan δ is defined by dielectric loss / dielectric constant, and is an index for judging the quality of a material.
（耐熱性）
耐熱性の指標としてガラス転移点（Ｔｇ）を測定した。測定は、示差走査型熱分析装置ＤＳＣ２１０（セイコーインスツルメンツ（株）社製）を用いて行った。得られたエポキシ樹脂硬化物のＴｇは、３０〜２３０℃の範囲を１０℃／分の昇温速度で走査したときの熱流曲線の変曲点から求めた。
(Heat-resistant)
The glass transition point (Tg) was measured as an index of heat resistance. The measurement was performed using a differential scanning thermal analyzer DSC210 (manufactured by Seiko Instruments Inc.). The Tg of the obtained cured epoxy resin was determined from the inflection point of the heat flow curve when the range of 30 to 230 ° C. was scanned at a heating rate of 10 ° C./min.
この結果、実施例８〜１７と比較例１〜４において、比誘電率εにあまり差は無かったが、比較例１〜４は耐熱性に劣っていた。比較例５、６は、耐熱性は良好であったが、比誘電率が低かった。 As a result, in Examples 8 to 17 and Comparative Examples 1 to 4, there was not much difference in the relative dielectric constant ε, but Comparative Examples 1 to 4 were inferior in heat resistance. In Comparative Examples 5 and 6, the heat resistance was good, but the relative dielectric constant was low.
（実施例１８）
テトラヒドロフラン５０ｇに２−メチル−４−エチル−２−イミダゾール０．０５６ｇ、エポキシ樹脂としてエピクロンＨＰ−７２００Ｈ（大日本インキ化学工業（株）社製）１１．３ｇ、実施例１のフェノールノボラック樹脂（１）８．７ｇを加え、攪拌しながら溶解させた。得られた溶液を、１８μｍの銅箔にアプリケーターで塗布し、５０℃で１０分乾燥後、さらに１５０℃で１０分乾燥して、厚み５０μｍの樹脂付き銅箔を得た。得られた樹脂付き銅箔の樹脂側を２枚張り合わせ、真空下、２ＭＰａの圧力をかけながら、室温から３℃／分で１７０℃まで昇温し、その後１時間プレスすることで、両面に銅箔を有する厚み７０μｍの基板を得た。
(Example 18)
50 g of tetrahydrofuran, 0.056 g of 2-methyl-4-ethyl-2-imidazole, 11.3 g of epiclone HP-7200H (manufactured by Dainippon Ink & Chemicals, Inc.) as an epoxy resin, phenol novolac resin of Example 1 (1 8.7 g was added and dissolved while stirring. The obtained solution was applied to an 18 μm copper foil with an applicator, dried at 50 ° C. for 10 minutes, and further dried at 150 ° C. for 10 minutes to obtain a copper foil with a resin having a thickness of 50 μm. Two resin sides of the obtained resin-coated copper foil were bonded together, and while applying a pressure of 2 MPa under vacuum, the temperature was raised from room temperature to 170 ° C. at 3 ° C./min, and then pressed for 1 hour, so that copper was applied to both sides. A substrate having a thickness of 70 μm having a foil was obtained.
（実施例１９）
実施例１８において、実施例１で得られたノボラック樹脂（１）を実施例２で得られたノボラック樹脂（２）に代えた以外は、実施例１８と同様にして両面に銅箔を有する厚み６５μｍの基板を得た。
(Example 19)
In Example 18, except that the novolak resin (1) obtained in Example 1 was replaced with the novolak resin (2) obtained in Example 2, the thickness having copper foil on both sides was the same as in Example 18. A 65 μm substrate was obtained.
（実施例２０）
実施例１８において、実施例１で得られたノボラック樹脂（１）を実施例６で得られたノボラック樹脂（６）に代えた以外は、実施例１８と同様にして両面に銅箔を有する厚み７０μｍの基板を得た。
(Example 20)
In Example 18, except that the novolak resin (1) obtained in Example 1 was replaced with the novolak resin (6) obtained in Example 6, the thickness having copper foil on both sides in the same manner as in Example 18. A 70 μm substrate was obtained.
（実施例２１）
実施例１８において、実施例１で得られたノボラック樹脂（１）を実施例７で得られたノボラック樹脂（７）に代えた以外は、実施例１８と同様にして両面に銅箔を有する厚み６５μｍの基板を得た。
(Example 21)
In Example 18, except that the novolak resin (1) obtained in Example 1 was replaced with the novolak resin (7) obtained in Example 7, the thickness having copper foil on both surfaces was the same as in Example 18. A 65 μm substrate was obtained.
（比較例７）
特許文献１に記載の実施例１に従い、１２％のシアノエチル化プルラン溶液を作製し、これを１８μｍの銅箔にアプリケーターで塗布、１００℃で５時間乾燥し、厚み４５μｍの樹脂付き銅箔を得た。得られた樹脂付き銅箔の樹脂側を２枚張り合わせ、真空下、１６０℃、２ＭＰａで５分プレスすることにより、両面に銅箔を有する厚み５０μｍの基板を得た。
(Comparative Example 7)
According to Example 1 described in Patent Document 1, a 12% cyanoethylated pullulan solution was prepared, applied to an 18 μm copper foil with an applicator, and dried at 100 ° C. for 5 hours to obtain a copper foil with a resin having a thickness of 45 μm. It was. Two sheets of resin side of the obtained resin-coated copper foil were bonded together and pressed under vacuum at 160 ° C. and 2 MPa for 5 minutes to obtain a 50 μm thick substrate having copper foil on both sides.
（比較例８）
特許文献３に記載の実施例１に従い合成したシアノエチル化エポキシ樹脂１０部と、硬化剤としてエピクロンＢ−０５３（大日本インキ化学工業（株）社製）４．３部を混合、脱泡した後、これを１８μｍの銅箔にアプリケーターで塗布、１００℃で１５分加熱し、厚み１００μｍの樹脂付き銅箔を得た。得られた樹脂付き銅箔の樹脂側を２枚張り合わせ、１６０℃、２ＭＰａで１時間プレスすることにより両面に銅箔を有する厚み１２０μｍの基板を得た。
(Comparative Example 8)
After mixing and defoaming 10 parts of a cyanoethylated epoxy resin synthesized according to Example 1 described in Patent Document 3 and 4.3 parts of Epicron B-053 (manufactured by Dainippon Ink & Chemicals, Inc.) as a curing agent This was applied to an 18 μm copper foil with an applicator and heated at 100 ° C. for 15 minutes to obtain a resin-coated copper foil having a thickness of 100 μm. Two sheets of the resin side of the obtained copper foil with resin were bonded together and pressed at 160 ° C. and 2 MPa for 1 hour to obtain a 120 μm thick substrate having copper foil on both surfaces.
（比較例９）
実施例１８において、実施例１のノボラック樹脂（１）を、シアノアルキル変性していないフェノールノボラック樹脂「ＴＤ−２０９０」に代えた以外は、実施例９と同様にして両面に銅箔を有する厚み７５μｍの基板を得た。
実施例１８〜２１、及び、比較例７〜９の基板の比誘電率を、前記比誘電率の評価方法に従い行った。耐熱性は、２６０℃のハンダ浴に３０秒浸漬することでハンダ耐熱性を観察した。その結果を表４に示す。
(Comparative Example 9)
In Example 18, except that the novolak resin (1) of Example 1 was replaced with a phenol novolak resin “TD-2090” that was not cyanoalkyl-modified, a thickness having copper foil on both sides in the same manner as in Example 9. A 75 μm substrate was obtained.
The specific dielectric constants of the substrates of Examples 18 to 21 and Comparative Examples 7 to 9 were measured according to the evaluation method of the specific dielectric constant. The heat resistance was observed by immersing in a solder bath at 260 ° C. for 30 seconds. The results are shown in Table 4.
表４の結果より、本発明のエポキシ樹脂硬化物を用いて作製した金属箔付きの基板は、高誘電率でかつ耐熱性に優れていることがわかる。 From the results of Table 4, it can be seen that the substrate with metal foil produced using the cured epoxy resin of the present invention has a high dielectric constant and excellent heat resistance.
本発明のエポキシ樹脂硬化物は、優れた高誘電率及び耐熱性を有することから、基板状やフィルム状の形状にして、コンデンサ、電子写真用材料、圧電材料等の種々の電気分野や電子分野に使用する電子材料として好適に使用することができる。特に、金属箔を片側又は両側に設けた基板は、特に耐熱性を有する電子材料の他、ビルドアップの層間絶縁材用のコート材、樹脂付き銅箔にも好適に用いることができる。また、シリカやマイカなどの充填材を含有した状態で硬化させた硬化物は、リジッドプリント配線基板及びそのプリプレグとして好適に使用できる。
Since the cured epoxy resin of the present invention has an excellent high dielectric constant and heat resistance, it can be formed into a substrate-like or film-like shape in various electric and electronic fields such as capacitors, electrophotographic materials, and piezoelectric materials. It can be suitably used as an electronic material used in the above. In particular, a substrate provided with a metal foil on one side or both sides can be suitably used for a coating material for a build-up interlayer insulating material and a copper foil with resin, in addition to an electronic material having particularly heat resistance. Moreover, the hardened | cured material hardened | cured in the state containing fillers, such as a silica and a mica, can be used conveniently as a rigid printed wiring board and its prepreg.
Claims (9)
（式中、Ａはベンゼン環又はナフタレン環を表し、Ｂは−Ｏ−Ｘ１−ＣＮ、又は−Ｘ２−ＣＮを表し、Ｘ１は炭素原子数２〜４のアルキレン基を表し、Ｘ２は炭素原子数１〜４のアルキレン基を表す。） The novolac resin according to claim 7, wherein the novolac resin has a repeating unit represented by the general formula (1).
(In the formula, A represents a benzene ring or a naphthalene ring, B represents —O—X 1 —CN, or —X 2 —CN, X 1 represents an alkylene group having 2 to 4 carbon atoms, and X 2 Represents an alkylene group having 1 to 4 carbon atoms.)
（式中、Ａはベンゼン環又はナフタレン環を表し、Ｄは水素原子、−Ｏ−Ｘ１−ＣＮ、又は−Ｘ２−ＣＮを表し、Ｘ１は炭素原子数２〜４のアルキレン基を表し、Ｘ２は炭素原子数１〜４のアルキレン基を表す）
The novolak resin according to claim 7, wherein the novolak resin has repeating units represented by the general formula (2) and the general formula (3).
(In the formula, A represents a benzene ring or a naphthalene ring, D represents a hydrogen atom, —O—X 1 —CN, or —X 2 —CN, and X 1 represents an alkylene group having 2 to 4 carbon atoms. X 2 represents an alkylene group having 1 to 4 carbon atoms)
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| WO2012081403A1 (en) * | 2010-12-17 | 2012-06-21 | 富士フイルム株式会社 | Polymer composite piezoelectric body and method for producing same |
| WO2013008781A1 (en) * | 2011-07-12 | 2013-01-17 | 富士フイルム株式会社 | Piezoelectric element |
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