JP2009242560A - Epoxy resin composition and cured product of the same - Google Patents
Epoxy resin composition and cured product of the same Download PDFInfo
- Publication number
- JP2009242560A JP2009242560A JP2008090448A JP2008090448A JP2009242560A JP 2009242560 A JP2009242560 A JP 2009242560A JP 2008090448 A JP2008090448 A JP 2008090448A JP 2008090448 A JP2008090448 A JP 2008090448A JP 2009242560 A JP2009242560 A JP 2009242560A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- group
- hydrocarbon group
- resin composition
- aromatic hydrocarbon
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 167
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 167
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- -1 ester compound Chemical class 0.000 claims abstract description 135
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 239000005011 phenolic resin Substances 0.000 claims abstract description 39
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 31
- 125000003118 aryl group Chemical group 0.000 claims abstract description 31
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 29
- 150000002989 phenols Chemical class 0.000 claims abstract description 24
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 21
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 20
- 150000004820 halides Chemical class 0.000 claims abstract description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- 150000002430 hydrocarbons Chemical group 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 45
- 229920005989 resin Polymers 0.000 description 44
- 239000011347 resin Substances 0.000 description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 238000001723 curing Methods 0.000 description 35
- 239000003960 organic solvent Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 32
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 24
- 229920003986 novolac Polymers 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000002313 adhesive film Substances 0.000 description 17
- 238000005259 measurement Methods 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000011342 resin composition Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 150000001491 aromatic compounds Chemical class 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 239000011810 insulating material Substances 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 11
- 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 10
- 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 10
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 229930003836 cresol Natural products 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 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 10
- 238000002156 mixing Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 9
- 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 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000010030 laminating Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000002783 friction material Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000013329 compounding Methods 0.000 description 4
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008393 encapsulating agent Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 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
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012796 inorganic flame retardant Chemical class 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229920000877 Melamine resin Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
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- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 238000003851 corona treatment Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
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- 239000000539 dimer Substances 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
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- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000000486 o-cresyl group Chemical group [H]C1=C([H])C(O*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- QLORRTLBSJTMSN-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C QLORRTLBSJTMSN-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、硬化物の耐熱性と低誘電正接とを兼備させた、特に多層プリント基板絶縁材料に適したエポキシ樹脂組成物及びその硬化物に関する。 The present invention relates to an epoxy resin composition that combines heat resistance and low dielectric loss tangent of a cured product, and particularly suitable for a multilayer printed board insulating material, and a cured product thereof.
エポキシ樹脂及びその硬化剤を必須成分とするエポキシ樹脂組成物は、その硬化物において優れた耐熱性と絶縁性を発現することから、半導体や多層プリント基板などの電子部品用途において広く用いられている。 Epoxy resin compositions containing an epoxy resin and a curing agent as an essential component exhibit excellent heat resistance and insulation in the cured product, and are widely used in electronic component applications such as semiconductors and multilayer printed boards. .
この電子部品用途のなかでも多層プリント基板絶縁材料の技術分野では、プリプレグ製造工程における作業性の向上、或いは、ビルドアップ用接着剤フィルム用途における製造時の塗工性の向上という観点から樹脂成分を有機溶剤に溶解させた際の粘度の低減が求められている。一方、電子部品における高周波化や小型化の傾向から耐熱性に優れ、かつ、誘電正接の低い絶縁材料が求められており、とりわけビルドアップ用接着剤フィルム用途ではガラスクロスなど補強基材を使用することなく絶縁フィルムとすることから樹脂材料自体に要求される耐熱性や低誘電正接などの諸特性はより高度なものとなっている。 Among these electronic component applications, in the technical field of multilayer printed circuit board insulating materials, resin components are used from the viewpoint of improving workability in the prepreg manufacturing process, or improving coating properties during manufacturing in the use of adhesive film for buildup. There is a demand for a reduction in viscosity when dissolved in an organic solvent. On the other hand, insulation materials with excellent heat resistance and low dielectric loss tangent are required due to the trend toward higher frequency and smaller size in electronic components. In particular, reinforcing substrates such as glass cloth are used for adhesive film for build-up. Since the insulating film is used without any problems, various properties such as heat resistance and low dielectric loss tangent required for the resin material itself are more advanced.
従来より、電子部品用絶縁材料の技術分野において耐熱性と低誘電正接とを兼備させたエポキシ樹脂系材料として、クレゾールノボラック型エポキシ樹脂などのエポキシ樹脂を主剤として用い、かつ、イソフタル酸クロリドとα−ナフトールとのエステルと、ジシクロペンタジエン型フェノール樹脂等の多価フェノールとイソフタル酸クロリドとα−ナフトールとのエステルとをエポキシ樹脂用硬化剤として併用する技術が知られている（下記、特許文献１参照）。 Conventionally, as an epoxy resin material having both heat resistance and low dielectric loss tangent in the technical field of insulating materials for electronic parts, an epoxy resin such as a cresol novolac type epoxy resin has been used as a main ingredient, and isophthalic acid chloride and α A technique is known in which an ester with naphthol, a polyhydric phenol such as dicyclopentadiene-type phenol resin, an ester of isophthalic acid chloride and α-naphthol is used in combination as a curing agent for an epoxy resin (the following patent document) 1).
然し乍ら、前記エステルのうち、イソフタル酸クロリドとα−ナフトールとの反応生成物であるエステルは誘電正接の低減には効果が認められるものの溶剤溶解性が殆どなく、ワニス化することが困難であるため多層プリント基板用途に適用できないものであった。一方、前記ジシクロペンタジエン型フェノール樹脂とイソフタル酸クロリドとα−ナフトールとを反応させて得られるエステルは、前記特許文献１記載の如くクレゾールノボラック型エポキシ樹脂と組み合わせて使用した場合には、誘電正接の低減効果が十分でなく、また、耐湿性にも劣るものであった。このように高耐熱性・高耐湿性と低誘電正接とを高度に兼備した多層プリント基板絶縁材料に適する絶縁材料は知られていないのが現状であった。 However, among the esters, the ester, which is a reaction product of isophthalic acid chloride and α-naphthol, is effective in reducing the dielectric loss tangent, but has almost no solvent solubility and is difficult to be varnished. It could not be applied to multilayer printed circuit board applications. On the other hand, when the ester obtained by reacting the dicyclopentadiene type phenol resin, isophthalic acid chloride and α-naphthol is used in combination with a cresol novolac type epoxy resin as described in Patent Document 1, a dielectric loss tangent is obtained. The effect of reducing the above was not sufficient, and the moisture resistance was poor. As described above, there is no known insulating material suitable for a multilayer printed board insulating material that has both high heat resistance, high moisture resistance and low dielectric loss tangent.
従って、本発明が解決しようとする課題は、耐熱性、耐湿性、及び低誘電正接を高度に兼備したエポキシ樹脂組成物及びその硬化物を提供することにある。 Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition having high heat resistance, moisture resistance, and low dielectric loss tangent, and a cured product thereof.
本発明者等は上記課題を解決すべく鋭意検討を重ねた結果、アルコキシ基含有縮合多環式芳香族炭化水素基を分子構造内に有するノボラック型エポキシ樹脂を主剤として用い、かつ、脂肪族環状炭化水素基を介してフェノール類が結節された分子構造を有するフェノール樹脂、芳香族ジカルボン酸又はそのハライド、及び、芳香族モノヒドロキシ化合物とを所定割合で反応させて得られるエステル化合物をエポキシ樹脂用硬化剤として用いることにより、硬化物の耐熱性及び耐湿性に優れると共に、誘電正接が低くなることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a novolac type epoxy resin having an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group in the molecular structure as a main component, and an aliphatic cyclic group. For epoxy resins, phenolic resins having a molecular structure in which phenols are knotted through hydrocarbon groups, aromatic dicarboxylic acids or their halides, and aromatic monohydroxy compounds reacted at a predetermined ratio It has been found that by using it as a curing agent, the cured product is excellent in heat resistance and moisture resistance, and the dielectric loss tangent is lowered, and the present invention has been completed.
即ち、本発明は、エポキシ樹脂（Ｉ）、及び活性エステル化合物（II）を必須成分とするエポキシ樹脂組成物であって、
前記エポキシ樹脂（Ｉ）が、
グリシジルオキシ基含有芳香族炭化水素基（Ｅ）、
アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）、並びに、
メチレン基、アルキリデン基、及び芳香族炭化水素構造含有メチレン基から選択される２価の炭化水素基（Ｙ）
の各構造部位を有しており、かつ、前記グリシジルオキシ基含有芳香族炭化水素基（Ｅ）及び前記アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）が、前記メチレン基、アルキリデン基、及び芳香族炭化水素構造含有メチレン基から選択される２価の炭化水素基（Ｙ）を介して結合した構造を分子構造内に有しており、かつ、
前記活性エステル化合物（II）が、
脂肪族環状炭化水素基を介してフェノール類が結節された分子構造を有するフェノール樹脂（ii−１）、
芳香族ジカルボン酸又はそのハライド（ii−２）、及び、
芳香族モノヒドロキシ化合物（ii−３）
を反応させて得られる構造を有するものである
ことを特徴とするエポキシ樹脂組成物に関する。
That is, the present invention is an epoxy resin composition containing the epoxy resin (I) and the active ester compound (II) as essential components,
The epoxy resin (I) is
Glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an methylene group containing an aromatic hydrocarbon structure
And the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are the methylene group and the alkylidene group. And a structure bonded in a molecular structure through a divalent hydrocarbon group (Y) selected from methylene groups containing an aromatic hydrocarbon structure, and
The active ester compound (II) is
A phenol resin (ii-1) having a molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group,
An aromatic dicarboxylic acid or a halide thereof (ii-2), and
Aromatic monohydroxy compound (ii-3)
The present invention relates to an epoxy resin composition characterized by having a structure obtained by reacting.
本発明は、更に、上記エポキシ樹脂を硬化させてなる硬化物に関する。 The present invention further relates to a cured product obtained by curing the epoxy resin.
本発明によれば、高耐熱性、耐湿性及び低誘電正接を高度に兼備したエポキシ樹脂組成物及びその硬化物を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which combined high heat resistance, moisture resistance, and low dielectric loss tangent highly, and its hardened | cured material can be provided.
本発明で用いるエポキシ樹脂（Ｉ）は、
グリシジルオキシ基含有芳香族炭化水素基（Ｅ）、
アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）、並びに、
メチレン基、アルキリデン基、及び芳香族炭化水素構造含有メチレン基から選択される２価の炭化水素基（Ｙ）
の各構造部位を有しており、かつ、前記グリシジルオキシ基含有芳香族炭化水素基（Ｅ）及び前記アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）が、前記メチレン基、アルキリデン基、及び芳香族炭化水素構造含有メチレン基から選択される２価の炭化水素基（Ｙ）を介して結合した構造を分子構造内に有するものである。
The epoxy resin (I) used in the present invention is
Glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an methylene group containing an aromatic hydrocarbon structure
And the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are the methylene group and the alkylidene group. And a structure in which the molecular structure is bonded via a divalent hydrocarbon group (Y) selected from methylene groups containing an aromatic hydrocarbon structure.
本発明で用いるエポキシ樹脂（Ｉ）は、各構造部位（Ｅ）、（Ｘ）及び（Ｙ）の上記各具体例で示した構造の任意の組み合わせを採り得る。このような各構成部位から構成されるフェノール樹脂の分子構造は、グリシジルオキシ基含有芳香族炭化水素基（Ｅ）、アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）、およびメチレン基等（Ｙ）の各構造単位をそれぞれ、「Ｅ」、「Ｘ」、「Ｙ」で表した場合、下記構造部位Ａ１ The epoxy resin (I) used in the present invention can take any combination of the structures shown in the specific examples of the structural sites (E), (X), and (Y). The molecular structure of the phenol resin composed of such constituent parts is such that the glycidyloxy group-containing aromatic hydrocarbon group (E), the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), the methylene group, etc. When each structural unit of (Y) is represented by “E”, “X”, “Y”, the following structural site A1
下記構造式Ａ４又はＡ５
で表される構造を繰り返し単位とするノボラック構造の分子末端に、下記構造式Ａ６
Structural formula A4 or A5
At the molecular end of the novolak structure having the structure represented by
で表される構造を繰り返し単位とする交互共重合体構造が挙げられる。
The alternating copolymer structure which makes the structure represented by repeating unit a repeating unit is mentioned.
本発明においては、前記エポキシ樹脂（Ｉ）は、上記のように各種の構造をとり得るが、その分子末端に前記構造式Ａ６で表される構造を有することにより、エポキシ樹脂硬化物の誘電正接を著しく低減できることができる。よって、特に前記構造式Ａ３の構造を有するエポキシ樹脂、或いは、前記Ａ４又はＡ７を繰り返し単位とし、かつ、その分子末端に前記構造式Ａ６で表される構造を有するエポキシ樹脂が好ましく、特に本発明の効果が顕著に現れる点から、前記構造式Ａ３の構造を有するエポキシ樹脂、或いは、前記Ａ４を繰り返し単位とし、かつ、その分子末端に前記構造式Ａ６で表される構造を有するエポキシ樹脂が好ましい。 In the present invention, the epoxy resin (I) can have various structures as described above. By having a structure represented by the structural formula A6 at the molecular end, the dielectric loss tangent of the cured epoxy resin is obtained. Can be significantly reduced. Accordingly, an epoxy resin having the structure of the structural formula A3 or an epoxy resin having the structure represented by the structural formula A6 at the molecular end thereof and having the repeating unit of A4 or A7 is particularly preferable. From the standpoint of the effect of the above, an epoxy resin having the structure of the structural formula A3 or an epoxy resin having the structure represented by the structural formula A6 at the molecular end of the A4 as a repeating unit is preferable. .
ここで、グリシジルオキシ基含有芳香族炭化水素基（Ｅ）は、具体的には、以下のＥ１〜Ｅ１６の構造式で表されるグリシジルオキシベンゼン類、グリシジルオキシナフタレン類、及びこれらの芳香核上の置換基としてアルキル基を有する化合物が難燃性に優れるという点で好ましい。 Here, the glycidyloxy group-containing aromatic hydrocarbon group (E) specifically includes glycidyloxybenzenes, glycidyloxynaphthalenes, and aromatic nuclei represented by the following structural formulas E1 to E16. A compound having an alkyl group as a substituent is preferable in that it has excellent flame retardancy.
ここで、前記各構造は、前記構造式Ａ２のように該構造が分子末端に位置する場合には、１価の芳香族炭化水素基となる。また、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。 Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end as in the structural formula A2. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.
次に、エポキシ樹脂（Ｉ）構造中に含まれる前記アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）は、縮合多環式芳香核上の置換基としてアルコキシ基を有する１価の芳香族炭化水素基であり、具体的には下記構造式Ｅ１〜Ｅ１１で表されるアルコシキナフタレン構造、又は、下記構造式Ｅ１２で表されるアルコキシアントラセン構造が挙げられる。 Next, the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) contained in the epoxy resin (I) structure is a monovalent aromatic having an alkoxy group as a substituent on the condensed polycyclic aromatic nucleus. A hydrocarbon group, specifically, an alkoxynaphthalene structure represented by the following structural formulas E1 to E11 or an alkoxyanthracene structure represented by the following structural formula E12.
ここで前記各構造は、該構造が分子末端に位置する場合には、１価の芳香族炭化水素基となる。また、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。 Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.
以上詳述した前記アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）のうち、とりわけ、エポキシ樹脂硬化物の難燃性が良好なものとなる点からアルコキシナフタレン型の構造を有するものが好ましく、近年、電子部品分野において要求の高いハロゲンフリーの材料の設計が可能となる点から、前記構造式Ｘ１〜Ｘ１０に代表される、メトキシ基又はエトキシ基を置換基として有するナフタレン構造、およびそれらに更にメチル基を置換基として有する構造から形成される芳香族炭化水素基であることが好ましい。 Among the alkoxy group-containing condensed polycyclic aromatic hydrocarbon groups (X) described in detail above, those having an alkoxynaphthalene type structure from the viewpoint that the flame retardancy of the cured epoxy resin is particularly good. Preferably, a naphthalene structure having a methoxy group or an ethoxy group as a substituent, represented by the structural formulas X1 to X10, and the like, in view of the fact that it is possible to design a halogen-free material that is highly demanded in the field of electronic components in recent years. Furthermore, it is preferably an aromatic hydrocarbon group formed from a structure having a methyl group as a substituent.
次に、前記したメチレン基、アルキリデン基、及び芳香族炭化水素構造含有メチレン基から選択される２価の炭化水素基（Ｙ）の各構造部位は、メチレン基の他、アルキリデン基としては、エチリデン基、１，１−プロピリデン基、２，２−プロピリデン基、ジメチレン基、プロパン−１，１，３，３−テトライル基、ｎ−ブタン−１，１，４，４−テトライル基、ｎ−ペンタン−１，１，５，５−テトライル基が挙げられる。また、芳香族炭化水素構造含有メチレン基は、下記Ｙ１〜Ｙ４の構造のものが挙げられる。 Next, each structural site of the divalent hydrocarbon group (Y) selected from the above-mentioned methylene group, alkylidene group, and aromatic hydrocarbon structure-containing methylene group includes methylene group and alkylidene group as ethylidene group. Group, 1,1-propylidene group, 2,2-propylidene group, dimethylene group, propane-1,1,3,3-tetrayl group, n-butane-1,1,4,4-tetrayl group, n-pentane A -1,1,5,5-tetrayl group is mentioned. In addition, examples of the aromatic hydrocarbon structure-containing methylene group include the following Y1 to Y4 structures.
これらの中でも誘電効果に優れる点、更に有機溶剤へ溶解させた際の粘度が低い点から、とりわけメチレン基であることが好ましい。
従って、エポキシ樹脂（Ｉ）は、特に下記構造式（１）
Among these, a methylene group is particularly preferable because of its excellent dielectric effect and its low viscosity when dissolved in an organic solvent.
Accordingly, the epoxy resin (I) particularly has the following structural formula (1)
（式中、Ｅはグリシジルオキシ基含有芳香族炭化水素基を、Ｘはアルコキシ基含有縮合多環式芳香族炭化水素基、Ｘ’はアルコキシ基含有縮合多環式芳香族炭化水素基又はグリシジルオキシ基含有芳香族炭化水素基を表し、ｎは繰り返し単位で１〜１００の整数である。）で表される構造を有するものがとりわけ好ましい。
ここで、Ｘ’のアルコキシ基含有縮合多環式芳香族炭化水素基又はグリシジルオキシ基含有芳香族炭化水素基とは、Ｘ’が任意にアルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）又はグリシジルオキシ基含有芳香族炭化水素基（Ｅ）であることを示すものである。
(In the formula, E represents a glycidyloxy group-containing aromatic hydrocarbon group, X represents an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ represents an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or glycidyloxy. A group-containing aromatic hydrocarbon group is preferred, and n is a repeating unit and is preferably an integer of 1 to 100).
Here, the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or the glycidyloxy group-containing aromatic hydrocarbon group represented by X ′ is an X ′ is optionally an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X Or a glycidyloxy group-containing aromatic hydrocarbon group (E).
また、エポキシ樹脂（Ｉ）は、特に前記構造式（１）で表される構造を有するものである場合、該樹脂中には、通常、下記構造式（１’） In addition, when the epoxy resin (I) has a structure represented by the structural formula (1), the resin usually contains the following structural formula (1 ′).
（式中、Ｅはグリシジルオキシ基含有芳香族炭化水素基（Ｅ）を表す。）
で表される化合物が含まれることになるが、その含有率はエポキシ樹脂（Ｉ）中、５質量％以下となる割合、特に１．０〜３．５質量％なる範囲であることが難燃性の点から好ましい。
(In the formula, E represents a glycidyloxy group-containing aromatic hydrocarbon group (E).)
In the epoxy resin (I), the content is 5% by mass or less, particularly 1.0 to 3.5% by mass flame retardant. From the viewpoint of sex.
本発明では、このようにエポキシ樹脂（Ｉ）の主たる成分として下記構造式 In the present invention, as the main component of the epoxy resin (I), the following structural formula
で表される構造単位を繰り返し単位とする主骨格の末端にＸはアルコキシ基含有縮合多環式芳香族炭化水素基を導入すること該エポキシ樹脂（Ｉ）の硬化物の難燃性を飛躍的に改善できる。
Introducing an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group to the terminal of the main skeleton having the structural unit represented by the formula as a repeating unit, the flame retardancy of the cured product of the epoxy resin (I) is dramatically improved Can be improved.
また、前記構造式（１）中のｎの値は、ＧＰＣ測定から導出される繰り返し単位数である。ここでＧＰＣ測定の条件は、具体的には以下の通りである。 The value of n in the structural formula (1) is the number of repeating units derived from GPC measurement. Here, the conditions for the GPC measurement are specifically as follows.
［ＧＰＣの測定条件］
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
検出器： ＲＩ（示差屈折径）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
このようにして求められるｎの値は、前記した通り、１〜１００の範囲であるが、とりわけ本発明では分子末端に存在するアルコキシ基含有縮合多環式芳香族炭化水素基の含有率が高くなって難燃効果が顕著なものとなる点から特に１〜５０の範囲であることが好ましい。 The value of n thus determined is in the range of 1 to 100 as described above. In particular, in the present invention, the content of the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group present at the molecular end is high. From the point that the flame retardant effect becomes remarkable, the range of 1 to 50 is particularly preferable.
以上詳述したグリシジルオキシ基含有芳香族炭化水素基（Ｅ）は、特に芳香核上の置換基としてメチル基を有するものは、エポキシ樹脂硬化物自体に特に優れた難燃性を付与でき、近年、電子部品分野において要求の高いハロゲンフリーの材料の設計が可能となる。
前記エポキシ樹脂（Ｉ）は、更に、前記構造式（１）で表される構造のほか、前記構造式（１）におけるアルコキシ基含有縮合多環式芳香族炭化水素基（Ｂ）が隣接するフェノール性水酸基と脱アルコール反応することによって生成する環状構造を有する化合物を含んでいてもよい。
The glycidyloxy group-containing aromatic hydrocarbon group (E) described in detail above, particularly those having a methyl group as a substituent on the aromatic nucleus can give particularly excellent flame retardancy to the cured epoxy resin itself, This makes it possible to design halogen-free materials that are highly demanded in the field of electronic components.
In addition to the structure represented by the structural formula (1), the epoxy resin (I) is a phenol in which the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B) in the structural formula (1) is adjacent. It may contain a compound having a cyclic structure produced by a dealcoholization reaction with a functional hydroxyl group.
前記エポキシ樹脂（Ｉ）は、具体的には、前記構造式（１）中、ｎ＝１の化合物、ｎ＝２の化合物、ｎ＝３の化合物、及びｎ＝４の化合物の合計質量を、前記構造式（１）で表される全ての化合物の全質量で除した値が０．３〜０．８となるものであることが、その硬化物の難燃性はもとより、硬化物における低誘電率、低誘電正接といった誘電特性が良好なものとなる点から好ましい。 Specifically, the epoxy resin (I) is the total mass of the compound of n = 1, the compound of n = 2, the compound of n = 3, and the compound of n = 4 in the structural formula (1). The value obtained by dividing the total mass of all the compounds represented by the structural formula (1) is 0.3 to 0.8, in addition to the flame retardancy of the cured product, This is preferable from the viewpoint that dielectric properties such as dielectric constant and low dielectric loss tangent are good.
また、前記エポキシ樹脂（Ｉ）は、エポキシ当量が高い場合には組成物の硬化性が良好なものとなり、エポキシ当量が低い場合には硬化物の難燃性が良好となる。よって、これらのバランスが良好なものとなる点から、そのエポキシ当量は２００〜６００ｇ／ｅｑ．の範囲、特に２５０〜５５０ｇ／ｅｑ．の範囲であることが好ましい。 The epoxy resin (I) has a good curability of the composition when the epoxy equivalent is high, and the flame retardancy of the cured product is good when the epoxy equivalent is low. Accordingly, the epoxy equivalent is 200 to 600 g / eq. In the range of 250 to 550 g / eq. It is preferable that it is the range of these.
更に、前記エポキシ樹脂（Ｉ）は、グリシジルオキシ基含有芳香族炭化水素基（Ｅ）と、前記アルコキシ基含有縮合多環式芳香族炭化水素基（Ｂ）との存在比が、モル比で前者／後者＝３０／７０〜９８／２なる範囲であるであることが、硬化物の難燃性が一層良好となる点から好ましい。 Further, the epoxy resin (I) has a molar ratio of the abundance ratio between the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B). / The latter = 30/70 to 98/2 is preferable because the flame retardancy of the cured product is further improved.
以上詳述したエポキシ樹脂（Ｉ）は、以下の第一段階乃至第三段階を経て製造することができる。
第一段階：ヒドロキシ基含有芳香族系化合物（ｘ１）とホルムアルデヒドとを仕込み、アルカリ触媒の存在下でメチロール化反応を行う。
第二段階：中和剤を用いて前記アルカリ触媒を中和した後、アルコキシ基含有縮合多環式芳香族化合物（ｘ２）を仕込み、酸触媒下に反応させてフェノール樹脂を得る。
第三段階：第二段階で得られたフェノール樹脂と、エピハロヒドリンとを反応させることによって目的とするエポキシ樹脂を製造する。
The epoxy resin (I) detailed above can be produced through the following first to third steps.
First stage: A hydroxy group-containing aromatic compound (x1) and formaldehyde are charged, and a methylolation reaction is carried out in the presence of an alkali catalyst.
Second stage: After neutralizing the alkali catalyst with a neutralizing agent, an alkoxy group-containing condensed polycyclic aromatic compound (x2) is charged and reacted under an acid catalyst to obtain a phenol resin.
Third stage: A target epoxy resin is produced by reacting the phenol resin obtained in the second stage with epihalohydrin.
第一段階は、前記した通り、ヒドロキシ基含有芳香族系化合物（ｘ１）とホルムアルデヒドとをアルカリ触媒の存在下で反応させてメチロールを生成させる工程である。ここで用いるヒドロキシ基含有芳香族化合物（ｘ１）は、具体的には、フェノール、レゾルシノール、ヒドロキノンなどの無置換フェノール類、クレゾール、フェニルフェノール、エチルフェノール、ｎ−プロピルフェノール、ｉｓｏ−プロピルフェノール、ｔ−ブチルフェノールなどの一置換フェノール類、キシレノール、メチルプロピルフェノール、メチルブチルフェノール、メチルヘキシルフェノール、ジプロピルフェノール、ジブチルフェノールなどの二置換フェノール類、メシトール、２，３，５−トリメチルフェノール、２，３，６−トリメチルフェノール等の三置換フェノール類、１−ナフトール、２−ナフトール、メチルナフトールなどのナフトール類が挙げられる。これらは、２種類以上を併用してもよい。 As described above, the first stage is a process for producing methylol by reacting the hydroxy group-containing aromatic compound (x1) with formaldehyde in the presence of an alkali catalyst. Specific examples of the hydroxy group-containing aromatic compound (x1) used herein include unsubstituted phenols such as phenol, resorcinol and hydroquinone, cresol, phenylphenol, ethylphenol, n-propylphenol, iso-propylphenol, t -Monosubstituted phenols such as butylphenol, disubstituted phenols such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol, dibutylphenol, mesitol, 2,3,5-trimethylphenol, 2,3, Examples thereof include trisubstituted phenols such as 6-trimethylphenol, and naphthols such as 1-naphthol, 2-naphthol, and methylnaphthol. Two or more of these may be used in combination.
これらのなかでも、前記したとおり、硬化物の難燃性の点から１−ナフトール、２−ナフトール、クレゾール、フェノールが特に好ましい。 Among these, as described above, 1-naphthol, 2-naphthol, cresol, and phenol are particularly preferable from the viewpoint of flame retardancy of the cured product.
第一段階で用いられるアルカリ触媒としては、特に限定されるものではないが、アルカリ金属あるいはアルカリ土類金属の水酸化物が好ましく、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化マグネシウムなどが挙げられる。その使用量は仕込みヒドロキシ基含有芳香族系化合物（ｘ１）のモル数に対して、０．１〜３．０倍モルになる範囲であることが好ましい。 The alkali catalyst used in the first stage is not particularly limited, but an alkali metal or alkaline earth metal hydroxide is preferable. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide Examples include calcium and magnesium hydroxide. The amount used is preferably in the range of 0.1 to 3.0 times the number of moles of the charged hydroxy group-containing aromatic compound (x1).
第一段階の反応は、例えば、０〜８０℃の温度条件下に攪拌し乍ら行うことができる。 The first stage reaction can be performed, for example, with stirring under a temperature condition of 0 to 80 ° C.
次に、第二段階は、第一段階で得られた反応液に、中和剤を加えて反応溶液を中和し、次いで、アルコキシ基含有縮合多環式芳香族化合物（ｘ２）を仕込み、酸触媒下に反応させてフェノール樹脂を得る工程である。ここで用いる中和剤としては、特に限定されるものではないが、例えば、塩酸、硫酸、リン酸などの無機酸、メタンスルホン酸、ｐ−トルエンスルホン酸、シュウ酸などの有機酸、三弗化ホウ素、無水塩化アルミニウム、塩化亜鉛などのルイス酸などが挙げられる。 Next, the second stage neutralizes the reaction solution by adding a neutralizing agent to the reaction liquid obtained in the first stage, and then charges the alkoxy group-containing condensed polycyclic aromatic compound (x2), This is a step of obtaining a phenol resin by reacting under an acid catalyst. The neutralizing agent used here is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and trifluoride. Examples thereof include Lewis acids such as boron fluoride, anhydrous aluminum chloride, and zinc chloride.
また、第二段階で用いるアルコキシ基含有縮合多環式芳香族化合物（ｘ２）は、具体的には、１−メトキシナフタレン、２−メトキシナフタレン、１−メチル−２−メトキシナフタレン、１−メトキシ−２−メチルナフタレン、１，３，５−トリメチル−２−メトキシナフタレン、２，６−ジメトキシナフタレン、２，７−ジメトキシナフタレン、１−エトキシナフタレン、１，４−ジメトキシナフタレン、１−ｔ−ブトキシナフタレン、１−メトキシアントラセン等が挙げられる。これらの中でも特に得られるエポキシ樹脂の硬化物における難燃性の改善効果が顕著なものとなる点から２−メトキシナフタレンが好ましい。 Further, the alkoxy group-containing condensed polycyclic aromatic compound (x2) used in the second step is specifically 1-methoxynaphthalene, 2-methoxynaphthalene, 1-methyl-2-methoxynaphthalene, 1-methoxy- 2-methylnaphthalene, 1,3,5-trimethyl-2-methoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1-ethoxynaphthalene, 1,4-dimethoxynaphthalene, 1-t-butoxynaphthalene , 1-methoxyanthracene and the like. Among these, 2-methoxynaphthalene is preferable because the effect of improving the flame retardancy in the cured epoxy resin is particularly remarkable.
第二段階で用いられる酸触媒としては、特に限定されるものではないが、例えば、塩酸、硫酸、リン酸などの無機酸、メタンスルホン酸、ｐ−トルエンスルホン酸、シュウ酸などの有機酸、三弗化ホウ素、無水塩化アルミニウム、塩化亜鉛などのルイス酸などが挙げられる。その使用量は仕込み原料の総質量に対して、０．１〜５質量％なる範囲であることが好ましい。 The acid catalyst used in the second stage is not particularly limited, but examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, Examples include Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The amount used is preferably in the range of 0.1 to 5% by mass with respect to the total mass of the charged raw materials.
ここで、第一段階及び第二段階におけるヒドロキシ基含有芳香族系化合物（ｘ１）とアルコキシ基含有縮合多環式芳香族化合物（ｘ２）とホルムアルデヒドとの反応仕込み比率は、ヒドロキシ基含有芳香族系化合物（ｘ１）とアルコキシ基含有芳香族系化合物（ｘ２）とのモル比（ｘ１）／（ｘ２）が３０／７０〜９８／２であり、且つ、ヒドロキシ基含有芳香族系化合物（ｘ１）とアルコキシ基含有縮合多環式芳香族化合物（ｘ２）との合計モル数とホルムアルデヒドのモル数との比が４０／６０〜９７／３であることが好ましい。 Here, the reaction charge ratio of the hydroxy group-containing aromatic compound (x1), the alkoxy group-containing condensed polycyclic aromatic compound (x2) and formaldehyde in the first step and the second step is the hydroxy group-containing aromatic system. The molar ratio (x1) / (x2) between the compound (x1) and the alkoxy group-containing aromatic compound (x2) is 30/70 to 98/2, and the hydroxy group-containing aromatic compound (x1) The ratio of the total number of moles of the alkoxy group-containing condensed polycyclic aromatic compound (x2) and the number of moles of formaldehyde is preferably 40/60 to 97/3.
第二段階の反応を行う際、必要に応じて水または有機溶剤を使用することができる。使用できる有機溶剤の具体例としては、メチルセロソルブ、エチルセロソルブ、トルエン、キシレン、メチルイソブチルケトンなどが挙げられるがこれらに限定されるものではない。有機溶剤の使用量としては仕込み原料の総質量に対して通常１０〜５００質量％、好ましくは３０〜２５０質量％である。また第一段階のメチロール化反応の反応温度としては通常２０〜１５０℃であり、３０〜１００℃の範囲がより好ましく、反応時間としては通常１〜１０時間である。続いて、第二段階の反応温度としては通常４０〜２５０℃であり、１００〜２００℃の範囲がより好ましい。また反応時間としては通常１〜１０時間である。 In carrying out the second stage reaction, water or an organic solvent can be used as necessary. Specific examples of the organic solvent that can be used include, but are not limited to, methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is usually 10 to 500% by mass, preferably 30 to 250% by mass, based on the total mass of the charged raw materials. The reaction temperature of the first-stage methylolation reaction is usually 20 to 150 ° C., more preferably 30 to 100 ° C., and the reaction time is usually 1 to 10 hours. Subsequently, the reaction temperature in the second stage is usually from 40 to 250 ° C, and more preferably from 100 to 200 ° C. The reaction time is usually 1 to 10 hours.
また得られる該多価ヒドロキシ化合物の着色が大きい場合は、それを抑制するために、酸化防止剤や還元剤を添加しても良い。前記酸化防止剤としては特に限定されないが、例えば２，６−ジアルキルフェノール誘導体などのヒンダードフェノール系化合物や２価のイオウ系化合物や３価のリン原子を含む亜リン酸エステル系化合物などを挙げることができる。前記還元剤としては特に限定されないが、例えば次亜リン酸、亜リン酸、チオ硫酸、亜硫酸、ハイドロサルファイトまたはこれら塩や亜鉛などが挙げられる。 Further, when the resulting polyvalent hydroxy compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. be able to. Although it does not specifically limit as said reducing agent, For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, zinc, etc. are mentioned.
反応終了後、反応混合物のｐＨ値が３〜７、好ましくは４〜７になるまで中和あるいは水洗処理を行う。中和処理や水洗処理は常法にしたがって行えばよい。例えば酸触媒を用いた場合は水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、アンモニア、トリエチレンテトラミン、アニリン等の塩基性物質を中和剤として用いることができる。中和の際には、事前にリン酸等のバッファーを入れておいても良いし、また、一旦塩基サイドにしたのちシュウ酸などでｐＨ値が３〜７としてもよい。中和あるいは水洗処理を行った後、減圧加熱下で、主にヒドロキシ基含有芳香族系化合物（ｘ１）とアルコキシ基含有縮合多環式芳香族化合物（ｘ２）を含む未反応原料や有機溶剤、副生物を留去し生成物の濃縮を行い、目的の多価ヒドロキシ化合物を得ることが出来る。ここで回収した未反応原料は再利用することもできる。反応終了後の処理操作のなかに、精密濾過工程を導入することが無機塩や異物類を精製除去することが可能となる点から好ましい。 After completion of the reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 4 to 7. What is necessary is just to perform a neutralization process and a water washing process in accordance with a conventional method. For example, when an acid catalyst is used, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, and aniline can be used as the neutralizing agent. At the time of neutralization, a buffer such as phosphoric acid may be added in advance, or the pH may be adjusted to 3 to 7 with oxalic acid after the base side is once used. After the neutralization or water washing treatment, an unreacted raw material or organic solvent mainly containing a hydroxy group-containing aromatic compound (x1) and an alkoxy group-containing condensed polycyclic aromatic compound (x2) under reduced pressure heating, By-products are distilled off and the product is concentrated to obtain the target polyvalent hydroxy compound. The unreacted raw material recovered here can be reused. It is preferable to introduce a microfiltration step in the processing operation after the completion of the reaction because inorganic salts and foreign substances can be purified and removed.
次に第三段階は、第二段階で得られたフェノール樹脂と、エピハロヒドリンとを反応させることによって目的とするエポキシ樹脂を製造する工程である。具体的には、例えばフェノール樹脂中のフェノール性水酸基１モルに対し、エピハロヒドリン２〜１０モルを添加し、更に、フェノール性水酸基１モルに対し０．９〜２．０モルの塩基性触媒を一括添加または徐々に添加しながら２０〜１２０℃の温度で０．５〜１０時間反応させる方法が挙げられる。この塩基性触媒は固形でもその水溶液を使用してもよく、水溶液を使用する場合は、連続的に添加すると共に、反応混合物中から減圧下、または常圧下、連続的に水及びエピハロヒドリン類を留出せしめ、更に分液して水は除去しエピハロヒドリンは反応混合物中に連続的に戻す方法でもよい。 Next, the third stage is a process for producing the target epoxy resin by reacting the phenol resin obtained in the second stage with epihalohydrin. Specifically, for example, 2 to 10 mol of epihalohydrin is added to 1 mol of phenolic hydroxyl group in the phenol resin, and 0.9 to 2.0 mol of basic catalyst is collectively added to 1 mol of phenolic hydroxyl group. The method of making it react for 0.5 to 10 hours at the temperature of 20-120 degreeC, adding or adding gradually is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. Alternatively, the solution may be separated and further separated to remove water and the epihalohydrin is continuously returned to the reaction mixture.
なお、工業生産を行う際、エポキシ樹脂生産の初バッチでは仕込みに用いるエピハロヒドリン類の全てが新しいものであるが、次バッチ以降は、粗反応生成物から回収されたエピハロヒドリン類と、反応で消費される分で消失する分に相当する新しいエピハロヒドリン類とを併用することが好ましい。この時、使用するエピハロヒドリンは特に限定されないが、例えばエピクロルヒドリン、エピブロモヒドリン、β−メチルエピクロルヒドリン等が挙げられる。なかでも工業的入手が容易なことからエピクロルヒドリンが好ましい。 In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed in reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.
また、前記塩基性触媒は、具体的には、アルカリ土類金属水酸化物、アルカリ金属炭酸塩及びアルカリ金属水酸化物等が挙げられる。特にエポキシ樹脂合成反応の触媒活性に優れる点からアルカリ金属水酸化物が好ましく、例えば水酸化ナトリウム、水酸化カリウム等が挙げられる。使用に際しては、これらの塩基性触媒を１０〜５５質量％程度の水溶液の形態で使用してもよいし、固形の形態で使用しても構わない。また、有機溶媒を併用することにより、エポキシ樹脂の合成における反応速度を高めることができる。このような有機溶媒としては特に限定されないが、例えば、アセトン、メチルエチルケトン等のケトン類、メタノール、エタノール、１−プロピルアルコール、イソプロピルアルコール、１−ブタノール、セカンダリーブタノール、ターシャリーブタノール等のアルコール類、メチルセロソルブ、エチルセロソルブ等のセロソルブ類、テトラヒドロフラン、１、４−ジオキサン、１、３−ジオキサン、ジエトキシエタン等のエーテル類、アセトニトリル、ジメチルスルホキシド、ジメチルホルムアミド等の非プロトン性極性溶媒等が挙げられる。これらの有機溶媒は、それぞれ単独で使用してもよいし、また、極性を調整するために適宜二種以上を併用してもよい。 Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.
前述のエポキシ化反応の反応物を水洗後、加熱減圧下、蒸留によって未反応のエピハロヒドリンや併用する有機溶媒を留去する。また更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、得られたエポキシ樹脂を再びトルエン、メチルイソブチルケトン、メチルエチルケトンなどの有機溶媒に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えてさらに反応を行うこともできる。この際、反応速度の向上を目的として、４級アンモニウム塩やクラウンエーテル等の相関移動触媒を存在させてもよい。相関移動触媒を使用する場合のその使用量としては、用いるエポキシ樹脂に対して０．１〜３．０質量％の範囲が好ましい。反応終了後、生成した塩を濾過、水洗などにより除去し、更に、加熱減圧下トルエン、メチルイソブチルケトンなどの溶剤を留去することにより高純度のエポキシ樹脂を得ることができる。 After the reaction product of the epoxidation reaction is washed with water, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the epoxy resin used. After completion of the reaction, the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.
本発明のエポキシ樹脂組成物は、以上詳述したエポキシ樹脂（Ｉ）の他、本発明の効果を損なわない範囲で他のエポキシ樹脂を併用してもよい。併用する場合には、エポキシ樹脂全体に占める本発明のエポキシ樹脂（Ｉ）の割合は３０質量％以上となる割合であることが好ましく、特に４０質量％以上となる割合が好ましい。 In the epoxy resin composition of the present invention, in addition to the epoxy resin (I) detailed above, other epoxy resins may be used in combination as long as the effects of the present invention are not impaired. When using together, it is preferable that the ratio of the epoxy resin (I) of this invention to the whole epoxy resin is a ratio used as 30 mass% or more, and the ratio used as 40 mass% or more is especially preferable.
前記エポキシ樹脂（Ｉ）と併用され得る他のエポキシ樹脂としては、種々のエポキシ樹脂を用いることができるが、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂等が挙げられる。これらのなかでもフェノールアラルキル型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂や、ナフタレン骨格を含有するナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂や、結晶性のビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂や、キサンテン型エポキシ樹脂が、難燃性に優れる硬化物が得られる点から特に好ましい。 As other epoxy resins that can be used in combination with the epoxy resin (I), various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl Type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed Novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins. Among these, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins, naphthol novolak type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolacs. Type epoxy resin, crystalline biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, and xanthene type epoxy resin are particularly preferable because a cured product having excellent flame retardancy can be obtained.
次に、本発明で用いる前記活性エステル化合物（II）は、前記した通り、脂肪族環状炭化水素基を介してフェノール類が結節された分子構造を有するフェノール樹脂（ii−１）、芳香族ジカルボン酸又はそのハライド（ii−２）、及び、芳香族モノヒドロキシ化合物（ii−３）を反応させて得られる構造を有するものである。 Next, as described above, the active ester compound (II) used in the present invention includes a phenol resin (ii-1) having a molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group, and an aromatic dicarboxylic acid. It has a structure obtained by reacting an acid or its halide (ii-2) and an aromatic monohydroxy compound (ii-3).
本発明ではとりわけ硬化物の誘電正接が低く、かつ有機溶剤へ溶解させた際の粘度が十分に低くなる点から、前記活性エステル化合物（II）は、前記芳香族ジカルボン酸又はそのハライド（ii−２）中のカルボキシル基又は酸ハライド基１モルに対して、
前記フェノール樹脂（ii−１）中のフェノール性水酸基が０．０５〜０．７５モル、
前記芳香族モノヒドロキシ化合物（ii−３）が０．２５〜０．９５モル
となる割合で反応させて得られる構造を有するものであることが好ましい。
In the present invention, the active ester compound (II) is preferably the aromatic dicarboxylic acid or its halide (ii-) because the dielectric loss tangent of the cured product is particularly low and the viscosity when dissolved in an organic solvent is sufficiently low. 2) With respect to 1 mol of the carboxyl group or acid halide group in
0.05 to 0.75 mol of phenolic hydroxyl group in the phenol resin (ii-1),
The aromatic monohydroxy compound (ii-3) preferably has a structure obtained by reacting at a ratio of 0.25 to 0.95 mol.
本発明では、活性エステル化合物（II）を構成する原料比率を調節すること、具体的には、前記芳香族カルボン酸又はそのハライド（ii−２）の官能基数に対し、前記フェノール樹脂（ii−１）中の官能基数を少なく、かつ、前記芳香族モノヒドロキシ化合物（ii−３）の使用量（モル数）を多くなる様に上記範囲に調節することにより、得られる活性エステル化合物の硬化物において誘電正接を著しく低減させることができる。具体的には、硬化剤成分として前記活性エステル化合物（II）を、前記したイソフタル酸クロリドとα−ナフトールとの反応生成物であるエステルと併用することなく、単独で用いた場合であっても優れた低誘電正接を実現させることができる。更に、活性エステル化合物（II）自体の軟化点が低くなり、有機溶剤に溶解させた際の溶液粘度も低いものとなる。加えて、硬化物の耐熱性は極めて高いものとなる。このように低粘度でありながら高い耐熱性を発現する点は特筆すべき点である。 In the present invention, the ratio of the raw materials constituting the active ester compound (II) is adjusted, specifically, the phenol resin (ii−) with respect to the number of functional groups of the aromatic carboxylic acid or halide (ii-2) thereof. 1) The cured product of the active ester compound obtained by adjusting the amount within the above range so that the number of functional groups in the mixture is small and the amount (mole) of the aromatic monohydroxy compound (ii-3) is increased. Can significantly reduce the dielectric loss tangent. Specifically, even when the active ester compound (II) is used alone as a curing agent component without being used in combination with an ester which is a reaction product of the above-described isophthalic acid chloride and α-naphthol. An excellent low dielectric loss tangent can be realized. Furthermore, the softening point of the active ester compound (II) itself is lowered, and the solution viscosity when dissolved in an organic solvent is also lowered. In addition, the heat resistance of the cured product is extremely high. In this way, it should be noted that it exhibits high heat resistance while having low viscosity.
ここでフェノール樹脂（ii−１）において、脂肪族環状炭化水素基を介してフェノール類が結節された分子構造とは、１分子中に二重結合を２個含有する不飽和脂肪族環状炭化水素化合物とフェノール類とを重付加反応させて得られる構造が挙げられる。ここで、フェノール類としては、フェノール、及びアルキル基、アルケニル基、アリル基、アリール基、アラルキル基或いはハロゲン基等が１個または複数個置換した置換フェノール類が挙げられる。具体的には、クレゾール、キシレノール、エチルフェノール、イソプロピルフェノール、ブチルフェノール、オクチルフェノール、ノニルフェノール、ビニルフェノール、イソプロペニルフェノール、アリルフェノール、フェニルフェノール、ベンジルフェノール、クロルフェノール、ブロムフェノール、ナフトール、ジヒドロキシナフタレン等が例示されるが、これらに限定されるものではない。またこれらの混合物を用いても構わない。これらの中でも流動性および硬化性が優れる点からフェノールが特に好ましい。 Here, in the phenol resin (ii-1), the molecular structure in which phenols are knotted through an aliphatic cyclic hydrocarbon group is an unsaturated aliphatic cyclic hydrocarbon containing two double bonds in one molecule. Examples include a structure obtained by polyaddition reaction of a compound and phenols. Here, examples of the phenols include substituted phenols having one or more substituted phenols, alkyl groups, alkenyl groups, allyl groups, aryl groups, aralkyl groups, halogen groups, or the like. Specific examples include cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, naphthol, and dihydroxynaphthalene. However, it is not limited to these. Moreover, you may use these mixtures. Among these, phenol is particularly preferable from the viewpoint of excellent fluidity and curability.
また、不飽和脂環族環状炭化水素化合物としては、具体的には、ジシクロペンタジエン、テトラヒドロインデン、４−ビニルシクロヘキセン、５−ビニルノルボナ−２−エン、α−ピネン、β−ピネン、リモネン等が挙げられる。これらの中でも特性バランス、特に耐熱性、吸湿性の点からジシクロペンタジエンが好ましい。またジシクロペンタジエンは石油留分中に含まれることから、工業用ジシクロペンタジエンには他の脂肪族或いは芳香族性ジエン類等が不純物として含有されることがあるが、耐熱性、硬化性、成形性等を考慮すると、ジシクロペンタジエンの純度９０質量％以上の製品であることが望ましい。 Specific examples of unsaturated alicyclic hydrocarbon compounds include dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, and limonene. Can be mentioned. Among these, dicyclopentadiene is preferred from the viewpoint of property balance, particularly heat resistance and hygroscopicity. In addition, since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain other aliphatic or aromatic dienes as impurities, but heat resistance, curability, In consideration of moldability and the like, a product having a purity of 90% by mass or more of dicyclopentadiene is desirable.
次に、前記芳香族ジカルボン酸又はそのハライド（ii−２）は、イソフタル酸、テレフタル酸、１，４−、２，３−、あるいは２，６−ナフタレンジカルボン酸等の芳香族ジカルボン酸、及びこれらの酸フッ化物、酸塩化物、酸臭化物、酸ヨウ化物等の酸ハロゲン化物が挙げられる。これらのなかでも特に反応性が良好である点から芳香族ジカルボン酸の酸塩化物であること、なかでもイソフタル酸のジクロライド、テレフタル酸のジクロライドが好ましく、特にイソフタル酸のジクロライドが好ましい。 Next, the aromatic dicarboxylic acid or its halide (ii-2) is an aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, 1,4-, 2,3-, or 2,6-naphthalenedicarboxylic acid, and These acid halides include acid fluorides, acid chlorides, acid bromides, acid iodides and the like. Among these, an acid chloride of an aromatic dicarboxylic acid is preferable from the viewpoint of good reactivity, and isophthalic acid dichloride and terephthalic acid dichloride are particularly preferable, and isophthalic acid dichloride is particularly preferable.
次に、芳香族モノヒドロキシ化合物（ii−３）としては、例えば、フェノール；ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、３，５−キシレノール等のアルキルフェノール類；ｏ−フェニルフェノール、ｐ−フェニルフェノール、２−ベンジルフェノール、４−ベンジルフェノール、４−（α−クミル）フェノール等のアラルキルフェノール類；α−ナフトール、β−ナフトール等のナフトール類が挙げられる。これらのなかでも、特に硬化物の誘電正接が低くなる点からα−ナフトール、β−ナフトールが好ましい。 Next, as the aromatic monohydroxy compound (ii-3), for example, phenol; alkylphenols such as o-cresol, m-cresol, p-cresol, 3,5-xylenol; o-phenylphenol, p-phenyl Examples thereof include aralkylphenols such as phenol, 2-benzylphenol, 4-benzylphenol and 4- (α-cumyl) phenol; and naphthols such as α-naphthol and β-naphthol. Among these, α-naphthol and β-naphthol are preferable from the viewpoint of lowering the dielectric loss tangent of the cured product.
上記した活性エステル化合物（II）は、フェノール樹脂（ii−１）、芳香族ジカルボン酸又はそのハライド（ii−２）、及び、芳香族モノヒドロキシ化合物（ii−３）を反応させて得られる構造を有するものであるが、特に、下記構造式（２） The active ester compound (II) described above is a structure obtained by reacting a phenol resin (ii-1), an aromatic dicarboxylic acid or its halide (ii-2), and an aromatic monohydroxy compound (ii-3). In particular, the following structural formula (2)
（式中、Ｘはベンゼン環又はナフタレン環であり、ｋは０又は１を表し、ｎは繰り返し単位の平均値で０．０５〜２．５である。）
で表される構造のものがとりわけ硬化物の誘電正接が低く、かつ、有機溶剤に溶解させた際の溶液粘度が低くなる点から好ましい。
特に、上記構造式（２）においてｎの値、即ち、繰り返し単位の平均値が０．２５〜１．５の範囲にあるものが、溶液粘度が低くビルドアップ用接着フィルムへの製造が容易となる点から好ましい。また、上記構造式（１）中、ｋの値は０であることが、本発明の効果が顕著なものとなる点から好ましい。
(In the formula, X represents a benzene ring or a naphthalene ring, k represents 0 or 1, and n represents an average value of repeating units of 0.05 to 2.5.)
In particular, the structure represented by the formula is preferred because the cured product has a low dielectric loss tangent and a low solution viscosity when dissolved in an organic solvent.
In particular, in the above structural formula (2), the value of n, that is, the average value of the repeating units is in the range of 0.25 to 1.5, the solution viscosity is low and the production of the build-up adhesive film is easy. This is preferable. In the structural formula (1), the value of k is preferably 0 from the viewpoint that the effect of the present invention becomes remarkable.
ここで上記構造式（１）中のｎは以下の様にして求めることができる。
［構造式（１）中のｎの求め方］
下記の条件にて行ったＧＰＣ測定によりｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４のそれぞれに対応するスチレン換算分子量（α１、α２、α３、α４）と、ｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４のそれぞれの理論分子量（β１、β２、β３、β４）との比率（β１／α１、β２／α２、β３／α３、β４／α４）を求め、これら（β１／α１〜β４／α４）の平均値を求める。ＧＰＣで求めた数平均分子量（Ｍｎ）にこの平均値を掛け合わせた数値を平均分子量とする。次いで、前記構造式ａの分子量を前記平均分子量としてｎの値を算出する。
Here, n in the structural formula (1) can be determined as follows.
[How to find n in Structural Formula (1)]
According to GPC measurement performed under the following conditions, styrene equivalent molecular weights (α1, α2, α3, α4) corresponding to n = 1, n = 2, n = 3, and n = 4, and n = 1 and n = The ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) to the respective theoretical molecular weights (β1, β2, β3, β4) of 2, n = 3, and n = 4 were determined, and these (β1 / The average value of α1 to β4 / α4) is obtained. A value obtained by multiplying the number average molecular weight (Mn) obtained by GPC by this average value is defined as an average molecular weight. Next, the value of n is calculated using the molecular weight of the structural formula a as the average molecular weight.
（ＧＰＣ測定条件）
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
検出器： ＲＩ（示差屈折径）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
フェノール樹脂（ii−１）、芳香族ジカルボン酸又はそのハライド（ii−２）、及び、芳香族モノヒドロキシ化合物（ii−３）を反応させる方法は、具体的には、これらの各成分をアルカリ触媒の存在下に反応させることができる。
ここで使用し得るアルカリ触媒としては、水酸化ナトリウム、水酸化カリウム、トリエチルアミン、ピリジン等が挙げられる。これらのなかでも特に水酸化ナトリウム、水酸化カリウムが水溶液の状態で使用することができ、生産性が良好となる点から好ましい。
Specifically, the method in which the phenol resin (ii-1), the aromatic dicarboxylic acid or its halide (ii-2), and the aromatic monohydroxy compound (ii-3) are reacted with each other is alkalinized. The reaction can be carried out in the presence of a catalyst.
Examples of the alkali catalyst that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because they can be used in the form of an aqueous solution and the productivity is good.
前記反応は、具体的には有機溶媒の存在下、フェノール樹脂（ii−１）、芳香族ジカルボン酸又はそのハライド（ii−２）、及び、芳香族モノヒドロキシ化合物（ii−３）を混合し、前記アルカリ触媒又はその水溶液を連続的乃至断続的に滴下しながら反応させる方法が挙げられる。その際、アルカリ触媒の水溶液の濃度は、３．０〜３０％の範囲であることが好ましい。また、ここで使用し得る有機溶媒としては、トルエン、ジクロロメタンなどが挙げられる。 Specifically, in the reaction, a phenol resin (ii-1), an aromatic dicarboxylic acid or its halide (ii-2), and an aromatic monohydroxy compound (ii-3) are mixed in the presence of an organic solvent. And a method of reacting the alkali catalyst or an aqueous solution thereof while dropping continuously or intermittently. At that time, the concentration of the aqueous solution of the alkali catalyst is preferably in the range of 3.0 to 30%. Examples of the organic solvent that can be used here include toluene and dichloromethane.
反応終了後は、アルカリ触媒の水溶液を用いている場合には、反応液を静置分液し、水層を取り除き、残った有機層を洗浄後の水層がほぼ中性になるまで繰り返し、目的とする樹脂を得ることができる。 After completion of the reaction, if an aqueous solution of an alkali catalyst is used, the reaction solution is allowed to stand for separation, the aqueous layer is removed, and the remaining organic layer is repeated until the aqueous layer after washing becomes almost neutral, The target resin can be obtained.
このようにして得られる活性エステル化合物（II）は、通常、有機溶媒溶液として得られる為、積層板用ワニスやビルドアップ用接着フィルムとして用いる場合には、そのままで他の配合成分と混合し、更に、適宜、有機溶媒量を調節して目的とするエポキシ樹脂組成物を製造することができる。なお、本発明では前記した通り、該活性エステル化合物（II）を有機溶媒に溶解させて樹脂溶液とした際の溶融粘度が低いことを特徴としており、具体的には、不揮発分６５％のトルエン溶液の活性エステル化合物にした場合の溶液粘度が３００〜１０，０００ｍＰａ・Ｓ（２５℃）となる。 Since the active ester compound (II) thus obtained is usually obtained as an organic solvent solution, when used as a laminate varnish or build-up adhesive film, it is mixed with other ingredients as it is, Furthermore, the target epoxy resin composition can be produced by appropriately adjusting the amount of the organic solvent. As described above, the present invention is characterized by low melt viscosity when the active ester compound (II) is dissolved in an organic solvent to form a resin solution. Specifically, toluene having a nonvolatile content of 65% is used. The solution viscosity when the solution is an active ester compound is 300 to 10,000 mPa · S (25 ° C.).
本発明のエポキシ樹脂組成物では、エポキシ樹脂用硬化剤として前記活性エステル化合物（II）の他、本発明の効果を損なわない範囲でアミン系化合物、アミド系化合物、酸無水物系化合物、フェノ−ル系化合物など、その他のエポキシ樹脂用硬化剤（II’）を併用してもよい。 In the epoxy resin composition of the present invention, in addition to the active ester compound (II) as an epoxy resin curing agent, an amine compound, an amide compound, an acid anhydride compound, a pheno-amine as long as the effects of the present invention are not impaired. Other epoxy resin curing agents (II ′) such as ruthenium compounds may be used in combination.
ここで使用し得る、アミン系化合物は、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、イミダゾ−ル、ＢＦ３−アミン錯体、グアニジン誘導体等が挙げられる。
アミド系化合物は、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等が挙げられる。
Examples of amine compounds that can be used here include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complex, and guanidine derivatives.
Examples of the amide compounds include polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.
酸無水物系化合物は、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。 Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydroanhydride Examples include phthalic acid.
フェノール系化合物は、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂、α−ナフトールアラルキル樹脂、β−ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール−フェノール共縮ノボラック樹脂、ナフトール−クレゾール共縮ノボラック樹脂、アミノトリアジン変性フェノール樹脂等が挙げられる。また、前記アミノトリアジン変性フェノール樹脂は、具体的には、メラミンやベンゾグアナミン等のアミノ基含有トリアジン化合物と、フェノール、クレゾール等のフェノール類と、ホルムアルデヒドとの共重合体が挙げられる。 Phenol compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin. , Trimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, aminotriazine-modified phenol resin, and the like. Specific examples of the aminotriazine-modified phenol resin include copolymers of formaldehyde and amino group-containing triazine compounds such as melamine and benzoguanamine, phenols such as phenol and cresol, and formaldehyde.
これらの中でも、特に、硬化物の線膨張係数がより低くなり、熱的衝撃及び物理的衝撃に強く靱性に優れる点から多価フェノール系化合物が好ましく、フェノールノボラック樹脂、クレゾールノボラック樹脂、フェノールアラルキル樹脂、α−ナフトールアラルキル樹脂、β−ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂、アミノトリアジン変性フェノール樹脂が好ましい。 Among these, polyhydric phenol compounds are particularly preferred because the linear expansion coefficient of the cured product is lower, and they are resistant to thermal and physical impacts and are excellent in toughness. Phenol novolac resins, cresol novolac resins, phenol aralkyl resins Α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin, and aminotriazine-modified phenol resin are preferable.
本発明のエポキシ樹脂組成物において、前記エポキシ樹脂用硬化剤（II’）の配合量は、前記エポキシ樹脂（Ｉ）中のエポキシ基と、硬化剤（II’）中の活性水素との比率が、前者のエポキシ基／後者の活性水素のモル比で０．０５〜０．９５となる配合割合であることが、線膨張係数が低く、熱的衝撃／物理的衝撃に強い強靭な硬化物を得ることができる点から好ましい。 In the epoxy resin composition of the present invention, the compounding amount of the curing agent for epoxy resin (II ′) is such that the ratio of the epoxy group in the epoxy resin (I) to the active hydrogen in the curing agent (II ′) is as follows. In addition, the molar ratio of the former epoxy group / the latter active hydrogen is 0.05 to 0.95, and a tough cured product having a low coefficient of linear expansion and strong against thermal shock / physical impact is obtained. It is preferable because it can be obtained.
本発明のエポキシ樹脂組成物は、上記した各成分に加え、更に、硬化促進剤（III）を併用してもよい。 The epoxy resin composition of the present invention may further contain a curing accelerator (III) in addition to the above-described components.
ここで使用し得る硬化促進剤（III）は、例えば、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。この中でも、硬化物の低線膨張係数化の効果が顕著なものとなる点からイミダゾール類が好ましい。 Examples of the curing accelerator (III) that can be used here include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. Among these, imidazoles are preferable because the effect of reducing the linear expansion coefficient of the cured product becomes remarkable.
また、硬化促進剤（III）の添加量は、目標とする硬化時間等によって適宜調整することができるが、前記したエポキシ樹脂成分、硬化剤成分及び前記硬化促進剤（III）の総質量に対して０．１〜７質量％となる範囲であることが好ましい。 The addition amount of the curing accelerator (III) can be appropriately adjusted depending on the target curing time, etc., but is based on the total mass of the epoxy resin component, the curing agent component and the curing accelerator (III). Is preferably in the range of 0.1 to 7% by mass.
本発明のエポキシ樹脂組成物は、使用用途に応じて、上記した各成分に加え、更に有機溶剤（ＩＶ）を使用することができる。例えば、エポキシ樹脂組成物を積層板用ワニスとして用いる場合には基材への含浸性が改善される他、ビルドアップフィルムとして用いる場合には、基材シートへの塗工性が良好になる。ここで使用し得る有機溶剤（ＩＶ）は、例えば、メタノール、エタノール、イソプロピルアルコール、メチルセロソルブ、エチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール性溶媒、
アセトン、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、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類、セロソルブ、ブチルカルビトール等のカルビトール類、トルエン、キシレン等の芳香族炭化水素類、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等が挙げられる。
The epoxy resin composition of the present invention can further use an organic solvent (IV) in addition to the above-described components, depending on the intended use. For example, when the epoxy resin composition is used as a varnish for a laminated board, the impregnation property to the base material is improved, and when it is used as a build-up film, the coating property to the base material sheet is improved. The organic solvent (IV) that can be used here is, for example, an alcoholic solvent such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether,
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, carbitols such as cellosolve, butyl carbitol, toluene And aromatic hydrocarbons such as xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
なお、前記した通り、本発明で用いる活性エステル化合物（II）は、通常、有機溶媒溶液として得られる為、本発明のエポキシ樹脂組成物を積層板用ワニスやビルドアップ用接着フィルムとして用いる場合には、活性エステル化合物（II）の有機溶剤溶液をそのまま他の配合成分と混合し、適宜、前記有機溶剤（ＩＶ）を加えて有機溶媒量を調節すればよい。 As described above, the active ester compound (II) used in the present invention is usually obtained as an organic solvent solution. Therefore, when the epoxy resin composition of the present invention is used as a laminate varnish or a build-up adhesive film. The organic solvent solution of the active ester compound (II) may be mixed with other ingredients as it is, and the organic solvent (IV) may be added as appropriate to adjust the amount of the organic solvent.
本発明のエポキシ樹脂組成物は、使用用途に応じ、上記した各成分の他、適宜、無機質充填材、改質剤、難燃付与剤等を配合してもよい。 The epoxy resin composition of the present invention may contain an inorganic filler, a modifier, a flame retardant, and the like as appropriate in addition to the components described above, depending on the intended use.
ここで用いる前記無機質充填材は、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ、水酸化マグネシウム等が挙げられる。これらのなかでも特に溶融シリカが無機充填材の充填率を高めることができる点から好ましい。ここで、溶融シリカは破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め且つ成形材料の溶融粘度の上昇を抑制するためには、球状のものを主に用いる方が好ましい。更に球状シリカの配合量を高めるためには、球状シリカの粒度分布を適当に調整することが好ましい。 Examples of the inorganic filler used here include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and magnesium hydroxide. Among these, fused silica is particularly preferable from the viewpoint that the filling rate of the inorganic filler can be increased. Here, the fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress the increase in the melt viscosity of the molding material, it is preferable to mainly use the spherical one. preferable. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica.
無機充填材の配合割合は用途や所望特性によって、望ましい範囲が異なるが、例えば半導体封止材用途に使用する場合は、線膨張係数や難燃性を鑑みれば高い方が好ましく、エポキシ樹脂組成物全体量に対して６５〜９５質量％の範囲、特に８５〜９５質量％の範囲であることが好ましい。また導電ペーストや導電フィルムなどの用途に使用する場合は、銀粉や銅粉等の導電性充填剤を用いることができる。 The desired range of the blending ratio of the inorganic filler varies depending on the application and desired characteristics. For example, when used for a semiconductor sealing material, a higher ratio is preferable in view of the linear expansion coefficient and flame retardancy, and the epoxy resin composition It is preferable that it is the range of 65-95 mass% with respect to the whole quantity, especially the range of 85-95 mass%. Moreover, when using for uses, such as an electrically conductive paste and an electrically conductive film, electroconductive fillers, such as silver powder and copper powder, can be used.
前記改質剤として使用される熱硬化性樹脂および熱可塑性樹脂としては種々のものが全て使用できるが、例えばフェノキシ樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリエーテルサルホン樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリエステル樹脂、ポリスチレン樹脂、ポリエチレンテレフタレート樹脂などが例示できる。 Various types of thermosetting resins and thermoplastic resins can be used as the modifier. For example, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether Examples thereof include resins, polyphenylene sulfide resins, polyester resins, polystyrene resins, and polyethylene terephthalate resins.
前記難燃付与剤は、例えば、ハロゲン化合物、燐原子含有化合物や窒素原子含有化合物や無機系難燃化合物などが挙げられる。具体的には、テトラブロモビスフェノールＡ型エポキシ樹脂やブロム化フェノールノボラック型エポキシ樹脂などのハロゲン化合物、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリ−２−エチルヘキシルホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、２−エチルヘキシルジフェニルホスフェート、トリス（２，６ジメチルフェニル）ホスフェート、レゾルシンジフェニルホスフェートなどのリン酸エステル、ポリリン酸アンモニウム、ポリリン酸アミド、赤リン、リン酸グアニジン、ジアルキルヒドロキシメチルホスホネートなどの縮合リン酸エステル化合物などの燐原子含有化合物、メラミンなどの窒素原子含有化合物、水酸化アルミニウム、水酸化マグネシウム、硼酸亜鉛、硼酸カルシウムなどの無機系難燃化合物が挙げられる。
然しながら、本発明のエポキシ樹脂組成物は、環境負荷の高いハロゲン系の難燃剤を使用しなくとも優れた難燃効果を発現することを特徴とする為、上記した難燃付与剤を用いる場合には、燐原子含有化合物や窒素原子含有化合物や無機系難燃化合物を用いることが好ましい。
Examples of the flame retardant imparting agent include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specifically, halogen compounds such as tetrabromobisphenol A type epoxy resin and brominated phenol novolak type epoxy resin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, Phosphate esters such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, ammonium polyphosphate, Condensation of polyphosphate amide, red phosphorus, guanidine phosphate, dialkylhydroxymethylphosphonate, etc. Phosphorus atom-containing compounds such as phosphate ester compounds, nitrogen-containing compounds such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, and inorganic flame retardant compounds such as calcium borate.
However, the epoxy resin composition of the present invention is characterized by exhibiting an excellent flame retardant effect without using a halogen-based flame retardant having a high environmental load. It is preferable to use a phosphorus atom-containing compound, a nitrogen atom-containing compound, or an inorganic flame retardant compound.
本発明のエポキシ樹脂組成物は、前述のエポキシ樹脂（Ｉ）と、前記活性エステル化合物（II）と、必要に応じて配合されるその他の配合剤を均一に混合することによって得る事が出来る。この際、前記した通り、作業性を向上させる等の目的や、用途や加熱硬化条件に応じて、適宜、有機溶剤（ＩＶ）を配合して粘度調整を行っても良い。 The epoxy resin composition of the present invention can be obtained by uniformly mixing the aforementioned epoxy resin (I), the active ester compound (II), and other compounding agents blended as necessary. Under the present circumstances, as above-mentioned, according to the objective of improving workability | operativity, a use, and heat-curing conditions, you may mix | blend organic solvent (IV) suitably and may adjust a viscosity.
本発明のエポキシ樹脂組成物の熱硬化の条件は特に制限されるものではなく、通常のフェノール樹脂を硬化させる条件で硬化せしめることが可能であり、樹脂成分が軟化する温度以上であれば問題なく、通常、１２０℃以上２００℃以下の温度で行うことができる。特に成形性が良好となる点から１３０〜１８０℃の温度範囲であることが好ましい。また、耐熱性に優れた摩擦材を得るためには、成形後、焼成することが好ましい。 The conditions for thermosetting the epoxy resin composition of the present invention are not particularly limited, and can be cured under conditions for curing a normal phenol resin. Usually, it can be performed at a temperature of 120 ° C. or higher and 200 ° C. or lower. In particular, a temperature range of 130 to 180 ° C. is preferable from the viewpoint of good moldability. Moreover, in order to obtain the friction material excellent in heat resistance, it is preferable to fire after molding.
以上詳述した本発明のエポキシ樹脂組成物は、レジストインキ用樹脂組成物、摩擦材用結合剤、銅張積層板用樹脂組成物、ビルドアッププリント基板の層間絶縁材料、ビルドアップ用接着フィルム、電子部品の封止材用樹脂組成物、導電ペースト、樹脂注型材料、接着剤、絶縁塗料等のコーティング材料等に用いることができる。 The epoxy resin composition of the present invention described in detail above is a resin composition for resist ink, a binder for friction material, a resin composition for copper-clad laminate, an interlayer insulating material for a build-up printed board, an adhesive film for build-up, It can be used for a resin composition for a sealing material of an electronic component, a conductive paste, a resin casting material, an adhesive, a coating material such as an insulating paint, and the like.
本発明のエポキシ樹脂組成物をレジストインキ用樹脂組成物として用いる方法としては、例えば、前記エポキシ樹脂（Ｉ）と、前記活性エステル化合物（II）に、更に、有機溶剤（ＩＶ’）、顔料、タルク、及びフィラーを加えてレジストインキ用組成物とした後、スクリーン印刷方式にてプリント基板上に塗布した後、レジストインキ硬化物とする方法が挙げられる。ここで用いる有機溶剤（ＩＶ’）としては、例えば、メチルセロソルブ、エチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、シクロヘキサノン、ジメチルスルホキシド、ジメチルホルムアミド、ジオキソラン、テトラヒドロフラン、プロピレングリコ−ルモノメチルエーテルアセテート、エチルラクテート等が挙げられる。 Examples of the method of using the epoxy resin composition of the present invention as a resin composition for resist ink include, for example, the epoxy resin (I) and the active ester compound (II), an organic solvent (IV ′), a pigment, A method for preparing a resist ink composition by adding talc and a filler, and then applying the resist ink composition on a printed circuit board by a screen printing method is described. Examples of the organic solvent (IV ′) used here include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, dimethylsulfoxide, dimethylformamide, dioxolane, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl lactate Etc.
本発明のエポキシ樹脂組成物を摩擦材用結着剤に用いる場合、前記エポキシ樹脂（Ｉ）、前記活性エステル化合物（ＩＩ）に加え、更に、ヘキサメチレンテトラミン、パラホルムアルデヒド等の加熱によりホルムアルデヒドを発生する物質を用い、その他、前記硬化促進剤（III）を配合することによって摩擦材用結着剤を製造することができる。かかる摩擦材用結着剤を用いて摩擦材を調整するには、上記各成分に充填剤、添加剤等を添加、熱硬化させる方法、繊維基材に上記各成分を含浸させ熱硬化させる方法が挙げられる。ここで用いる充填剤、添加剤は、例えばシリカ、硫酸バリウム、炭酸カルシウム、炭化珪素、カシュー油重合物、二硫化モリブデン、水酸化アルミニウム、タルク、クレー、黒鉛、グラファイト、ゴム粒、アルミニウム粉、銅粉、真ちゅう粉等が挙げられる。 When the epoxy resin composition of the present invention is used as a binder for friction materials, in addition to the epoxy resin (I) and the active ester compound (II), formaldehyde is generated by heating hexamethylenetetramine, paraformaldehyde, etc. In addition, a binder for a friction material can be produced by blending the curing accelerator (III) with the substance to be used. In order to adjust the friction material using such a binder for friction material, a method of adding a filler, an additive and the like to each of the above components and thermally curing, a method of impregnating each of the above components into a fiber substrate and thermosetting it Is mentioned. Fillers and additives used here are, for example, silica, barium sulfate, calcium carbonate, silicon carbide, cashew oil polymer, molybdenum disulfide, aluminum hydroxide, talc, clay, graphite, graphite, rubber particles, aluminum powder, copper Examples thereof include powder and brass powder.
本発明のエポキシ樹脂組成物から銅張積層板用樹脂組成物を製造する方法は、具体的には、前記エポキシ樹脂（Ｉ）、前記活性エステル化合物（II）、有機溶剤（ＩＶ）、必要により前記したその他のエポキシ樹脂用硬化剤（II’）及び硬化促進剤（III）を配合してワニス化する方法が挙げられる。 Specifically, the method for producing a resin composition for copper clad laminates from the epoxy resin composition of the present invention includes the epoxy resin (I), the active ester compound (II), an organic solvent (IV), and if necessary. Examples of the method include blending the above-described other curing agent for epoxy resin (II ′) and curing accelerator (III) into a varnish.
次に、上記銅張積層板用樹脂組成物から銅張積層板を製造する方法は、具体的には、以下の方法が挙げられる。 Next, specific examples of the method for producing a copper clad laminate from the above resin composition for copper clad laminate include the following methods.
上記方法により得られたワニスを紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布などの各種補強基材に含浸させ、用いた溶剤種に応じた加熱温度、好ましくは５０〜１７０℃で加熱することによって、硬化物であるプリプレグを得る。この際、用いるエポキシ樹脂組成物と補強基材の配合割合は、通常、プリプレグ中の樹脂分が２０〜６０質量％となるように調整することが好ましい。 The varnish obtained by the above method is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, and the heating temperature according to the solvent type used, preferably A prepreg which is a cured product is obtained by heating at 50 to 170 ° C. Under the present circumstances, it is preferable to adjust normally the compounding ratio of the epoxy resin composition to be used and a reinforcement base material so that the resin content in a prepreg may be 20-60 mass%.
得られたプリプレグを積層し、更に銅箔を重ねて、１〜１０ＭＰａの加圧下に１７０〜２５０℃で１０分〜３時間、加熱圧着させることにより、目的とする銅張積層板を得ることができる。 By laminating the obtained prepreg, further stacking copper foil, and heat-pressing at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa, an intended copper clad laminate can be obtained. it can.
また、本発明の銅張積層板用樹脂組成物は、更に、ビルドアッププリント基板の層間絶縁材料としても極めて有用である。
かかるビルドアッププリント基板の層間絶縁材料は、前記したワニス化の方法のなかでも、特に、前記エポキシ樹脂（Ｉ）、前記活性エステル化合物（II）、前記有機溶剤（ＩＶ）、必要により前記したその他のエポキシ樹脂用硬化剤（II’）、硬化促進剤（III）、前記無機質充填材を配合する方法により調整することができる。このようにして得られたビルドアップ基板用層間絶縁材料からビルドアップ基板を製造する方法は、具体的には、以下の方法が挙げられる。
Moreover, the resin composition for copper clad laminates of the present invention is extremely useful as an interlayer insulating material for build-up printed boards.
Among the above-mentioned varnishing methods, the interlayer insulating material for such a build-up printed circuit board is, in particular, the epoxy resin (I), the active ester compound (II), the organic solvent (IV), and the others described above as necessary. The curing agent for epoxy resin (II ′), the curing accelerator (III), and the inorganic filler can be adjusted by a method of blending. Specific examples of the method for producing a build-up substrate from the interlayer insulation material for a build-up substrate thus obtained include the following methods.
すなわち、該ビルドアップ基板用層間絶縁材料を、回路を形成した配線基板にスプレーコーティング法、カーテンコーティング法等を用いて塗布した後、硬化させ、次いで、必要に応じて所定のスルーホール部等の穴あけを行った後、粗化剤により処理し、その表面を湯洗することによって、凹凸を形成させ、銅などの金属をめっき処理する。前記めっき方法は、無電解めっき、電解めっき処理が好ましく、また前記粗化剤としては酸化剤、アルカリ、有機溶剤等が挙げられる。このような操作を所望に応じて順次繰り返し、樹脂絶縁層及び所定の回路パターンの導体層を交互にビルドアップして形成することにより、ビルドアップ基板を得ることができる。但し、スルーホール部の穴あけは、最外層の樹脂絶縁層の形成後に行うことが好ましく、また、銅箔上で当該樹脂組成物を半硬化させた樹脂付き銅箔を、回路を形成した配線基板上に、１７０〜２５０℃で加熱圧着することで、粗化面を形成、メッキ処理の工程を省き、ビルドアップ基板を作製することも可能である。 That is, the interlayer insulating material for a build-up substrate is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured, and then, if necessary, a predetermined through-hole portion or the like After drilling, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and a metal such as copper is plated. The plating method is preferably electroless plating or electrolytic plating, and examples of the roughening agent include oxidizing agents, alkalis, and organic solvents. Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern. However, it is preferable to drill the through-hole portion after the outermost resin insulation layer is formed, and a wiring board on which a circuit is formed from a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil. Further, it is possible to produce a build-up substrate by forming a roughened surface and omitting the plating process by thermocompression bonding at 170 to 250 ° C.
また、前記ビルドアッププリント基板の層間絶縁材料は、前記した塗料状の材料のみならずビルドアップ用接着フィルムとして用いることができる。本発明のエポキシ樹脂組成物は、樹脂成分自体が優れた耐熱性を発現することから、ビルドアップ用接着フィルムとして特に有用である。 Further, the interlayer insulating material of the build-up printed board can be used as an adhesive film for build-up as well as the paint-like material described above. The epoxy resin composition of the present invention is particularly useful as an adhesive film for buildup because the resin component itself exhibits excellent heat resistance.
本発明のエポキシ樹脂組成物からビルドアップ用接着フィルムを製造する方法は、例えば、本発明のエポキシ樹脂組成物を、支持フィルム上に塗布し樹脂組成物層を形成させて多層プリント配線板用の接着フィルムとする方法が挙げられる。 The method for producing an adhesive film for buildup from the epoxy resin composition of the present invention is, for example, applied to the support film by forming the epoxy resin composition of the present invention on a support film to form a resin composition layer. The method of using an adhesive film is mentioned.
本発明のエポキシ樹脂組成物をビルドアップ用接着フィルムに用いる場合、該接着フィルムは、真空ラミネート法におけるラミネートの温度条件（通常７０℃〜１４０℃）で軟化し、回路基板のラミネートと同時に、回路基板に存在するビアホール或いはスルーホール内の樹脂充填が可能な流動性（樹脂流れ）を示すことが肝要であり、このような特性を発現するよう上記各成分を配合することが好ましい。 When the epoxy resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and at the same time as laminating the circuit board, It is important to show fluidity (resin flow) capable of filling the via hole or through hole in the substrate, and it is preferable to blend the above-described components so as to exhibit such characteristics.
ここで、多層プリント配線板のスルーホールの直径は通常０．１〜０．５ｍｍ、深さは通常０．１〜１．２ｍｍであり、通常この範囲で樹脂充填を可能とするのが好ましい。なお回路基板の両面をラミネートする場合はスルーホールの１／２程度充填されることが望ましい。 Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.
上記した接着フィルムを製造する方法は、具体的には、ワニス状の本発明のエポキシ樹脂組成物を調製した後、支持フィルム（Ｙ）の表面に、このワニス状の組成物を塗布し、更に加熱、あるいは熱風吹きつけ等により有機溶剤を乾燥させてエポキシ樹脂組成物の層（Ｘ）を形成させることにより製造することができる。 Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like epoxy resin composition of the present invention, coating the varnish-like composition on the surface of the support film (Y), and further It can be produced by drying the organic solvent by heating or blowing hot air to form the layer (X) of the epoxy resin composition.
形成される層（Ｘ）の厚さは、通常、導体層の厚さ以上とする。回路基板が有する導体層の厚さは通常５〜７０μｍの範囲であるので、樹脂組成物層の厚さは１０〜１００μｍの厚みを有するのが好ましい。 The thickness of the formed layer (X) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.
なお、本発明における層（Ｘ）は、後述する保護フィルムで保護されていてもよい。保護フィルムで保護することにより、樹脂組成物層表面へのゴミ等の付着やキズを防止することができる。 In addition, the layer (X) in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.
前記した支持フィルム及び保護フィルムは、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリイミド、更には離型紙や銅箔、アルミニウム箔等の金属箔などを挙げることができる。なお、支持フィルム及び保護フィルムはマッド処理、コロナ処理の他、離型処理を施してあってもよい。 The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.
支持フィルムの厚さは特に限定されないが、通常１０〜１５０μｍの範囲であり、好ましくは２５〜５０μｍの範囲で用いられる。また保護フィルムの厚さは１〜４０μｍの範囲であることが好ましい。 Although the thickness of a support film is not specifically limited, Usually, it is the range of 10-150 micrometers, Preferably it is used in the range of 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film is the range of 1-40 micrometers.
上記した支持フィルム（Ｙ）は、回路基板にラミネートした後に、或いは加熱硬化することにより絶縁層を形成した後に、剥離される。接着フィルムを加熱硬化した後に支持フィルム（Ｙ）を剥離すれば、硬化工程でのゴミ等の付着を防ぐことができる。硬化後に剥離する場合、通常、支持フィルムには予め離型処理が施される。 The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.
次に、上記のようして得られた接着フィルムを用いて多層プリント配線板を製造する方法は、例えば、層（Ｘ）が保護フィルムで保護されている場合はこれらを剥離した後、層（Ｘ）を回路基板に直接接するように、回路基板の片面又は両面に、例えば真空ラミネート法によりラミネートする。ラミネートの方法はバッチ式であってもロールでの連続式であってもよい。またラミネートを行う前に接着フィルム及び回路基板を必要により加熱（プレヒート）しておいてもよい。 Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (X) is protected by a protective film, after peeling these layers ( X) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.
ラミネートの条件は、圧着温度（ラミネート温度）を好ましくは７０〜１４０℃、圧着圧力を好ましくは１〜１１ｋｇｆ／ｃｍ２（９．８×１０４〜１０７．９×１０４Ｎ／ｍ２）とし、空気圧２０ｍｍＨｇ（２６．７ｈＰａ）以下の減圧下でラミネートすることが好ましい。 The lamination conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C. and a pressure bonding pressure of preferably 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 10 4 N / m 2 ), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.
また、前記した前記ビルドアッププリント基板の層間絶縁材料や、ビルドアップ用接着フィルム用途においては、本発明における優れた耐熱性を発現するという特質から、コンデンサ等の受動部品やＩＣチップ等の能動部品を基板内に埋め込んだ所謂電子部品内蔵基板における絶縁材料としてとりわけ有用である。 In addition, in the above-described interlayer insulation material for build-up printed circuit boards and adhesive film for build-up, active components such as capacitors and passive components such as capacitors and active components such as IC chips are obtained due to the characteristic of exhibiting excellent heat resistance in the present invention. It is particularly useful as an insulating material in a so-called electronic component built-in substrate in which is embedded in a substrate.
本発明のエポキシ樹脂組成物を電子部品の封止材用樹脂組成物として用いる場合の具体的用途は、半導体封止材料、半導体のテープ状封止剤、ポッティング型液状封止剤、アンダーフィル用樹脂、半導体の層間絶縁膜等が挙げられる。 Specific uses when the epoxy resin composition of the present invention is used as a resin composition for encapsulants of electronic components include semiconductor encapsulants, semiconductor tape encapsulants, potting liquid encapsulants, and underfill Examples thereof include resins and semiconductor interlayer insulating films.
本発明のエポキシ樹脂組成物を半導体封止材料用に調整するためには、前記前記エポキシ樹脂（Ｉ）、前記活性エステル化合物（II）、必要に応じて配合されるその他のカップリング剤、離型剤などの添加剤や無機充填材などを予備混合した後、押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に混合する手法が挙げられる。半導体のテープ状封止剤として使用する場合には、前述の手法によって得られた樹脂組成物を加熱して半硬化シートを作製し、封止剤テープとした後、この封止剤テープを半導体チップ上に置き、１００〜１５０℃に加熱して軟化させ成形し、１７０〜２５０℃で完全に硬化させる方法を挙げることができる。 In order to prepare the epoxy resin composition of the present invention for a semiconductor sealing material, the epoxy resin (I), the active ester compound (II), other coupling agents blended as necessary, a release agent. An example is a method in which additives such as molds and inorganic fillers are premixed and then sufficiently mixed until uniform using an extruder, kneader, roll or the like. When used as a semiconductor tape-like sealant, the resin composition obtained by the above-mentioned method is heated to prepare a semi-cured sheet, which is used as a sealant tape, and then this sealant tape is used as a semiconductor. A method of placing on a chip, heating to 100 to 150 ° C., softening and molding, and completely curing at 170 to 250 ° C. can be mentioned.
更にポッティング型液状封止剤として使用する場合には、前述の手法によって得られた樹脂組成物を必要に応じて溶剤に溶解した後、半導体チップや電子部品上に塗布し、直接、硬化させればよい。 Further, when used as a potting type liquid sealant, the resin composition obtained by the above-mentioned method is dissolved in a solvent as necessary, and then applied onto a semiconductor chip or an electronic component and directly cured. That's fine.
本発明のエポキシ樹脂組成物をアンダーフィル用樹脂として使用する方法は、例えば、予め基板ないし半導体素子上にワニス状のエポキシ樹脂組成物を塗布、次いで半硬化させてから、加熱して半導体素子と基板を密着させ、完全硬化させるコンプレッションフロー法等が挙げられる。 The method of using the epoxy resin composition of the present invention as an underfill resin is, for example, by previously applying a varnish-like epoxy resin composition on a substrate or a semiconductor element, then semi-curing it, and then heating the semiconductor element. For example, a compression flow method in which the substrate is brought into close contact and completely cured can be used.
本発明のエポキシ樹脂組成物を半導体の層間絶縁材料として使用する方法は、例えば、前記エポキシ樹脂（Ｉ）、前記活性エステル化合物（II）に加え、硬化促進剤、シランカップリング剤を配合して組成物を調整し、これをシリコン基板上にスピンコーティング等により塗布する方法が挙げられる。この場合、硬化塗膜は半導体に直接接することになるため、高温環境下において線膨張率の差によるクラックが生じないよう、絶縁材の線膨張率を半導体の線膨張率に近づけることが好ましい。 The method of using the epoxy resin composition of the present invention as a semiconductor interlayer insulating material includes, for example, a curing accelerator and a silane coupling agent in addition to the epoxy resin (I) and the active ester compound (II). A method of preparing the composition and applying it on a silicon substrate by spin coating or the like can be mentioned. In this case, since the cured coating film is in direct contact with the semiconductor, it is preferable that the linear expansion coefficient of the insulating material be close to the linear expansion coefficient of the semiconductor so that cracks due to the difference in linear expansion coefficient do not occur in a high temperature environment.
次に、本発明のエポキシ樹脂組成物から導電ペーストを調整する方法は、例えば、微細導電性粒子を該エポキシ樹脂組成物中に分散させ異方性導電膜用組成物とする方法、室温で液状である回路接続用ペースト樹脂組成物や異方性導電接着剤とする方法が挙げられる。 Next, a method for preparing a conductive paste from the epoxy resin composition of the present invention is, for example, a method in which fine conductive particles are dispersed in the epoxy resin composition to form a composition for an anisotropic conductive film, which is liquid at room temperature. And a paste resin composition for circuit connection and an anisotropic conductive adhesive.
本発明のエポキシ樹脂組成物を接着剤用樹脂組成物に調整する方法は、例えば、前記エポキシ樹脂（Ｉ）、前記活性エステル化合物（II）、必要に応じて樹脂類、硬化促進剤、溶剤、添加剤等を室温または加熱下で混合ミキサー等を用いて均一に混合する方法が挙げられ、各種の基材に塗布した後、室温又は加熱下に放置することによって基材の接着を行うことができる。 The method for adjusting the epoxy resin composition of the present invention to a resin composition for an adhesive is, for example, the epoxy resin (I), the active ester compound (II), if necessary, resins, a curing accelerator, a solvent, Examples include a method of uniformly mixing an additive or the like using a mixing mixer or the like at room temperature or under heating. After applying to various base materials, the base material can be adhered by leaving it to stand at room temperature or under heating. it can.
本発明のエポキシ樹脂組成物から複合材料を調整する方法は、前記エポキシ樹脂（Ｉ）、前記活性エステル化合物（II）を用途に応じた粘度に調製するために有機溶剤（ＩＶ）を用いてワニス化し、該当ワニスを補強基材に含浸し、加熱してプリプレグを得た後、それを繊維の方向を少しずつ変えて、擬似的に等方性を持たせるように積層し、その後加熱することにより硬化成形する方法が挙げられる。加熱温度としては、用いる溶剤の種類により適宜選択することができるが、５０〜１５０℃なる範囲であることが好ましい。また、前記補強基材としては、例えば炭素繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布が挙げられる。樹脂分と補強基材の割合も特に限定されないが、通常、プリプレグ中の樹脂分が２０〜６０質量％となるように調整するのが好ましい。 A method for preparing a composite material from the epoxy resin composition of the present invention is a method of preparing a varnish using an organic solvent (IV) in order to prepare the epoxy resin (I) and the active ester compound (II) to have a viscosity according to the use. After impregnating the varnish into a reinforcing base material and heating to obtain a prepreg, the fiber direction is changed little by little, and the layers are laminated so as to have pseudo-isotropic properties, and then heated. And a method of curing and molding. The heating temperature can be appropriately selected depending on the type of solvent used, but is preferably in the range of 50 to 150 ° C. Examples of the reinforcing substrate include carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The ratio of the resin component and the reinforcing substrate is not particularly limited, but it is usually preferable to adjust the resin component in the prepreg to 20 to 60% by mass.
上記した各種の用途のなかでも、本発明のエポキシ樹脂組成物は、硬化物の耐熱性と誘電正接が低く、かつ、溶液粘度が低いことから銅張積層板用樹脂組成物、ビルドアップ用接着フィルム用途としてとりわけ有用である。 Among the various uses described above, the epoxy resin composition of the present invention has a low heat resistance and dielectric loss tangent of the cured product and a low solution viscosity. It is particularly useful as a film application.
本発明の硬化物は、以上詳述した本発明のエポキシ樹脂組成物を成形硬化させて得られるものであり、用途に応じて積層物、注型物、接着剤、塗膜、フィルム等として使用できる。前記した通り、プリント基板用の銅張積層板として特に有用である。 The cured product of the present invention is obtained by molding and curing the epoxy resin composition of the present invention described in detail above, and is used as a laminate, cast product, adhesive, coating film, film, etc. depending on the application. it can. As described above, it is particularly useful as a copper clad laminate for printed circuit boards.
本発明のエポキシ樹脂組成物を硬化させるには、配合成分、用途等に応じて適宜適切な温度条件で加熱硬化させればよいが、具体的には、２５℃〜２００℃の温度条件で硬化させることが好ましい。 In order to cure the epoxy resin composition of the present invention, it may be cured by heating under an appropriate temperature condition as appropriate depending on the compounding component, application, etc., specifically, it is cured at a temperature condition of 25 ° C. to 200 ° C. It is preferable to make it.
以下、実施例により本発明を詳細に説明する。各種性状の測定方法は以下の通りである。
合成例１（エポキシ樹脂（Ｉ）の合成）
〔フェノール樹脂（Ａ−１）の合成〕
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、ｏ−クレゾール３２４．４２ｇ（３．００モル）と水３００．００ｇと４９質量％水酸化ナトリウム水溶液２１０．００ｇ（２．５７モル）を仕込み、４０℃迄昇温した。３７質量％ホルムアルデヒド水溶液４８６．９７ｇ（６．００モル）を１時間で滴下し、４０℃で４時間保持した。その後、適量の９８%硫酸を用いて中和した。続いて、シュウ酸１５．９８ｇと２−メトキシナフタレン４７４．６０ｇ（３．００モル）を加え、１３０℃まで昇温し１３０℃で１時間反応させた。この間、流出する水は分留管で捕集した。反応終了後、メチルイソブチルケトン１５００ｇを加え、分液ロートに移し水洗した。洗浄水が中性を示すまで水洗後、有機層から未反応のｏ−クレゾールと２−メトキシナフタレン、及びメチルイソブチルケトンを加熱減圧下に除去し、下記構造式（Ａ−１）
Hereinafter, the present invention will be described in detail by way of examples. The measurement methods for various properties are as follows.
Synthesis Example 1 (Synthesis of epoxy resin (I))
[Synthesis of phenol resin (A-1)]
In a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 324.42 g (3.00 mol) of o-cresol, 300.00 g of water, and a 49 mass% sodium hydroxide aqueous solution 210. 00 g (2.57 mol) was charged and the temperature was raised to 40 ° C. 486.97 g (6.00 mol) of 37% by mass aqueous formaldehyde solution was added dropwise over 1 hour, and the mixture was kept at 40 ° C. for 4 hours. Thereafter, neutralization was performed using an appropriate amount of 98% sulfuric acid. Subsequently, 15.98 g of oxalic acid and 474.60 g (3.00 mol) of 2-methoxynaphthalene were added, and the temperature was raised to 130 ° C. and reacted at 130 ° C. for 1 hour. During this time, the outflowing water was collected by a fractionating tube. After completion of the reaction, 1500 g of methyl isobutyl ketone was added, transferred to a separatory funnel and washed with water. After washing with water until the washing water shows neutrality, unreacted o-cresol, 2-methoxynaphthalene, and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula (A-1)
（式中、Ｘはメトキシナフタレン骨格、Ｘ’はメトキシナフタレン骨格又はクレゾール骨格、Ｐはクレゾール骨格である。）
で表される分子構造を有する化合物を主成分とするフェノール樹脂（Ａ−１）７５１．６ｇを得た。
フェノール樹脂（Ａ−１）は構造式（Ａ−１）におけるｎ＝１〜１７の化合物を含有するものであった。また、フェノール樹脂（Ａ−１）において、前記構造式（Ａ−１）中、ｎ＝１〜４で表される化合物は全てＸ’がメトキシナフタレン骨格のものであり、ｎ＝１〜４の化合物の合計質量を、構造式（Ａ−１）で表される全ての化合物の全質量で除した値は０．６７７であった。
また、フェノール樹脂（Ａ−１）は、の軟化点は１１１℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１３．０ｄＰａ・ｓ、水酸基当量は３６３ｇ／ｅｑ．であった。更に、フェノール樹脂（Ａ−１）の理論水酸基当量と実測の水酸基当量との比較から、反応に用いたメトキシナフタレンの２２質量％がｏ−クレゾール構造部位との脱メタノール反応による環状構造を形成していることが確認できた。
また、ＧＰＣ分析の結果、フェノール樹脂（Ａ−１）中の下記構造式
(Wherein, X is a methoxynaphthalene skeleton, X ′ is a methoxynaphthalene skeleton or a cresol skeleton, and P is a cresol skeleton.)
The phenol resin (A-1) 751.6g which has as a main component the compound which has the molecular structure represented by this was obtained.
The phenol resin (A-1) contained the compound of n = 1-17 in Structural formula (A-1). Moreover, in the phenol resin (A-1), in the structural formula (A-1), all of the compounds represented by n = 1 to 4 have a methoxynaphthalene skeleton, and n = 1 to 4 A value obtained by dividing the total mass of the compounds by the total mass of all the compounds represented by the structural formula (A-1) was 0.677.
The phenol resin (A-1) has a softening point of 111 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 13.0 dPa · s, and a hydroxyl group equivalent of 363 g. / Eq. Met. Furthermore, from a comparison between the theoretical hydroxyl group equivalent of phenol resin (A-1) and the measured hydroxyl group equivalent, 22% by mass of methoxynaphthalene used in the reaction formed a cyclic structure by demethanol reaction with the o-cresol structure site. It was confirmed that
Moreover, as a result of the GPC analysis, the following structural formula in the phenol resin (A-1)
で表される構造に該当する化合物の含有率は１．４質量％であった。回収した未反応のｏ−クレゾール及び２−メトキシナフタレンの質量測定の結果から、該フェノール樹脂（Ａ−１）中のクレゾール骨格の構造単位と、メトキシナフタレン骨格の構造単位とのモル比率は、前者／後者＝５０／５０であった。
The content rate of the compound corresponding to the structure represented by was 1.4 mass%. From the results of mass measurement of the recovered unreacted o-cresol and 2-methoxynaphthalene, the molar ratio between the structural unit of the cresol skeleton and the structural unit of the methoxynaphthalene skeleton in the phenol resin (A-1) is / The latter = 50/50.
〔エポキシ樹脂（Ｉ−ａ）の合成〕
温度計、滴下ロート、冷却管、撹拌機を取り付けたフラスコに、窒素ガスパージを施しながら、合成例１で得られたフェノール樹脂（Ａ−１）を３６３ｇ（水酸基１当量）、エピクロルヒドリン４６３ｇ（５．０モル）、ｎ−ブタノール１３９ｇ、テトラエチルベンジルアンモニウムクロライド２ｇを仕込み溶解させた。６５℃に昇温した後、共沸する圧力まで減圧して、４９質量％水酸化ナトリウム水溶液９０ｇ（１．１モル）を５時間かけて滴下した。その後、同条件で０．５時間撹拌を続けた。この間、共沸によって留出してきた留出分をディーンスタークトラップで分離し、水層を除去し、油層を反応系内に戻しながら、反応を行った。その後、未反応のエピクロルヒドリンを減圧蒸留によって留去させた。それで得られた粗エポキシ樹脂にメチルイソブチルケトン５９０ｇとｎ−ブタノール１７７ｇとを加え溶解した。更にこの溶液に１０％水酸化ナトリウム水溶液１０ｇを添加して８０℃で２時間反応させた後に洗浄液のｐＨが中性となるまで水１５０ｇで水洗を３回繰り返した。次いで共沸によって系内を脱水し、精密濾過を経た後に、溶媒を減圧下で留去して、下記構造式（Ｅ−１）
[Synthesis of Epoxy Resin (Ia)]
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas while 363 g (1 equivalent of hydroxyl group) of the phenol resin (A-1) obtained in Synthesis Example 1 and 463 g of epichlorohydrin (5. 0 mol), 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After the temperature was raised to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49 mass% sodium hydroxide aqueous solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 150 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain the following structural formula (E-1)
（式中、Ｘはメトキシナフタレン骨格、Ｘ’はメトキシナフタレン骨格又はクレゾール骨格、Ｅはｏ−グリシジルオキシメチルフェニレン基である。）
で表される分子構造を有する化合物を主成分とするエポキシ樹脂（Ｉ−ａ）３１７ｇを得た。
エポキシ樹脂（Ｉ−ａ）は構造式（Ｅ−１）におけるｎ＝１〜１７の化合物を含有するものであった。また、エポキシ樹脂（Ｉ−ａ）において、前記構造式（Ｅ−１）中、ｎ＝１〜４で表される化合物は全てＥ’がメトキシナフタレン骨格のものであり、ｎ＝１〜４の化合物の合計質量を、構造式（Ｅ−１）で表される全ての化合物の全質量で除した値は０．６１９であった。
得られたエポキシ樹脂の軟化点は１０１℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１３ｄＰａ・ｓ、エポキシ当量は５２９ｇ／ｅｑ．であり、下記構造式
(In the formula, X is a methoxynaphthalene skeleton, X ′ is a methoxynaphthalene skeleton or a cresol skeleton, and E is an o-glycidyloxymethylphenylene group.)
As a main component, 317 g of an epoxy resin (Ia) was obtained.
The epoxy resin (Ia) contained a compound of n = 1 to 17 in the structural formula (E-1). Moreover, in the epoxy resin (Ia), in the structural formula (E-1), all the compounds represented by n = 1 to 4 are those in which E ′ is a methoxynaphthalene skeleton, and n = 1 to 4 A value obtained by dividing the total mass of the compounds by the total mass of all the compounds represented by the structural formula (E-1) was 0.619.
The resulting epoxy resin had a softening point of 101 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 13 dPa · s, and an epoxy equivalent of 529 g / eq. And the following structural formula
で表される構造に該当する化合物の含有率は１．１質量％であった。
The content rate of the compound corresponding to the structure represented by was 1.1 mass%.
合成例２（活性エステル化合物の合成）
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにイソフタル酸クロリド ２０３．０ｇ（酸クロリド基のモル数：２．０モル）とトルエン １３３８ｇを仕込み系内を減圧窒素置換し溶解させた。次いで、α−ナフトール９６．０ｇ（０．６７モル）、ジシクロペンタジエンフェノール樹脂２２０ｇ（フェノール性水酸基のモル数：１．３３モル）を仕込み、系内を減圧窒素置換し溶解させた。その後、テトラブチルアンモニウムブロマイド １．１２ｇを溶解させ、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４００ｇを３時間かけて滴下した。次いでこの条件下で１．０時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているトルエン相に水を投入して約１５分間撹拌混合し、静置分液して水層を取り除いた。水層のｐＨが７になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去し不揮発分６５％のトルエン溶液状態にある活性エステル化合物（II−ａ）を得た。この不揮発分６５質量％のトルエン溶液の溶液粘度は３１６０ｍＰａ・Ｓ（２５℃）あった。また、得られた活性エステル化合物（II −ａ）は下記構造式ａ
Synthesis Example 2 (Synthesis of active ester compound)
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1338 g of toluene, and the system was purged with nitrogen under reduced pressure. And dissolved. Next, 96.0 g (0.67 mol) of α-naphthol and 220 g of dicyclopentadiene phenol resin (the number of moles of phenolic hydroxyl group: 1.33 mol) were charged, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Thereafter, 1.12 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while applying a nitrogen gas purge, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester compound (II-a) in a toluene solution state having a nonvolatile content of 65%. The solution viscosity of the toluene solution having a nonvolatile content of 65% by mass was 3160 mPa · S (25 ° C.). The obtained active ester compound (II-a) has the following structural formula a
においてｎが１．１０の構造を有するものであり、乾燥後の軟化点は１４０℃であった。
ここで、得られた活性エステル化合物（II −ａ）の軟化点及び上記構造式ａ中のｎは以下の様にして求めたものである。なお、以下の合成例２，３における軟化点及びｎの値も同様にして求めたものである。
［軟化点］
「ＪＩＳ Ｋ７２３４」に準拠して測定した。
［下記構造式ａ中のｎの求め方］
N had a structure of 1.10, and the softening point after drying was 140 ° C.
Here, the softening point of the obtained active ester compound (II-a) and n in the structural formula a are determined as follows. In addition, the softening point and the value of n in the following synthesis examples 2 and 3 were obtained in the same manner.
[Softening point]
Measurement was performed in accordance with “JIS K7234”.
[How to find n in the following structural formula a]
［構造式ａ中のｎの求め方］
下記の条件にて行ったＧＰＣ測定によりｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４のそれぞれに対応するスチレン換算分子量（α１、α２、α３、α４）と、ｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４のそれぞれの理論分子量（β１、β２、β３、β４）との比率（β１／α１、β２／α２、β３／α３、β４／α４）を求め、これら（β１／α１〜β４／α４）の平均値を求める。ＧＰＣで求めた数平均分子量（Ｍｎ）にこの平均値を掛け合わせた数値を平均分子量とする。次いで、前記構造式ａの分子量を前記平均分子量としてｎの値を算出する。
[How to find n in Structural Formula a]
According to GPC measurement performed under the following conditions, styrene equivalent molecular weights (α1, α2, α3, α4) corresponding to n = 1, n = 2, n = 3, and n = 4, and n = 1 and n = The ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) to the respective theoretical molecular weights (β1, β2, β3, β4) of 2, n = 3, and n = 4 were determined, and these (β1 / The average value of α1 to β4 / α4) is obtained. A value obtained by multiplying the number average molecular weight (Mn) obtained by GPC by this average value is defined as an average molecular weight. Next, the value of n is calculated using the molecular weight of the structural formula a as the average molecular weight.
（ＧＰＣ測定条件）
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
検出器： ＲＩ（示差屈折径）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
合成例２（活性エステル化合物の合成）
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにイソフタル酸クロリド ２０３．０ｇ（酸クロリド基のモル数：２．０モル）とトルエン１３１７ｇを仕込み系内を減圧窒素置換し溶解させた。次いで、α−ナフトール１４４．０ｇ（１．０モル）、ジシクロペンタジエンフェノール樹脂１６５ｇ（フェノール性水酸基のモル数：１モル）を仕込み、系内を減圧窒素置換し溶解させた。その後、テトラブチルアンモニウムブロマイド １．１０ｇを溶解させ、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４００ｇを３時間かけて滴下した。次いでこの条件下で１．０時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているトルエン相に水を投入して約１５分間撹拌混合し、静置分液して水層を取り除いた。水槽のｐＨが７になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去し不揮発分６５質量％のトルエン溶液状態にある活性エステル化合物（II −ｂ）を得た。この樹脂（II −ｂ）の粘度は８３０ｍＰａ・Ｓ（２５℃）あった。得られた活性エステル化合物（II −ｂ）は前記構造式ａにおいてｎが０．２４の構造を有するものであり、乾燥後の軟化点は１１９℃であった。
Synthesis Example 2 (Synthesis of active ester compound)
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1317 g of toluene, and the system was purged with nitrogen under reduced pressure. And dissolved. Next, 144.0 g (1.0 mol) of α-naphthol and 165 g of dicyclopentadiene phenol resin (mole number of phenolic hydroxyl group: 1 mol) were charged, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Thereafter, 1.10 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while applying a nitrogen gas purge, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the water tank reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester compound (II-b) in a toluene solution state having a nonvolatile content of 65% by mass. The viscosity of this resin (II-b) was 830 mPa · S (25 ° C.). The obtained active ester compound (II-b) has a structure where n is 0.24 in the structural formula a, and the softening point after drying was 119 ° C.
合成例３（活性エステル化合物の合成）
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにイソフタル酸クロリド ２０３．０ｇ（酸クロリド基のモル数：２．０モル）とトルエン １８００ｇを仕込み系内を減圧窒素置換し溶解させた。次いで、α−ナフトール ５７．６ｇ（０．４モル）、ジシクロペンタジエンフェノール樹脂 ４１２．５ｇ（フェノール性水酸基のモル数：２．５モル）を仕込み、系内を減圧窒素置換し溶解させた。その後、テトラブチルアンモニウムブロマイド １．１０ｇを溶解させ、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４００ｇを３時間かけて滴下した。次いでこの条件下で１．０時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているトルエン相に水を投入して約１５分間撹拌混合し、静置分液して水層を取り除いた。水槽のｐＨが７になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去し不揮発分６５質量％のトルエン溶液状態にある活性エステル化合物（II −ｃ）を得た。得られた活性エステル化合物（II −ｃ）の乾燥後の軟化点は１８４℃であった。
Synthesis Example 3 (Synthesis of active ester compound)
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1800 g of toluene, and the system was purged with nitrogen under reduced pressure. And dissolved. Next, 57.6 g (0.4 mol) of α-naphthol and 412.5 g of dicyclopentadiene phenol resin (mole number of phenolic hydroxyl group: 2.5 mol) were charged, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Thereafter, 1.10 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while applying a nitrogen gas purge, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the water tank reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester compound (II-c) in a toluene solution state having a nonvolatile content of 65% by mass. The softening point after drying of the obtained active ester compound (II-c) was 184 ° C.
比較合成例１（活性エステル化合物の合成）
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにイソフタル酸クロリド（２０３．０ｇ（１．０モル）とジメチルホルムアミド１２５４ｇを仕込み、系内を減圧窒素置換し溶解させた。次いで、α−ナフトール２８８．０ｇ（２．０モル）を仕込み、系内を減圧窒素置換し溶解させた。その後、テトラブチルアンモニウムブロマイド １．０５ｇを溶解させ、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４００ｇを３時間かけて滴下した。次いでこの条件下で１．０時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているトルエン相に水を投入して約１５分間撹拌混合し、静置分液して水層を取り除いた。水槽のｐＨが７になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去し不揮発分６５％のジメチルホルムアミド溶液の活性エステル化合物（II −ｄ）を合成した。
然し乍ら、かかる活性エステル化合物（II −ｄ）は、殆どトルエンに溶解せず、エポキシ樹脂と配合してワニス化することはできなかった。
Comparative Synthesis Example 1 (Synthesis of active ester compound)
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with isophthalic acid chloride (203.0 g (1.0 mol) and dimethylformamide 1254 g), and the system was purged with nitrogen under reduced pressure and dissolved. Next, 288.0 g (2.0 mol) of α-naphthol was charged, the inside of the system was purged with nitrogen under reduced pressure, and then 1.05 g of tetrabutylammonium bromide was dissolved and purged with nitrogen gas, Was added dropwise over a period of 3 hours, and stirring was continued for 1.0 hour under these conditions. Furthermore, water was added to the toluene phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand for separation to remove the aqueous layer until the pH of the water tank reached 7. The operation was repeated. Then, was synthesized active ester compound of dimethylformamide solution of a non-volatile content of 65% to remove moisture (II -d) in decanter dehydration.
However, such an active ester compound (II-d) was hardly dissolved in toluene and could not be varnished by mixing with an epoxy resin.
実施例１、２及び比較例１、２（エポキシ樹脂組成物の調整及び物性評価）
下記表１記載の配合に従い、エポキシ樹脂及びエステル化合物を配合し、最終的に各組成物の不揮発分（Ｎ．Ｖ．）が５５質量％となるようにトルエンを配合して調整した。
Examples 1 and 2 and Comparative Examples 1 and 2 (Adjustment of epoxy resin composition and evaluation of physical properties)
In accordance with the formulation shown in Table 1 below, an epoxy resin and an ester compound were blended, and toluene was blended and adjusted so that the nonvolatile content (NV) of each composition was finally 55% by mass.
次いで、下記の如き条件で硬化させて両面銅張積層板を試作し、各種の評価を行った。結果を表１に示す。
［積層板作製条件］
基材 ：１００μｍ； 日東紡績株式会社製 ガラスクロス「ＷＥＡ ２１１６」
プライ数 ：６
プリプレグ化条件：１６０℃／２分
銅 箔 ：１８μｍ； 日鉱金属株式会社製
硬化条件 ：１７０℃、２．９ＭＰａで１時間
成型後板厚 ：０．８ｍｍ 樹脂含有量 ：４０％
［オーブン耐熱性試験］
空気循環装置付恒温槽を用いて、２２０℃、２４０℃、２６０℃の条件において試験片（５０ｍｍ×５０ｍｍ）を１時間処理し、試験片面および端面のふくれ、はがれの無いものを○とした。これを更に２回繰り返し、合計３回評価した。
Subsequently, it was cured under the following conditions to produce a double-sided copper-clad laminate, and various evaluations were performed. The results are shown in Table 1.
[Laminate production conditions]
Base material: 100 μm; glass cloth “WEA 2116” manufactured by Nitto Boseki Co., Ltd.
Number of plies: 6
Prepregation conditions: 160 ° C / 2 minutes
Copper foil: 18 μm; made by Nikko Metal Co., Ltd. Curing conditions: 170 ° C., 2.9 MPa for 1 hour
Thickness after molding: 0.8mm Resin content: 40%
[Oven heat resistance test]
A test piece (50 mm × 50 mm) was treated for 1 hour under the conditions of 220 ° C., 240 ° C., and 260 ° C. using a thermostatic chamber with an air circulation device. This was repeated two more times for a total of three evaluations.
［誘電特性］
５０×２５×２ｍｍのサイズに試験片を切り出し、インピーダンスアナライザー４２９１Ｂ（アジレントテクノロジー製）とフィクスチャーを用いて、１ＧＨｚの周波数における誘電正接、誘電率を２３℃にて求めた。
［吸水率］
５０×２５×２ｍｍのサイズに試験片を切り出し、プレッシャークッカー試験機を使用し、１２１℃、２．１気圧、１００％ＲＨの条件において試験片を２時間保持後、その前後の重量変化を測定した。
吸水率（％）＝（試験後の質量―試験前の質量）／試験前の質量×１００
[Dielectric properties]
A test piece was cut out to a size of 50 × 25 × 2 mm, and a dielectric loss tangent and a dielectric constant at a frequency of 1 GHz were obtained at 23 ° C. using an impedance analyzer 4291B (manufactured by Agilent Technologies) and a fixture.
[Water absorption rate]
Cut out a test piece to a size of 50 x 25 x 2 mm, use a pressure cooker tester, hold the test piece for 2 hours at 121 ° C, 2.1 atm, and 100% RH, and measure the weight change before and after that. did.
Water absorption (%) = (mass after test−mass before test) / mass before test × 100
［溶剤溶解度］
各実施例及び比較例で用いた硬化剤の有機溶剤溶液を１５０℃、真空減圧にて１２時間乾燥させ、次いで、乾燥した固形分を２５℃においてトルエンに溶解させることにより、トルエン１００ｇに対する固形分の溶解量（ｇ）を評価した。
[Solvent solubility]
The organic solvent solution of the curing agent used in each Example and Comparative Example was dried at 150 ° C. for 12 hours under vacuum and reduced pressure, and then the solid content obtained by dissolving the dried solid content in toluene at 25 ° C. The dissolution amount (g) of was evaluated.
なお、表１中の略号は以下の通りである。
「エポキシ樹脂（Ｉ−ｂ）」：クレゾールノボラック型エポキシ樹脂（ＩＣＩ粘度：２３ｄＰａ・ｓ（１５０℃）、軟化点８４℃）
なお、表１中「１ｅｑ」は、エポキシ樹脂中のエポキシ基と、硬化剤中のエステル結合又はフェノール性水酸基とが当量となる割合であることを示すものであり、「ジメチルアミノピリジン 質量％／樹脂成分」とは、エポキシ樹脂と硬化剤との合計質量に対するジメチルアミノピリジンの質量基準の使用量である。
In addition, the symbol in Table 1 is as follows.
“Epoxy resin (Ib)”: Cresol novolac type epoxy resin (ICI viscosity: 23 dPa · s (150 ° C.), softening point 84 ° C.)
In Table 1, “1 eq” indicates that the epoxy group in the epoxy resin and the ester bond or the phenolic hydroxyl group in the curing agent are equivalent ratios, and “dimethylaminopyridine mass% / The “resin component” is the amount of dimethylaminopyridine based on the mass based on the total mass of the epoxy resin and the curing agent.
Claims (8)
前記エポキシ樹脂（Ｉ）が、
グリシジルオキシ基含有芳香族炭化水素基（Ｅ）、
アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）、並びに、
メチレン基、アルキリデン基、及び芳香族炭化水素構造含有メチレン基から選択される２価の炭化水素基（Ｙ）
の各構造部位を有しており、かつ、前記グリシジルオキシ基含有芳香族炭化水素基（Ｅ）及び前記アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）が、前記メチレン基、アルキリデン基、及び芳香族炭化水素構造含有メチレン基から選択される２価の炭化水素基（Ｙ）を介して結合した構造を分子構造内に有しており、かつ、
前記活性エステル化合物（II）が、
脂肪族環状炭化水素基を介してフェノール類が結節された分子構造を有するフェノール樹脂（ii−１）、
芳香族ジカルボン酸又はそのハライド（ii−２）、及び、
芳香族モノヒドロキシ化合物（ii−３）
を反応させて得られる構造を有するものである
ことを特徴とするエポキシ樹脂組成物。 An epoxy resin composition comprising an epoxy resin (I) and an active ester compound (II) as essential components,
The epoxy resin (I) is
Glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an methylene group containing an aromatic hydrocarbon structure
And the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are the methylene group and the alkylidene group. And a structure bonded in a molecular structure through a divalent hydrocarbon group (Y) selected from methylene groups containing an aromatic hydrocarbon structure, and
The active ester compound (II) is
A phenol resin (ii-1) having a molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group,
An aromatic dicarboxylic acid or a halide thereof (ii-2), and
Aromatic monohydroxy compound (ii-3)
An epoxy resin composition characterized in that it has a structure obtained by reacting.
（式中、Ｅはグリシジルオキシ基含有芳香族炭化水素基を、Ｘはアルコキシ基含有縮合多環式芳香族炭化水素基、Ｘ’はアルコキシ基含有縮合多環式芳香族炭化水素基又はグリシジルオキシ基含有芳香族炭化水素基を表し、ｎは繰り返し単位で０〜１００の整数である。）で表されるものである請求項１記載のエポキシ樹脂組成物 The epoxy resin (I) has the following structural formula (1)
(In the formula, E represents a glycidyloxy group-containing aromatic hydrocarbon group, X represents an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ represents an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or glycidyloxy. The epoxy resin composition according to claim 1, which represents a group-containing aromatic hydrocarbon group, and n is a repeating unit represented by an integer of 0 to 100.
前記芳香族ジカルボン酸又はそのハライド（ii -２）中のカルボキシル基又は酸ハライド基１モルに対して、
前記フェノール樹脂（ii -１）中のフェノール性水酸基が０．０５〜０．７５モル、
前記芳香族モノヒドロキシ化合物（ii -３）が０．２５〜０．９５モル
となる割合で反応させて得られる構造を有するものである請求項１又は２記載のエポキシ樹脂組成物。 A phenol resin (ii-1) having a molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group, an aromatic dicarboxylic acid or a halide thereof (ii-2), and an aromatic monohydroxy compound (ii- 3)
With respect to 1 mol of the carboxyl group or acid halide group in the aromatic dicarboxylic acid or its halide (ii-2),
0.05 to 0.75 mol of phenolic hydroxyl group in the phenol resin (ii-1),
The epoxy resin composition according to claim 1 or 2, which has a structure obtained by reacting the aromatic monohydroxy compound (ii-3) at a ratio of 0.25 to 0.95 mol.
（式中、Ｘはベンゼン環又はナフタレン環であり、ｋは０又は１を表し、ｎは繰り返し単位の平均で０．２５〜１．５である。）
で表される構造を有するものである請求項３記載のエポキシ樹脂組成物。 The active ester compound (II) is represented by the following structural formula (2)
(In the formula, X is a benzene ring or a naphthalene ring, k represents 0 or 1, and n is an average of repeating units of 0.25 to 1.5.)
The epoxy resin composition of Claim 3 which has a structure represented by these.
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