JP5862329B2 - Epoxy resin composition for laminate, laminate and integrated circuit - Google Patents
Epoxy resin composition for laminate, laminate and integrated circuit Download PDFInfo
- Publication number
- JP5862329B2 JP5862329B2 JP2012018339A JP2012018339A JP5862329B2 JP 5862329 B2 JP5862329 B2 JP 5862329B2 JP 2012018339 A JP2012018339 A JP 2012018339A JP 2012018339 A JP2012018339 A JP 2012018339A JP 5862329 B2 JP5862329 B2 JP 5862329B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- curing agent
- bisphenol
- laminate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000647 polyepoxide Polymers 0.000 title claims description 221
- 239000003822 epoxy resin Substances 0.000 title claims description 220
- 239000000203 mixture Substances 0.000 title claims description 60
- 239000003795 chemical substances by application Substances 0.000 claims description 57
- 229930185605 Bisphenol Natural products 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- -1 bisphenol compound Chemical class 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001723 curing Methods 0.000 description 66
- 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 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 229920005989 resin Polymers 0.000 description 31
- 239000011347 resin Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000010410 layer Substances 0.000 description 21
- 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 19
- 239000002904 solvent Substances 0.000 description 17
- 239000004593 Epoxy Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- AEBYJSOWHQYRPK-UHFFFAOYSA-N 1,1'-biphenyl;sodium Chemical compound [Na].C1=CC=CC=C1C1=CC=CC=C1 AEBYJSOWHQYRPK-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- STHGLRYNMROMHZ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-11-methyl-3-(8-methylnonyl)dodecane-1,3-diol Chemical compound C(CCCCCCC(C)C)C(O)(C(CO)(CO)CO)CCCCCCCC(C)C STHGLRYNMROMHZ-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- BGCSUUSPRCDKBQ-UHFFFAOYSA-N 2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OCOCC21COCOC2 BGCSUUSPRCDKBQ-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- WSOMHEOIWBKOPF-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)methyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CP2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 WSOMHEOIWBKOPF-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- SVNWKKJQEFIURY-UHFFFAOYSA-N 2-methyl-1-(2-methylpropyl)imidazole Chemical compound CC(C)CN1C=CN=C1C SVNWKKJQEFIURY-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ONTIGGPRJSEVGB-UHFFFAOYSA-N 6-decoxybenzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound C1=CC=C2P(OCCCCCCCCCC)(=O)OC3=CC=CC=C3C2=C1 ONTIGGPRJSEVGB-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Laminated Bodies (AREA)
Description
本発明は積層板用エポキシ樹脂組成物、積層板及び集積回路に関する。本発明は積層板用途として使用する際に重要となる誘電特性が特に優れ、吸水率が低く、また、耐熱性にも優れた積層板用エポキシ樹脂組成物と、この積層板用エポキシ樹脂組成物を用いた積層板及びこの積層板からなる集積回路に関する。 The present invention relates to an epoxy resin composition for laminates, laminates and integrated circuits. INDUSTRIAL APPLICABILITY The present invention is particularly excellent in dielectric properties that are important for use as a laminate, low in water absorption, and excellent in heat resistance, and this epoxy resin composition for laminate The present invention relates to a laminated board using a laminated board and an integrated circuit comprising the laminated board.
電子回路の高集積化に伴い、積層板を用いた多層の集積回路が一般的になっている。積層板とは、導電体である金属の回路を、絶縁膜を挟んで多層に重ね合わせたものである。電子回路における処理速度向上のために近年は電気信号の高周波数化が進んでおり、積層板に用いられる絶縁膜の誘電特性が無視できなくなってきた。積層板の絶縁膜の誘電特性が悪いと、信号遅延・信号減衰の原因となる。特に高周波数域では影響が顕著であり、誘電特性に優れた絶縁材料の要求が高まっている。 As electronic circuits are highly integrated, multilayer integrated circuits using laminated plates are becoming common. A laminated board is obtained by superposing metal circuits as conductors in multiple layers with an insulating film interposed therebetween. In recent years, the frequency of electric signals has been increased to improve the processing speed in electronic circuits, and the dielectric properties of insulating films used for laminated plates cannot be ignored. If the dielectric properties of the insulating film of the laminated plate are poor, it causes signal delay and signal attenuation. In particular, the influence is remarkable in a high frequency range, and the demand for an insulating material having excellent dielectric characteristics is increasing.
ここで、本発明において誘電特性の指標とする誘電率及び誘電正接について説明する。
電気信号の伝搬遅延時間は、一般的に次式で与えられる。
Ｔｄ＝Ｌ×εｒ １／２÷c
（Ｔｄ：伝搬遅延時間、Ｌ：伝搬距離、εｒ：比誘電率、ｃ：光速）
ここで「比誘電率」とは、材料の誘電率εと真空の誘電率ε０（定数）の比ε／ε０のことである。つまり、Ｌが一定（回路長が同じ）とすると、材料の誘電率が低い方が信号の伝搬遅延時間が短くなる。
Here, the dielectric constant and dielectric loss tangent, which are indices of dielectric characteristics in the present invention, will be described.
The propagation delay time of the electric signal is generally given by the following equation.
T d = L × ε r 1/2 ÷ c
(T d : propagation delay time, L: propagation distance, ε r : relative permittivity, c: speed of light)
Here, the “relative dielectric constant” is a ratio ε / ε 0 of the dielectric constant ε of the material and the dielectric constant ε 0 (constant) of the vacuum. That is, if L is constant (the circuit length is the same), the signal propagation delay time is shorter when the dielectric constant of the material is lower.
また、電子回路のように電場が常に変化する場合には、誘電率は以下のような複素関数（誘電関数）で表される。
ε（ω）＝ε’（ω）＋ε’’（ω）ｉ
（ω：電場の振動数、ｉ：虚数単位）
このとき、誘電正接（ｔａｎδ）＝ε’’／ε’と表され、虚数項ε’’（ω）は振動数ωにおける誘電損失である。誘電損失とは、電場の位相と材料の誘電分極のずれによって生じる熱エネルギーであり、ωが大きい、つまり高周波数になると誘電損失も大きくなることが知られており、誘電損失が大きいと、電気信号のエネルギーの一部が熱エネルギーに変換されて失われる。誘電正接はこのエネルギー損失の目安として用いられ、誘電正接の値が小さければ信号が減衰しにくくなる。
Further, when the electric field constantly changes as in an electronic circuit, the dielectric constant is expressed by a complex function (dielectric function) as follows.
ε (ω) = ε ′ (ω) + ε ″ (ω) i
(Ω: frequency of electric field, i: imaginary unit)
At this time, the dielectric loss tangent (tan δ) = ε ″ / ε ′ is expressed, and the imaginary term ε ″ (ω) is a dielectric loss at the frequency ω. Dielectric loss is the thermal energy generated by the difference between the phase of the electric field and the dielectric polarization of the material. It is known that the dielectric loss increases when ω is large, that is, when the frequency is high. Part of the signal energy is converted to heat energy and lost. The dielectric loss tangent is used as a measure of this energy loss. If the value of the dielectric loss tangent is small, the signal is difficult to attenuate.
以上で説明したように、本発明においては誘電率が低く、また、誘電正接が低いほど誘電特性が優れたものと評価される。 As described above, in the present invention, the lower the dielectric constant and the lower the dielectric loss tangent, the better the dielectric characteristics.
従来、誘電特性の良い材料としてはポリオレフィン系樹脂があるが、ポリオレフィン系樹脂はガラス転移温度（Ｔｇ）が低く、耐熱性に劣り、また金属との接着性が低いという問題があり、積層板用途には不適当である。 Conventionally, there are polyolefin resins as materials having good dielectric properties, but polyolefin resins have problems of low glass transition temperature (Tg), inferior heat resistance, and low adhesion to metals. Inappropriate for
Ｔｇが高く、耐熱性に優れた樹脂としてエポキシ樹脂があるが（例えば特許文献１）、ビスフェノールＡとエピハロヒドリンとを反応して得られる汎用のビスフェノールＡ型エポキシ樹脂は、吸水率が高いという欠点がある。 There is an epoxy resin as a resin having a high Tg and excellent heat resistance (for example, Patent Document 1), but a general-purpose bisphenol A type epoxy resin obtained by reacting bisphenol A and epihalohydrin has a drawback of high water absorption. is there.
一方、本発明で用いるビスフェノールＡＦとエピハロヒドリンとを反応させて得られるエポキシ樹脂（以下、「ビスフェノールＡＦ系エポキシ樹脂」と称す場合がある。）については、これを封止剤用途とする提案はなされているが（例えば特許文献２〜４）、積層板用途に必要な誘電特性を高めるための検討はなされていない。 On the other hand, with respect to an epoxy resin obtained by reacting bisphenol AF and epihalohydrin used in the present invention (hereinafter sometimes referred to as “bisphenol AF-based epoxy resin”), there is a proposal for using it as a sealant. However, for example, Patent Documents 2 to 4 have not been studied for enhancing the dielectric properties necessary for laminated plate applications.
積層板用途としては、シアネートエステル樹脂を主体とする組成物に、ビスフェノールＡＦ系エポキシ樹脂を配合した樹脂組成物を用いた銅張積層板（特許文献５）や、ビスフェノールＡＦ系エポキシ樹脂を基材に含浸させた積層板用プリプレグ（特許文献６）が提案されている。 As a laminated board application, a copper-clad laminated board (Patent Document 5) using a resin composition in which a bisphenol AF epoxy resin is blended with a composition mainly composed of a cyanate ester resin, or a bisphenol AF epoxy resin as a base material. A prepreg for a laminated plate impregnated in (Patent Document 6) has been proposed.
しかしながら、特許文献５及び６に記載された積層板用途の材料ではあるものの、その誘電特性は十分ではない。 However, although it is a material for laminates described in Patent Documents 5 and 6, its dielectric properties are not sufficient.
本発明は上記従来の問題点を解決し、積層板用途として使用する際に重要となる誘電特性が特に優れ、Ｔｇが高く耐熱性に優れ、吸水率が低い積層板用エポキシ樹脂組成物を提供することを課題とする。本発明はまた、この積層板用エポキシ樹脂組成物を用いた積層板及び集積回路を提供することを課題とする。 The present invention solves the above-mentioned conventional problems, and provides an epoxy resin composition for laminates that has particularly excellent dielectric properties, high Tg, excellent heat resistance, and low water absorption when used as a laminate application. The task is to do. Another object of the present invention is to provide a laminated board and an integrated circuit using the epoxy resin composition for laminated boards.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、ビスフェノールＡＦとエピハロヒドリンとを特定のモル比率で反応させて得られるエポキシ樹脂と特定のエポキシ樹脂硬化剤とを含むエポキシ樹脂組成物が、誘電特性が特に優れ、吸水率が低く、また、耐熱性にも優れることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have obtained an epoxy resin composition comprising an epoxy resin obtained by reacting bisphenol AF and epihalohydrin at a specific molar ratio and a specific epoxy resin curing agent. It was found that the product has particularly excellent dielectric properties, low water absorption, and excellent heat resistance.
本発明は、このような知見に基いて達成されたものであり、以下を要旨とする。 The present invention has been achieved based on such knowledge, and the gist thereof is as follows.
［１］ 下記成分（Ａ）及び成分（Ｂ）を含有してなる、積層板用エポキシ樹脂組成物。
成分（Ａ）：下記式（１）で表されるビスフェノール化合物とエピハロヒドリンとを反応して得られるエポキシ樹脂であって、下記式（１）で表されるビスフェノール化合物１モルに対して、エピハロヒドリン１．２５〜４．８０モルを反応させてなるエポキシ樹脂
成分（Ｂ）：フェノール系エポキシ樹脂硬化剤及び／又はジシアンジアミド系エポキシ樹脂硬化剤
[1] An epoxy resin composition for laminates comprising the following component (A) and component (B).
Component (A): An epoxy resin obtained by reacting a bisphenol compound represented by the following formula (1) with an epihalohydrin, and the epihalohydrin is used per 1 mol of the bisphenol compound represented by the following formula (1) Epoxy resin component (B) obtained by reacting 1.25 to 4.80 mol: phenolic epoxy resin curing agent and / or dicyandiamide epoxy resin curing agent
［２］ 前記成分（Ａ）の軟化点が１２０℃以下である、［１］に記載の積層板用エポキシ樹脂組成物。 [ 2 ] The epoxy resin composition for laminated boards according to [1 ], wherein the softening point of the component (A) is 120 ° C. or lower.
［３］ ［１］又は［２］に記載の積層板用エポキシ樹脂組成物を含む層と、導電性金属層とを有する積層板。 [ 3 ] A laminate having a layer containing the epoxy resin composition for laminates according to [1] or [ 2] and a conductive metal layer.
［４］ ［３］に記載の積層板からなる集積回路。 [ 4 ] An integrated circuit comprising the laminate according to [ 3 ].
本発明によれば、積層板用途として使用する際に重要となる誘電特性が特に優れ、Ｔｇが高く耐熱性に優れ、吸水率が低い積層板用エポキシ樹脂組成物と、これを用いた高性能の積層板及び集積回路が提供される。 According to the present invention, an epoxy resin composition for a laminated board having excellent dielectric characteristics, which is important when used as a laminated board, excellent Tg, excellent heat resistance, and low water absorption, and a high performance using the same. Laminates and integrated circuits are provided.
以下に本発明の実施の形態を詳細に説明するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。なお、本明細書において「〜」という表現を用いる場合、その前後の数値または物性値を含む表現として用いるものとする。 Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.
１．積層板用エポキシ樹脂組成物
本発明の積層板用エポキシ樹脂組成物（以下、「本発明のエポキシ樹脂組成物」と称す場合がある。）は、下記成分（Ａ）及び成分（Ｂ）を含有することを特徴とする。
成分（Ａ）：下記式（１）で表されるビスフェノール化合物とエピハロヒドリンとを反応して得られるエポキシ樹脂であって、式（１）で表されるビスフェノール化合物の水酸基１モルに対して、エピハロヒドリン１．００〜４．８０モルを反応させてなるエポキシ樹脂（以下、「エポキシ樹脂（Ａ）」と称す場合がある。）
成分（Ｂ）：フェノール系エポキシ樹脂硬化剤及び／又はジシアンジアミド系エポキシ樹脂硬化剤（以下、「エポキシ樹脂硬化剤（Ｂ）」と称す場合がある。）
1. The epoxy resin composition for laminated boards The epoxy resin composition for laminated boards of the present invention (hereinafter sometimes referred to as "the epoxy resin composition of the present invention") contains the following components (A) and (B). It is characterized by doing.
Component (A): An epoxy resin obtained by reacting a bisphenol compound represented by the following formula (1) with an epihalohydrin, and the epihalohydrin with respect to 1 mol of the hydroxyl group of the bisphenol compound represented by the formula (1) Epoxy resin obtained by reacting 1.00 to 4.80 moles (hereinafter sometimes referred to as “epoxy resin (A)”).
Component (B): Phenolic epoxy resin curing agent and / or dicyandiamide epoxy resin curing agent (hereinafter sometimes referred to as “epoxy resin curing agent (B)”)
［成分（Ａ）］
本発明のエポキシ樹脂組成物に用いるエポキシ樹脂（Ａ）は、下記式（１）で表される２，２−ビス（４−ヒドロキシフェニル）ヘキサフルオロプロパン（以下「ビスフェノール（１）」と称す場合がある。）とエピハロヒドリンとを反応して得られるエポキシ樹脂であって、ビスフェノール（１）１モルに対して、エピハロヒドリンを１．００〜４．８０モル反応させてなることを特徴とする（以下において、この反応モル比を「エピハロヒドリン／ビスフェノール（１）比」と称す場合がある。）。
[Component (A)]
The epoxy resin (A) used in the epoxy resin composition of the present invention is referred to as 2,2-bis (4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as “bisphenol (1)”) represented by the following formula (1): And an epihalohydrin, which is obtained by reacting 1.00 to 4.80 moles of epihalohydrin with respect to 1 mole of bisphenol (1 ) In this case, this reaction molar ratio is sometimes referred to as “epihalohydrin / bisphenol (1) ratio”).
＜エピハロヒドリン／ビスフェノール（１）比＞
エピハロヒドリン／ビスフェノール（１）比が１．００より小さいと、得られるエポキシ樹脂の軟化点が高くなり、エポキシ樹脂を配合して組成物を作成する際、エポキシ樹脂硬化剤と混合させるために高温にする必要があり、その際エポキシ樹脂硬化剤の揮発による配合比率のズレの発生や、高温下であることによる作業環境悪化の問題がある。一方、エピハロヒドリン／ビスフェノール（１）比が４．８０以下であることにより、誘電特性が非常に優れたものとなる。
<Epihalohydrin / bisphenol (1) ratio>
When the epihalohydrin / bisphenol (1) ratio is less than 1.00, the softening point of the resulting epoxy resin is increased, and when the composition is prepared by blending the epoxy resin, the epoxy resin curing agent is mixed at a high temperature. In this case, there is a problem of deviation of the blending ratio due to volatilization of the epoxy resin curing agent and deterioration of the working environment due to high temperature. On the other hand, when the epihalohydrin / bisphenol (1) ratio is 4.80 or less, the dielectric properties are very excellent.
エピハロヒドリン／ビスフェノール（１）比は、好ましくは、１．１０以上、より好ましくは１．２０以上、更に好ましくは１．２５以上であり、一方、好ましくは４．５０以下、より好ましくは４．００以下、更に好ましくは３．５０以下である。エピハロヒドリン／ビスフェノール（１）比が、上記下限値以上であることが、得られるエポキシ樹脂の軟化点を取り扱いに適した軟化点とするために好ましく、一方、上記上限値以下で小さい程誘電特性が優れたものとなる傾向にある。 The epihalohydrin / bisphenol (1) ratio is preferably 1.10 or more, more preferably 1.20 or more, still more preferably 1.25 or more, while preferably 4.50 or less, more preferably 4.00. Hereinafter, it is more preferably 3.50 or less. The epihalohydrin / bisphenol (1) ratio is preferably equal to or higher than the above lower limit value in order to make the softening point of the resulting epoxy resin suitable for handling. On the other hand, the smaller the value below the upper limit value, the more the dielectric characteristics. It tends to be excellent.
＜軟化点＞
本発明に用いるエポキシ樹脂（Ａ）の軟化点は、１２０℃以下であることが好ましく、特に４０〜１２０℃であることが好ましい。エポキシ樹脂（Ａ）の軟化点が１２０℃以下であると、他のエポキシ樹脂やエポキシ樹脂硬化剤と配合する際、前述したような配合比のズレが生じにくく、また、取り扱い性、作業性が良好となるために好ましい。エポキシ樹脂（Ａ）の軟化点が４０℃以上であると、エポキシ樹脂が融着するブロッキングが起こりにくく、常温での取り扱い性が良好となる傾向にある。
なお、エポキシ樹脂の軟化点は、後掲の実施例の項に記載される方法で測定される。
<Softening point>
The softening point of the epoxy resin (A) used in the present invention is preferably 120 ° C. or less, and particularly preferably 40 to 120 ° C. When the epoxy resin (A) has a softening point of 120 ° C. or less, when blended with another epoxy resin or an epoxy resin curing agent, the above-described misalignment of the blending ratio is difficult to occur, and handling properties and workability are improved. It is preferable because it becomes good. When the softening point of the epoxy resin (A) is 40 ° C. or higher, blocking that the epoxy resin is fused hardly occurs, and the handleability at room temperature tends to be good.
In addition, the softening point of an epoxy resin is measured by the method described in the item of an Example mentioned later.
＜エポキシ当量＞
本発明のエポキシ樹脂のエポキシ当量については特に制限はないが、２２０ｇ／当量以上が好ましく、２４０ｇ／当量以上がより好ましく、２６０ｇ／当量以上が更に好ましく、３００ｇ／当量以上が特に好ましく、一方、１５００ｇ／当量以下が好ましく、１２００ｇ／当量以下がより好ましく、９００ｇ／当量以下が更に好ましい。エポキシ当量が上記範囲であると、取り扱い性、作業性が良好となる。エポキシ当量は前述したエピハロヒドリン／ビスフェノール（１）比や触媒の種類、反応条件等の条件により制御することができる。
なお、本発明において、エポキシ当量とは、１当量のエポキシ基を含むエポキシ樹脂の質量を意味し、エポキシ当量は、後掲の実施例の項に記載される方法で測定される。
<Epoxy equivalent>
Although there is no restriction | limiting in particular about the epoxy equivalent of the epoxy resin of this invention, 220 g / equivalent or more is preferable, 240 g / equivalent or more is more preferable, 260 g / equivalent or more is further more preferable, 300 g / equivalent or more is especially preferable, 1500 g / Equivalent or less, preferably 1200 g / equivalent or less, more preferably 900 g / equivalent or less. When the epoxy equivalent is in the above range, the handleability and workability are good. The epoxy equivalent can be controlled by the above-described epihalohydrin / bisphenol (1) ratio, the type of catalyst, the reaction conditions, and the like.
In addition, in this invention, an epoxy equivalent means the mass of the epoxy resin containing 1 equivalent of epoxy groups, and an epoxy equivalent is measured by the method described in the term of the below-mentioned Example.
＜全塩素含有量＞
本発明に用いるエポキシ樹脂（Ａ）は、特に電気・電子部品に用いる場合、全塩素含有量が０．２質量％以下であることが好ましい。全塩素含有量が０．２質量％を超えると、銅やアルミニウム等の金属材料の腐食が発生することがある。全塩素含有量の下限については特に制限はないが、０．０１質量％未満に低減することは、それ以上の全塩素含有量低減の効果がさほど期待できない上に特殊な低減工程を要するために経済性が損なわれる。
なお、エポキシ樹脂の全塩素含有量は、後掲の実施例の項に記載される方法で測定される。
<Total chlorine content>
The epoxy resin (A) used in the present invention preferably has a total chlorine content of 0.2% by mass or less, particularly when used for electric / electronic parts. When the total chlorine content exceeds 0.2% by mass, corrosion of metal materials such as copper and aluminum may occur. There is no particular limitation on the lower limit of the total chlorine content, but reducing it to less than 0.01% by mass cannot be expected to reduce the total chlorine content further, and requires a special reduction process. Economic efficiency is impaired.
The total chlorine content of the epoxy resin is measured by the method described in the Examples section below.
＜エポキシ樹脂（Ａ）の製造方法＞
本発明に用いるエポキシ樹脂（Ａ）は、ビスフェノール（１）１モルに対し、エピハロヒドリンを、１．００〜４．８０モル、好ましくは１．１０〜４．５０モル、更に好ましくは１．２０〜４．００モル、特に好ましくは１．２５〜３．５０モルの割合で用いること以外は、これらを水酸化ナトリウム等のアルカリ金属水酸化物の存在下に常法に従って反応させることにより製造することができる。
<Method for producing epoxy resin (A)>
The epoxy resin (A) used for this invention is 1.00-4.80 mol with respect to 1 mol of bisphenol (1 ) , Preferably it is 1.10-4.50 mol, More preferably, it is 1.20. It is produced by reacting these in the presence of an alkali metal hydroxide such as sodium hydroxide in the usual manner except that it is used at a ratio of 4.00 mol, particularly preferably 1.25 to 3.50 mol. Can do.
具体的には、ビスフェノール（１）とエピクロルヒドリン等のエピハロヒドリンを混合し、アルカリ金属水酸化物を固体又は水溶液で加えて反応させる。この反応は常圧下、又は減圧下で行うことができ、反応温度は通常、常圧下の反応の場合は通常２０〜１５０℃であり、減圧下の反応の場合は通常３０〜８０℃である。反応は必要に応じて所定の温度を保持しながら反応液を共沸させ、揮発する蒸気を冷却して得られた凝縮液を油／水分離し、水分を除いた油分を反応系へ戻す方法により脱水しながら行われる。反応系へのアルカリ金属水酸化物の添加は、急激な反応を抑えるために、０．１〜１０時間かけて少量ずつ断続的もしくは連続的に添加することが好ましい。その全反応時間は通常１〜１５時間である。 Specifically, bisphenol (1) and epihalohydrin such as epichlorohydrin are mixed, and an alkali metal hydroxide is added as a solid or an aqueous solution to react. This reaction can be carried out under normal pressure or under reduced pressure, and the reaction temperature is usually 20 to 150 ° C. in the case of reaction under normal pressure and usually 30 to 80 ° C. in the case of reaction under reduced pressure. In the reaction, the reaction liquid is azeotroped while maintaining a predetermined temperature as required, the condensed liquid obtained by cooling the vaporized vapor is separated into oil / water, and the oil component excluding moisture is returned to the reaction system. Is performed while dehydrating. It is preferable to add the alkali metal hydroxide to the reaction system intermittently or continuously little by little over 0.1 to 10 hours in order to suppress a rapid reaction. The total reaction time is usually 1 to 15 hours.
反応終了後、不溶性の副生塩を濾別して除くか、水洗により除去した後、未反応のエピハロヒドリンを減圧留去して除くと、目的のエポキシ樹脂（Ａ）が得られる。 After completion of the reaction, the insoluble by-product salt is removed by filtration or removed by washing with water, and then the unreacted epihalohydrin is distilled off under reduced pressure to obtain the desired epoxy resin (A).
この反応におけるエピハロヒドリンとしては、通常、エピクロルヒドリン又はエピブロモヒドリンが用いられる。アルカリ金属水酸化物としては、通常、水酸化ナトリウム又は水酸化カリウムが用いられる。 As epihalohydrin in this reaction, epichlorohydrin or epibromohydrin is usually used. As the alkali metal hydroxide, sodium hydroxide or potassium hydroxide is usually used.
また、この反応のおいては、テトラメチルアンモニウムクロリド、テトラエチルアンモニウムブロミドなどの第四級アンモニウム塩；ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノールなどの第三級アミン；２−エチル−４−メチルイミダゾール、２−フェニルイミダゾールなどのイミダゾール類；エチルトリフェニルホスホニウムアイオダイドなどのホスホニウム塩；トリフェニルホスフィンなどのホスフィン類などの触媒を用いてもよい。 In this reaction, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; 2 Catalysts such as imidazoles such as ethyl-4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine may be used.
更に、この反応においては、エタノール、イソプロピルアルコールなどのアルコール類；アセトン、メチルエチルケトンなどのケトン類；ジオキサン、エチレングリコールなどのエーテル類；メトキシプロパノールなどのグリコールエーテル類；ジメチルスルホキシド、ジメチルホルムアミドなどの非プロトン性極性溶媒などの不活性な有機溶媒を使用してもよい。 Furthermore, in this reaction, alcohols such as ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol; glycol ethers such as methoxypropanol; aprotic such as dimethyl sulfoxide and dimethylformamide An inert organic solvent such as a polar solvent may be used.
また、上記のようにして得られたエポキシ樹脂（Ａ）の可鹸化ハロゲン量が多すぎる場合は、再処理して十分に可鹸化ハロゲン量が低下した精製エポキシ樹脂（Ａ）を得ることができる。この場合には、反応により得られた粗製エポキシ樹脂（Ａ）を、イソプロピルアルコール、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、ジオキサン、メトキシプロパノール、ジメチルスルホキシドなどの不活性な有機溶媒に再溶解し、アルカリ金属水酸化物を固体又は水溶液で加えて約２０〜１２０℃の温度で０．５〜８時間再閉環反応を行った後、水洗などの方法で過剰のアルカリ金属水酸化物や副生塩を除去し、更に有機溶媒を減圧留去して除くと、１段法により、精製されたエポキシ樹脂（Ａ）（ビスフェノール（１）のジグリシジルエーテル）を得ることができる。 Further, when the epoxy resin (A) obtained as described above has an excessive amount of saponifiable halogen, reprocessed epoxy resin (A) having a sufficiently reduced saponifiable halogen content can be obtained. . In this case, the crude epoxy resin (A) obtained by the reaction is redissolved in an inert organic solvent such as isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, dimethyl sulfoxide, After alkali metal hydroxide is added as a solid or aqueous solution and subjected to re-ringing reaction at a temperature of about 20 to 120 ° C. for 0.5 to 8 hours, excess alkali metal hydroxide or by-product salt is obtained by a method such as washing with water. When the organic solvent is removed by distillation under reduced pressure, a purified epoxy resin (A) (diglycidyl ether of bisphenol (1)) can be obtained by a one-stage method.
［成分（Ｂ）］
本発明のエポキシ樹脂組成物には、成分（Ｂ）のエポキシ樹脂硬化剤としてフェノール系エポキシ樹脂硬化剤及び／又はジシアンジアミド系エポキシ樹脂硬化剤が含まれる。この特定のエポキシ樹脂硬化剤（Ｂ）をエポキシ樹脂（Ａ）と組み合わせて用いることにより、積層板用途として重要な誘電特性、耐熱性、吸水性などが優れたものとなる。
[Component (B)]
The epoxy resin composition of the present invention contains a phenolic epoxy resin curing agent and / or a dicyandiamide epoxy resin curing agent as the epoxy resin curing agent of component (B). By using this specific epoxy resin curing agent (B) in combination with the epoxy resin (A), the dielectric properties, heat resistance, water absorption, etc., which are important for laminate applications, are excellent.
なお、本発明のエポキシ樹脂組成物において、全エポキシ樹脂硬化剤成分の含有量は、全エポキシ樹脂成分１００質量部に対して０．１〜８０質量部であることが好ましく、１〜７０質量部であることがより好ましく、５〜６０質量部であることが更に好ましい。なお、ここでいう「全エポキシ樹脂成分」とは、前記エポキシ樹脂（Ａ）と後述する「その他のエポキシ樹脂」との合計を意味し、また、「全エポキシ樹脂硬化剤成分」とは、エポキシ樹脂硬化剤（Ｂ）と後述する「その他のエポキシ樹脂硬化剤」との合計を意味する。 In addition, in the epoxy resin composition of this invention, it is preferable that content of all the epoxy resin hardening | curing agent components is 0.1-80 mass parts with respect to 100 mass parts of all epoxy resin components, and 1-70 mass parts. It is more preferable that it is 5-60 mass parts . The “total epoxy resin component” here means the total of the epoxy resin (A) and “other epoxy resin” described later, and the “all epoxy resin curing agent component” means an epoxy. It means the total of the resin curing agent (B) and “other epoxy resin curing agent” described later.
＜フェノール系エポキシ樹脂硬化剤＞
本発明で用いるフェノール系エポキシ樹脂硬化剤としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ビスフェノールＢ、ビスフェノールＡＤ、ビスフェノールＺ、テトラブロモビスフェノールＡ等のビスフェノール類；４，４’−ビフェノール、３，３’，５，５’−テトラメチル−４，４’−ビフェノール等のビフェノール類；カテコール、レゾルシン、ヒドロキノン、ジヒドロキシナフタレン類及び、これらの化合物のフェノール性水酸基を構成する水素原子を除く任意の水素原子が、ハロゲン基、アルキル基、アリール基、エーテル基、エステル基、硫黄、リン、珪素等のヘテロ元素を含む有機置換基等の非妨害性置換基で置換されたもの等が挙げられる。更に、これらのフェノール類やフェノール、クレゾール、アルキルフェノール等の単官能フェノール類とアルデヒド類の重縮合物であるノボラック類、例えば、フェノールノボラック、クレゾールノボラック、ビスフェノールＡノボラック等やレゾール類等が挙げられる。
エポキシ樹脂硬化剤としてフェノール系エポキシ樹脂硬化剤を用いることにより、得られるエポキシ樹脂組成物の誘電特性を特に向上させることができ好ましい。
<Phenolic epoxy resin curing agent>
Examples of the phenolic epoxy resin curing agent used in the present invention include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, and tetrabromobisphenol A; 4,4′-biphenol, 3,3 Biphenols such as', 5,5'-tetramethyl-4,4'-biphenol; catechol, resorcin, hydroquinone, dihydroxynaphthalene, and any hydrogen atom excluding the hydrogen atom constituting the phenolic hydroxyl group of these compounds Are substituted with a non-interfering substituent such as an organic substituent containing a hetero element such as a halogen group, an alkyl group, an aryl group, an ether group, an ester group, sulfur, phosphorus, or silicon. Furthermore, novolaks which are polycondensates of monofunctional phenols such as phenols, phenols, cresols, alkylphenols and aldehydes, such as phenol novolacs, cresol novolacs, bisphenol A novolacs, and resoles.
By using a phenolic epoxy resin curing agent as the epoxy resin curing agent, the dielectric properties of the resulting epoxy resin composition can be particularly improved, which is preferable.
＜ジシアンジアミド系エポキシ樹脂硬化剤＞
ジシアンジアミド系エポキシ樹脂硬化剤としてはジシアンジアミドとその誘導体が挙げられる。
エポキシ樹脂硬化剤としてジシアンジアミド系エポキシ樹脂硬化剤を用いることにより、得られるエポキシ樹脂組成物の誘電特性のみならず、耐熱性を向上させることができ特に好ましい。
<Dicyandiamide epoxy resin curing agent>
Examples of the dicyandiamide type epoxy resin curing agent include dicyandiamide and its derivatives.
By using a dicyandiamide epoxy resin curing agent as the epoxy resin curing agent, not only the dielectric properties of the resulting epoxy resin composition but also the heat resistance can be improved, which is particularly preferable.
上記フェノール系エポキシ樹脂硬化剤は、１種を単独で用いてもよく、２種以上を併用してもよい。また、上記ジシアンジアミド系エポキシ樹脂硬化剤も１種を単独で用いてもよく、２種以上を併用してもよい。また、本発明では、フェノール系エポキシ樹脂硬化剤の１種又は２種以上とジシアンジアミド系エポキシ樹脂硬化剤の１種又は２種以上を併用してもよい。 The said phenol type epoxy resin hardening | curing agent may be used individually by 1 type, and may use 2 or more types together. Moreover, the said dicyandiamide type epoxy resin hardening | curing agent may be used individually by 1 type, and may use 2 or more types together. In the present invention, one or more phenolic epoxy resin curing agents and one or more dicyandiamide epoxy resin curing agents may be used in combination.
フェノール系エポキシ樹脂硬化剤とジシアンジアミド系エポキシ樹脂硬化剤を併用する場合、その使用割合には特に制限はないが、これら２種類のエポキシ樹脂硬化剤を併用することによる誘電特性と耐熱性の向上効果を有効に得るために、これらの硬化剤における活性水素原子のモル比で、（フェノール系エポキシ樹脂硬化剤）：（ジシアンジアミド系エポキシ樹脂硬化剤）＝１：０．１〜０．９、特に１：０．３〜０．７の範囲で用いることが好ましい。ここで、「活性水素原子」とはフェノール系エポキシ樹脂硬化剤のフェノール性水酸基における水素原子とジシアンジアミド系硬化剤のアミノ基における水素原子を意味する。 When a phenolic epoxy resin curing agent and a dicyandiamide epoxy resin curing agent are used in combination, there is no particular limitation on the proportion of use, but the effect of improving dielectric properties and heat resistance by using these two types of epoxy resin curing agents in combination. In order to effectively obtain the above, the molar ratio of active hydrogen atoms in these curing agents is (phenolic epoxy resin curing agent) :( dicyandiamide epoxy resin curing agent) = 1: 0.1 to 0.9, especially 1. : It is preferable to use in the range of 0.3-0.7. Here, the “active hydrogen atom” means a hydrogen atom in the phenolic hydroxyl group of the phenolic epoxy resin curing agent and a hydrogen atom in the amino group of the dicyandiamide curing agent.
［任意成分］
本発明の積層板用エポキシ樹脂組成物には、前述のエポキシ樹脂（Ａ）以外のエポキシ樹脂（以下、「その他のエポキシ樹脂」と称することがある。）、エポキシ樹脂硬化剤（Ｂ）以外のエポキシ樹脂硬化剤（以下、「その他のエポキシ樹脂硬化剤」と称することがある。）、硬化促進剤（触媒）、エポキシ樹脂以外の硬化性樹脂、エラストマー等の熱可塑性樹脂、溶剤、酸化防止剤、サイジング剤、希釈剤、フィラーなどを含んでもよい。
[Optional ingredients]
In the epoxy resin composition for laminated boards of the present invention, an epoxy resin other than the above-mentioned epoxy resin (A) (hereinafter sometimes referred to as “other epoxy resin”), an epoxy resin curing agent (B). Epoxy resin curing agent (hereinafter sometimes referred to as "other epoxy resin curing agent"), curing accelerator (catalyst), curable resin other than epoxy resin, elastomer such as thermoplastic resin, solvent, antioxidant , Sizing agents, diluents, fillers, and the like.
＜その他のエポキシ樹脂＞
その他のエポキシ樹脂としては、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、ビスフェノールＳ型エポキシ樹脂、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、テトラブロモビスフェノールＡ型エポキシ樹脂、その他の多官能フェノール型エポキシ樹脂等のグリシジルエーテル型エポキシ樹脂、上記芳香族エポキシ樹脂の芳香環を水素添加したエポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂等のエポキシ樹脂等が挙げられる。
<Other epoxy resins>
Other epoxy resins include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin. , Glycidyl ether type epoxy resins such as tetrabromobisphenol A type epoxy resins, other polyfunctional phenol type epoxy resins, epoxy resins obtained by hydrogenating aromatic rings of the above aromatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxies Examples thereof include epoxy resins such as resins, linear aliphatic epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.
これらのその他のエポキシ樹脂は、１種を単独で用いてもよく、２種以上を併用してもよい。 These other epoxy resins may be used individually by 1 type, and may use 2 or more types together.
なお、本発明のエポキシ樹脂組成物がエポキシ樹脂（Ａ）以外のその他のエポキシ樹脂を含む場合、その含有量には特に制限はないが、本発明で用いるエポキシ樹脂（Ａ）の効果を有効に得るために、エポキシ樹脂（Ａ）１００質量部に対して、その他のエポキシ樹脂を１００質量部以下、例えば１〜８０質量部とすることが好ましい。 In addition, when the epoxy resin composition of this invention contains other epoxy resins other than an epoxy resin (A), there is no restriction | limiting in particular in the content, but the effect of the epoxy resin (A) used by this invention is effective. In order to obtain it, it is preferable to make another epoxy resin into 100 mass parts or less, for example, 1-80 mass parts with respect to 100 mass parts of epoxy resins (A).
＜その他のエポキシ樹脂硬化剤＞
成分（Ｂ）以外のその他のエポキシ樹脂硬化剤としては、エポキシ樹脂のエポキシ基を架橋しうるものであればどのようなものでもよい。例えば、アミン類、酸無水物類、チオール類、カチオン重合開始剤等が挙げられる。
<Other epoxy resin curing agents>
Any other epoxy resin curing agent other than the component (B) may be used as long as it can crosslink the epoxy group of the epoxy resin. Examples include amines, acid anhydrides, thiols, and cationic polymerization initiators.
アミン類の例としては、脂肪族の一級、二級、三級アミン、芳香族の一級、二級、三級アミン、環状アミン、グアニジン類、尿素誘導体等があり、具体的には、トリエチレンテトラミン、ジアミノジフェニルメタン、ジアミノジフェニルエーテル、メタキシレンジアミン、１，８−ジアザビシクロ（５，４，０）−７−ウンデセン、１，５−ジアザビシクロ（４，３，０）−５−ノネン、ジメチル尿素、グアニル尿素等が挙げられる。なお、本発明においては「ジシアンジアミド系硬化剤」は、その他の硬化剤としてのアミン類には分類しないものとする。 Examples of amines include aliphatic primary, secondary, tertiary amines, aromatic primary, secondary, tertiary amines, cyclic amines, guanidines, urea derivatives, etc., specifically, triethylene Tetramine, diaminodiphenylmethane, diaminodiphenyl ether, metaxylenediamine, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene, dimethylurea, guanyl Examples include urea. In the present invention, the “dicyandiamide curing agent” is not classified into amines as other curing agents.
酸無水物類の例としては、無水フタル酸、ヘキサヒドロ無水フタル酸、無水トリメリット酸、無水マレイン酸と不飽和化合物の縮合物等が挙げられる。 Examples of acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, condensates of maleic anhydride and unsaturated compounds, and the like.
カチオン重合開始剤は、熱又は活性エネルギー線照射によってカチオンを発生するものであり、芳香族オニウム塩等が挙げられる。具体的には、ＳｂＦ６ −、ＢＦ４ −、ＡｓＦ６ −、ＰＦ６ −、ＣＦ３ＳＯ３、Ｂ（Ｃ６Ｆ５）４ −等のアニオン成分とヨウ素、硫黄、窒素、リン等の原子を含む芳香族カチオン成分とからなる化合物等が挙げられる。特に、ジアリールヨードニウム塩、トリアリールスルフォニウム塩が好ましい。 Cationic polymerization initiators generate cations by heat or active energy ray irradiation, and include aromatic onium salts. Specifically, anion components such as SbF 6 − , BF 4 − , AsF 6 − , PF 6 − , CF 3 SO 3 , B (C 6 F 5 ) 4 − and atoms such as iodine, sulfur, nitrogen and phosphorus And a compound comprising an aromatic cation component containing In particular, diaryl iodonium salts and triaryl sulfonium salts are preferred.
これらのその他のエポキシ樹脂硬化剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 These other epoxy resin curing agents may be used alone or in combination of two or more.
なお、本発明において、エポキシ樹脂硬化剤として成分（Ｂ）以外のその他のエポキシ樹脂硬化剤を含む場合、その含有量には特に制限はないが、本発明で用いる成分（Ｂ）のエポキシ樹脂硬化剤の効果を有効に得るために、成分（Ｂ）のエポキシ樹脂硬化剤１００質量部に対して、その他のエポキシ樹脂硬化剤を１００質量部以下、例えば１〜８０質量部とすることが好ましい。 In addition, in this invention, when other epoxy resin hardening | curing agents other than a component (B) are included as an epoxy resin hardening | curing agent, although there is no restriction | limiting in particular, the epoxy resin hardening of the component (B) used by this invention In order to effectively obtain the effect of the agent, the amount of the other epoxy resin curing agent is preferably 100 parts by mass or less, for example, 1 to 80 parts by mass with respect to 100 parts by mass of the epoxy resin curing agent of the component (B).
＜硬化促進剤＞
本発明のエポキシ樹脂組成物には、硬化を促進する目的で、必要に応じて硬化促進剤を用いることができる。
<Curing accelerator>
In the epoxy resin composition of the present invention, a curing accelerator can be used as needed for the purpose of accelerating curing.
硬化促進剤としては、３級アミン類、イミダゾール類、有機ホスフィン化合物類又はこれらの塩類、オクチル酸亜鉛、オクチル酸スズ等の金属石鹸類といった、一般のエポキシ樹脂用硬化促進剤の１種又は２種以上を用いることができる。 As the curing accelerator, one or two of general curing accelerators for epoxy resins such as tertiary amines, imidazoles, organic phosphine compounds or salts thereof, and metal soaps such as zinc octylate and tin octylate are used. More than seeds can be used.
イミダゾール類の例としては、１−イソブチル−２−メチルイミダゾール、２−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、ベンズイミダゾール等が挙げられる。なお、イミダゾール類は先述したエポキシ樹脂硬化剤としての機能も果たすが、本発明においては硬化促進剤に分類するものとする。 Examples of imidazoles include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole and the like. . In addition, although imidazoles also fulfill | perform the function as an epoxy resin hardening | curing agent mentioned above, in this invention, it shall classify | categorize into a hardening accelerator.
硬化促進剤を配合する場合、その使用割合は本発明のエポキシ樹脂組成物中の全エポキシ樹脂成分１００質量部に対して０．０１〜１０質量部とすることが好ましい。なお、ここで、全エポキシ樹脂成分は、エポキシ樹脂（Ａ）と共に、前述のその他のエポキシ樹脂を併用する場合は、エポキシ樹脂組成物中に含まれるエポキシ樹脂（Ａ）とのその他のエポキシ樹脂との合計である。以下の酸化防止剤や任意成分の配合量においても同様である。 When mix | blending a hardening accelerator, it is preferable that the use ratio shall be 0.01-10 mass parts with respect to 100 mass parts of all the epoxy resin components in the epoxy resin composition of this invention. Here, when all the epoxy resin components are used in combination with the epoxy resin (A) and the other epoxy resins described above, other epoxy resins with the epoxy resin (A) contained in the epoxy resin composition Is the sum of The same applies to the amounts of the following antioxidants and optional components.
＜溶剤＞
本発明のエポキシ樹脂組成物には、粘度の調節やハンドリングの改善のために、必要に応じて溶剤を用いることができる。
この場合、使用できる溶剤は特に制限されるものではないが、溶解性を考慮するとケトン系溶剤、エステル系溶剤、アミド系溶剤、エーテル系溶剤、セロソルブ系溶剤、含硫黄系溶剤などが挙げられる。
<Solvent>
In the epoxy resin composition of the present invention, a solvent can be used as necessary for adjusting the viscosity and improving the handling.
In this case, the solvent that can be used is not particularly limited, but in consideration of solubility, ketone solvents, ester solvents, amide solvents, ether solvents, cellosolve solvents, sulfur-containing solvents and the like can be mentioned.
ケトン系溶剤としては、アセトン、メチルエチルケトン、ジイソプロピルケトン、メチルイソブチルケトン、シクロペンタノン、シクロペンテノン、シクロヘキサノン、シクロへキセノン、アセトフェノン、ベンジルメチルケトン、イソホロン、アセチルアセトンなどが挙げられる。
エステル系溶剤としては、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、γ−ブチロラクトンなどが挙げられる。
アミド系溶剤としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドンなどが挙げられる。
エーテル系溶剤としては、ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサンなどが挙げられる。
セロソルブ系溶剤としては、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、酢酸セロソルブなどが挙げられる。
含硫黄系溶剤としては、ジメチルスルホキシドなどが挙げられる。
Examples of the ketone solvent include acetone, methyl ethyl ketone, diisopropyl ketone, methyl isobutyl ketone, cyclopentanone, cyclopentenone, cyclohexanone, cyclohexenone, acetophenone, benzyl methyl ketone, isophorone, and acetylacetone.
Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and γ-butyrolactone.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
Examples of the ether solvent include diethyl ether, tetrahydrofuran, 1,4-dioxane and the like.
Examples of the cellosolve solvent include methyl cellosolve, ethyl cellosolve, butyl cellosolve, and cellosolve acetate.
Examples of the sulfur-containing solvent include dimethyl sulfoxide.
これらの中でも、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、Ｎ，Ｎ−ジメチルアセトアミドなどが、溶解性に優れ、適当な沸点を有することから好ましい。
これらの溶剤は、１種を単独で用いてもよく、２種以上を併用してもよい。
Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N, N-dimethylacetamide and the like are preferable because they have excellent solubility and an appropriate boiling point.
These solvents may be used alone or in combination of two or more.
また、これらの溶剤を用いて本発明のエポキシ樹脂組成物を溶液とする際の好ましい固形分濃度は加工プロセスにより異なるが、通常は１〜９９質量％、好ましくは１０〜９０質量％、更に好ましくは２０〜８５質量％である。なお、ここでいう固形分濃度とは、溶液全体の質量に対する溶剤以外の成分の質量％を表す。 Further, the preferable solid content concentration when the epoxy resin composition of the present invention is made into a solution using these solvents varies depending on the processing process, but is usually 1 to 99% by mass, preferably 10 to 90% by mass, and more preferably. Is 20-85 mass%. In addition, solid content concentration here represents the mass% of components other than a solvent with respect to the mass of the whole solution.
＜酸化防止剤＞
本発明のエポキシ樹脂組成物には、加熱時の酸化劣化を防止して、着色の少ない硬化物を得る必要がある場合には、酸化防止剤を配合してもよい。
<Antioxidant>
In the epoxy resin composition of the present invention, when it is necessary to prevent oxidative deterioration during heating and obtain a cured product with little coloration, an antioxidant may be blended.
この場合、使用できる酸化防止剤としては、フェノール系、硫黄系、リン系酸化防止剤が挙げられ、エポキシ樹脂組成物中の全エポキシ樹脂成分１００質量部に対して通常０．００５〜５質量部、好ましくは０．０１〜１質量部配合される。 In this case, examples of the antioxidant that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Usually, 0.005 to 5 parts by mass with respect to 100 parts by mass of all epoxy resin components in the epoxy resin composition. The amount is preferably 0.01 to 1 part by mass.
使用できる酸化防止剤の具体例としては、以下のようなものが挙げられる。 Specific examples of the antioxidant that can be used include the following.
（フェノール系酸化防止剤）
モノフェノール類；２，６−ジ−ｔ−ブチル−ｐ−クレゾール、ブチル化ヒドロキシアニソール、２，６−ジ−ｔ−ブチル−ｐ−エチルフェノール、ステアリル−β−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート等
(Phenolic antioxidant)
Monophenols; 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate, etc.
ビスフェノール類；２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４’−チオビス（３−メチル−６−ｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、３，９−ビス［１，１−ジメチル−２−｛β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝エチル］２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン等 Bisphenols; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-) 6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4) -Hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, etc.
高分子型フェノール類；１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、テトラキス−［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン、ビス［３，３’−ビス−（４’−ヒドロキシ−３’−ｔ−ブチルフェニル）ブチリックアシッド］グリコールエステル、１，３，５−トリス（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンジル）−Ｓ−トリアジン−２，４，６−（１Ｈ，３Ｈ，５Ｈ）トリオン、トコフェノール等 Polymeric phenols; 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3' -Bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc.
（硫黄系酸化防止剤）
ジラウリル−３，３’−チオジプロピオネート、ジミリスチル−３，３’−チオジプロピオネート、ジステアリル−３，３’−チオジプロピオネート等
(Sulfur-based antioxidant)
Dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, etc.
（リン系酸化防止剤）
ホスファイト類；トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、トリス（ノニルフェニル）ホスファイト、ジイソデシルペンタエリスリトールホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビス（オクタデシル）ホスファイト、サイクリックネオペンタンテトライルビス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビス（２，４−ジ−ｔ−ブチル−４−メチルフェニル）ホスファイト、ビス［２−ｔ−ブチル−６−メチル−４−｛２−（オクタデシルオキシカルボニル）エチル｝フェニル］ヒドロゲンホスファイト等
(Phosphorus antioxidant)
Phosphites; triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, Cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentane tetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis (2,4-di-t -Butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc.
オキサホスファフェナントレンオキサイド類；９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−デシロキシ−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド等 Oxaphosphaphenanthrene oxides; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.
これらの酸化防止剤はそれぞれ単独で使用できるが、フェノール系／硫黄系、又はフェノール系／リン系のように２種以上を組み合わせて使用することが特に好ましい。 These antioxidants can be used alone, but it is particularly preferable to use a combination of two or more types such as phenol / sulfur or phenol / phosphorus.
＜その他の成分＞
本発明のエポキシ樹脂組成物には、必要に応じて次の成分を添加配合することができる。
<Other ingredients>
In the epoxy resin composition of the present invention, the following components can be added and blended as necessary.
１）粉末状の補強剤や充填剤；例えば、酸化アルミニウム、酸化マグネシウム等の金属酸化物、微粉末シリカ、溶融シリカ、結晶シリカ等のケイ素化合物、ガラスビーズ等のフィラー、水酸化アルミニウム等の金属水酸化物、金、銀、銅、アルミニウム等の金属類、その他、カーボン、ゴム類、カオリン、マイカ、石英粉末、グラファイト、二硫化モリブデン、窒化ホウ素等 1) Powdery reinforcing agents and fillers; for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, fillers such as glass beads, and metals such as aluminum hydroxide Metals such as hydroxide, gold, silver, copper, aluminum, etc., carbon, rubber, kaolin, mica, quartz powder, graphite, molybdenum disulfide, boron nitride, etc.
これら粉末状の補強剤や充填剤の配合量は、エポキシ樹脂組成物中の全エポキシ樹脂成分１００質量部に対して、１５００質量部以下、例えば０．１〜１５００質量部が適当である。 The blending amount of these powdery reinforcing agents and fillers is suitably 1500 parts by mass or less, for example, 0.1 to 1500 parts by mass with respect to 100 parts by mass of all epoxy resin components in the epoxy resin composition.
２）着色剤又は顔料；例えば、二酸化チタン、モリブデン赤、紺青、群青、カドミウム黄、カドミウム赤、有機色素、カーボンブラック、蛍光体等
３）難燃剤；例えば、三酸化アンチモン、ブロム化合物、リン化合物等
上記２），３）の成分は、エポキシ樹脂組成物中の全エポキシ樹脂成分１００質量部に対して、各々、３０質量部以下、例えば０．０１〜３０質量部配合される。
2) Colorants or pigments; for example, titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red, organic dyes, carbon black, phosphors, etc. 3) Flame retardants; for example, antimony trioxide, bromine compounds, phosphorus compounds Etc. Each of the above components 2) and 3) is blended in an amount of 30 parts by mass or less, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of all the epoxy resin components in the epoxy resin composition.
更に、本発明のエポキシ樹脂組成物には、得られる硬化物の性質を改善する目的で種々の硬化性モノマー、オリゴマー、及び本発明のエポキシ樹脂以外の合成樹脂類を配合することができる。例えば、脂肪族モノエポキシ等のエポキシ樹脂用希釈剤、アクリル樹脂、フェノール樹脂、シリコーン樹脂等の熱硬化性樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、塩化ビニル樹脂、ナイロン樹脂、アクリル樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリイミド樹脂等の熱可塑性樹脂等の１種又は２種以上の組み合わせを挙げることができる。これらの化合物及び樹脂類の配合割合は、本発明のエポキシ樹脂組成物の本来の性質を損なわない範囲の量、即ち、本発明のエポキシ樹脂組成物１００質量部に対して、５０質量部以下が好ましい。 Furthermore, in the epoxy resin composition of the present invention, various curable monomers and oligomers and synthetic resins other than the epoxy resin of the present invention can be blended for the purpose of improving the properties of the resulting cured product. For example, diluent for epoxy resin such as aliphatic monoepoxy, thermosetting resin such as acrylic resin, phenol resin, silicone resin, polyethylene resin, polypropylene resin, polystyrene resin, vinyl chloride resin, nylon resin, acrylic resin, polyester resin 1 type, or 2 or more types of combinations, such as thermoplastic resins, such as polycarbonate resin and a polyimide resin, can be mentioned. The compounding ratio of these compounds and resins is within a range that does not impair the original properties of the epoxy resin composition of the present invention, that is, 50 parts by mass or less with respect to 100 parts by mass of the epoxy resin composition of the present invention. preferable.
２．積層板
本発明の積層板は、本発明の積層板用エポキシ樹脂組成物を含む層と導電性金属層とを含むものである。本発明の積層板としては、例えば、本発明の積層板用エポキシ樹脂組成物より得られる樹脂硬化物又は樹脂半硬化物よりなる樹脂層と導電性金属層とを交互に積層した構成としたものが挙げられる。
2. Laminate The laminate of the present invention comprises a layer containing the epoxy resin composition for a laminate of the present invention and a conductive metal layer. As a laminated board of this invention, it was set as the structure which laminated | stacked alternately the resin layer and conductive metal layer which consist of the resin cured material or resin semi-cured material obtained from the epoxy resin composition for laminated boards of this invention, for example Is mentioned.
＜樹脂硬化物・樹脂半硬化物＞
本発明のエポキシ樹脂組成物を硬化又は半硬化させて樹脂硬化物又は樹脂半硬化物とする際のエポキシ樹脂組成物の硬化方法は、エポキシ樹脂組成物中の配合成分や配合量によっても異なるが、通常、１００〜２００℃で６０〜１８０分の加熱条件が挙げられる。この加熱は１００〜１３０℃で１０〜３０分の一次加熱と、一次加熱温度よりも５０〜８０℃高い１５０〜２００℃で６０〜１５０分の二次加熱との二段処理で行うことが、硬化不良を少なくするという点で好ましい。
<Resin cured product / resin semi-cured product>
The curing method of the epoxy resin composition when the epoxy resin composition of the present invention is cured or semi-cured to obtain a resin cured product or a resin semi-cured product varies depending on the blending component and blending amount in the epoxy resin composition. Usually, the heating conditions are 60 to 180 minutes at 100 to 200 ° C. This heating may be performed by a two-stage treatment of primary heating at 100 to 130 ° C. for 10 to 30 minutes and secondary heating at 150 to 200 ° C. that is 50 to 80 ° C. higher than the primary heating temperature for 60 to 150 minutes, This is preferable from the viewpoint of reducing curing failure.
樹脂半硬化物を作製する際には、加熱等により形状が保てる程度にエポキシ樹脂組成物の硬化反応を進行させる。エポキシ樹脂組成物が溶剤を含んでいる場合には、加熱、減圧、風乾等の手法で大部分の溶剤を除去するが、樹脂半硬化物中に５質量％以下の溶剤が残留することもある。樹脂半硬化物における硬化反応の進行の程度は特に制限されないが、エポキシ基と硬化剤の硬化反応の反応率として通常５〜９５％である。 When producing the resin semi-cured product, the curing reaction of the epoxy resin composition is advanced to such an extent that the shape can be maintained by heating or the like. When the epoxy resin composition contains a solvent, most of the solvent is removed by techniques such as heating, decompression, and air drying, but a solvent of 5% by mass or less may remain in the resin semi-cured product. . The degree of progress of the curing reaction in the resin semi-cured product is not particularly limited, but the reaction rate of the curing reaction between the epoxy group and the curing agent is usually 5 to 95%.
本発明の積層板におけるこれらの樹脂硬化物又は樹脂半硬化物よりなる樹脂層の厚さは通常１０〜２００μｍ程度である。 The thickness of the resin layer made of these cured resin or semi-cured resin in the laminate of the present invention is usually about 10 to 200 μm.
＜導電性金属＞
本発明の積層板における導電性金属としては、銅、アルミニウム等の金属や、これらの金属を含む合金が挙げられる。
<Conductive metal>
Examples of the conductive metal in the laminate of the present invention include metals such as copper and aluminum, and alloys containing these metals.
本発明の積層板の導電性金属層としては、これらの金属の金属箔、あるいはメッキやスパッタリングで形成された金属層が用いられ、その厚さは通常０.２〜７０μｍ程度である。 As the conductive metal layer of the laminate of the present invention, a metal foil of these metals or a metal layer formed by plating or sputtering is used, and the thickness thereof is usually about 0.2 to 70 μm.
なお、積層板中には２種以上の樹脂硬化物層及び／又は樹脂半硬化物層が形成されていてもよく、また、２種以上の導電性金属層が形成されていてもよい。 In the laminate, two or more kinds of cured resin layers and / or semi-cured resin layers may be formed, or two or more kinds of conductive metal layers may be formed.
＜積層板の製造方法＞
本発明のエポキシ樹脂組成物の樹脂硬化物又は樹脂半硬化物よりなる樹脂層と導電性金属層とを積層してなる本発明の積層板の製造方法としては、次のような方法が挙げられる。
(1) ガラス繊維、ポリエステル繊維、アラミド繊維、セルロース、ナノファイバーセルロース等の無機及び／又は有機の繊維材料を用いた不織布やクロス等に、本発明のエポキシ樹脂組成物を含浸させてプリプレグとし、導電性金属箔及び／又はメッキにより導電性金属層を設けた後、フォトレジスト等を用いて回路を形成し、こうした層を必要数重ねて積層板とする。
(2) 上記(1)のプリプレグを心材とし、その上（片面あるいは両面）に、樹脂層と導電性金属層を積層する（ビルドアップ法）。この樹脂層は有機及び／又は無機のフィラーを含んでいてもよい。
(3) 心材を用いず、上記樹脂層と導電性金属層のみを交互に積層して積層板とする。
<Manufacturing method of laminated board>
The following method is mentioned as a manufacturing method of the laminated board of this invention formed by laminating | stacking the resin layer and conductive metal layer which consist of resin hardened | cured material or resin semi-hardened | cured material of the epoxy resin composition of this invention. .
(1) Non-woven fabric or cloth using inorganic and / or organic fiber materials such as glass fiber, polyester fiber, aramid fiber, cellulose, nanofiber cellulose, etc., impregnated with the epoxy resin composition of the present invention to form a prepreg; After providing a conductive metal layer by conductive metal foil and / or plating, a circuit is formed using a photoresist or the like, and a necessary number of such layers are stacked to form a laminate.
(2) Using the prepreg of (1) as a core material, a resin layer and a conductive metal layer are laminated on it (one side or both sides) (build-up method). This resin layer may contain an organic and / or inorganic filler.
(3) Without using a core material, only the resin layer and the conductive metal layer are alternately laminated to form a laminate.
３．集積回路
本発明の積層板は、一般的にＩＣやＬＳＩと呼ばれる集積回路用の基板として特に有効である。より具体的には、本発明の積層板は、半導体チップ（ダイ）が実装されるインターポーザ基板や、これを樹脂封止して製造されるパッケージが更に実装される基板等に有効に用いることができる。
3. Integrated Circuit The laminate of the present invention is particularly effective as a substrate for an integrated circuit generally called IC or LSI. More specifically, the laminate of the present invention is effectively used for an interposer substrate on which a semiconductor chip (die) is mounted, a substrate on which a package manufactured by resin-sealing this is further mounted, and the like. it can.
以下、実施例を用いて本発明を更に具体的に説明するが、本発明はその要旨を逸脱しない限り、以下の実施例の記載に限定されるものではない。なお、以下の実施例における各種の製造条件や評価結果の値は、本発明の実施態様における上限又は下限の好ましい値としての意味をもつものであり、好ましい範囲は前記した上限又は下限の値と、下記実施例の値又は実施例同士の値との組み合わせで規定される範囲であってもよい。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely using an Example, this invention is not limited to description of a following example, unless it deviates from the summary. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.
以下においてエポキシ樹脂及びエポキシ樹脂硬化物の物性の測定ないし特性の評価方法は次の通りである。 In the following, methods for measuring physical properties and evaluating properties of epoxy resins and cured epoxy resins are as follows.
［エポキシ樹脂のエポキシ当量］
ＪＩＳ Ｋ７２３６に準じて測定した。
[Epoxy equivalent of epoxy resin]
The measurement was performed according to JIS K7236.
［エポキシ樹脂の軟化点］
ＪＩＳ Ｋ７２３４ 環球法により測定した。
[Softening point of epoxy resin]
Measured by JIS K7234 ring and ball method.
［エポキシ樹脂の全塩素含有量］
サンプル０．１ｇをトルエン１２．５ｍｌ／ジメチルセロソルブ１２．５ｍｌの混合溶媒へ溶解し、ビフェニルナトリウム４ｍｌを添加し、室温で２分間攪拌した後、０．０１Ｎの硝酸銀溶液で滴定することにより求めた。
[Total chlorine content of epoxy resin]
0.1 g of a sample was dissolved in a mixed solvent of 12.5 ml of toluene / 12.5 ml of dimethyl cellosolve, 4 ml of biphenyl sodium was added, and the mixture was stirred at room temperature for 2 minutes and then titrated with a 0.01N silver nitrate solution. .
［エポキシ樹脂硬化物の誘電特性］
＜試験片の作製＞
縦２０ｃｍ、横２０ｃｍ、厚さ８ｍｍの軟質ガラス板の片面に離型ＰＥＴフィルムを貼り付けたものを２枚作製した。フィルムを貼り付けたガラス板１枚をフィルムが上になるように置き、その上に外径６ｍｍ、内径４ｍｍのシリコーンチューブをＵ字状に置いた。更に厚さ４ｍｍの金属製の板をガラス板の４隅に置き、あらかじめ作製したフィルムを貼り付けたもう一枚のガラス板をフィルムが下面になるように重ね合わせ、小型万力で締めて固定した。そこにエポキシ樹脂組成物を注ぎ、オーブン中にて１６０℃で１．５時間、次いで、２００℃で１．５時間硬化させて、厚さ４ｍｍのエポキシ樹脂硬化物を得た。この方法で作成した硬化物をダイヤモンドカッターで一辺５ｃｍ角にカットし、その両面に直径３.８ｃｍの円形に導電性ペースト（商品名：ドータイト、藤倉化成（株）製）を塗布した後、１３０℃で３時間乾燥させて試験片Ｉを得た。
＜誘電特性の測定＞
試験片Ｉについて、安藤電気（株）製 ＴＲ−１１００形誘電体損自動測定装置を用いて誘電率及び誘電正接を測定した。誘電率（ε）が低いほど、集積回路とした際の信号遅延時間が短くなるために好ましいものと評価し、また、誘電正接（ｔａｎδ）が低いほど、集積回路とした際の信号減衰がより少なくなるために好ましいものと評価した。具体的には、誘電率３．７０以下と誘電正接０．０３００以下とを同時に満たすことが好ましい。
[Dielectric properties of cured epoxy resin]
<Preparation of test piece>
Two sheets were prepared by attaching a release PET film to one side of a soft glass plate having a length of 20 cm, a width of 20 cm, and a thickness of 8 mm. One glass plate to which the film was attached was placed so that the film was on top, and a silicone tube having an outer diameter of 6 mm and an inner diameter of 4 mm was placed on the U-shape. Place a metal plate with a thickness of 4 mm at the four corners of the glass plate, and stack another glass plate with a pre-made film on it so that the film is on the bottom, and tighten and fix with a small vise. did. The epoxy resin composition was poured therein and cured in an oven at 160 ° C. for 1.5 hours and then at 200 ° C. for 1.5 hours to obtain a cured epoxy resin product having a thickness of 4 mm. The cured product created by this method was cut into 5 cm squares with a diamond cutter, and a conductive paste (trade name: Dotite, manufactured by Fujikura Kasei Co., Ltd.) was applied in a circular shape with a diameter of 3.8 cm on both sides. Test piece I was obtained by drying at 0 ° C. for 3 hours.
<Measurement of dielectric properties>
About the test piece I, the dielectric constant and the dielectric loss tangent were measured using TR-1100 type dielectric loss automatic measuring apparatus by Ando Electric Co., Ltd. It is evaluated that the lower the dielectric constant (ε), the shorter the signal delay time when the integrated circuit is made, and the lower the dielectric loss tangent (tan δ), the more the signal attenuation when the integrated circuit is made. Since it decreased, it evaluated as preferable. Specifically, it is preferable to satisfy the dielectric constant of 3.70 or less and the dielectric loss tangent of 0.0300 or less simultaneously.
［エポキシ樹脂硬化物の吸水率］
＜試験片の作製＞
厚さ３ｍｍのステンレス製鋼板を直径５０ｍｍの円形に打ち抜いた試験片作成用治具を使用して、この治具（鋼板）の片面に離型ＰＥＴフィルムを貼り付け、ＰＥＴフィルムを底面とする容器の状態とした。そこにエポキシ樹脂組成物を注ぎ、オーブン中にて１６０℃で１．５時間、次いで、２００℃で１．５時間硬化させて直径５０ｍｍ、厚さ３ｍｍの円盤状硬化物を得、これを試験片IIとした。
[Water absorption of cured epoxy resin]
<Preparation of test piece>
A container with a release PET film attached to one side of this jig (steel plate) using a test piece preparation jig in which a stainless steel plate with a thickness of 3 mm is punched into a circle with a diameter of 50 mm. State. The epoxy resin composition was poured therein and cured in an oven at 160 ° C. for 1.5 hours and then at 200 ° C. for 1.5 hours to obtain a disk-shaped cured product having a diameter of 50 mm and a thickness of 3 mm, which was tested. It was set as the piece II.
＜吸水率の測定＞
試験片IIを１２１℃、１００％ＲＨの恒温恒湿槽に２時間放置した後の吸水率を下記式で算出した。
（吸水率）＝［｛（１２１℃、１００％ＲＨに２時間放置後の試験片IIの質量）
−（処理前の試験片IIの質量）｝／（処理前の試験片IIの質量）］
×１００
<Measurement of water absorption rate>
The water absorption after the test piece II was left in a constant temperature and humidity chamber at 121 ° C. and 100% RH for 2 hours was calculated by the following formula.
(Water absorption rate) = [{(mass of test piece II after standing at 121 ° C., 100% RH for 2 hours)
-(Mass of specimen II before treatment)} / (mass of specimen II before treatment)]
× 100
［エポキシ樹脂組成物のガラス転移温度（Ｔｇ）］
ＳＩＩナノテクノロジー（株）製 示差走査熱量計「ＤＳＣ７０２０」を用い、３０〜２００℃まで１０℃／分で昇温して測定した。
[Glass Transition Temperature (Tg) of Epoxy Resin Composition]
Using a differential scanning calorimeter “DSC7020” manufactured by SII Nanotechnology, the temperature was increased from 30 to 200 ° C. at 10 ° C./min.
［エポキシ樹脂の製造］
＜製造例１＞
攪拌機、滴下ロート及び温度計を備えた２Ｌ容ガラス製フラスコに、ビスフェノール（１）（セントラル硝子社 商品名：Ｂｉｓ−ＡＦ（Ｈ））２００ｇ、エピクロルヒドリン８１．５ｇ（ビスフェノール（１）１モル当たり１．４８モル）、水３１６．２ｇを仕込み、予め４０℃に加熱した後２５質量％水酸化ナトリウム水溶液１５９．２ｇを０．２５時間かけて滴下しながら、１００℃まで昇温した。その後、１００℃に保ちながら０．４５時間保持し反応を完了させ、次いでメチルイソブチルケトン４５６．７ｇを加えた後、水洗により副生塩及び過剰の水酸化ナトリウムを除去した。有機層から加熱減圧によりメチルイソブチルケトンと未反応のエピクロルヒドリンを留去して、目的のエポキシ樹脂２３０ｇを得た。このエポキシ樹脂を「エポキシ樹脂Ｉ」とする。
エポキシ樹脂Ｉの分析値は、エポキシ当量；７０５ｇ／当量、軟化点；９７℃、全塩素含有量；３６０質量ｐｐｍであった。
[Manufacture of epoxy resin]
<Production Example 1>
In a 2 L glass flask equipped with a stirrer, a dropping funnel and a thermometer, 200 g of bisphenol (1) (Central Glass Co., Ltd., trade name: Bis-AF (H)), 81.5 g of epichlorohydrin (1 per mol of bisphenol (1 )) .48 mol) and 316.2 g of water were charged, heated to 40 ° C. in advance, and then heated to 100 ° C. while 159.2 g of 25% by mass aqueous sodium hydroxide solution was added dropwise over 0.25 hours. Thereafter, the reaction was completed by maintaining the temperature at 100 ° C. for 0.45 hours, and then 456.7 g of methyl isobutyl ketone was added, and then by-product salt and excess sodium hydroxide were removed by washing with water. Methyl isobutyl ketone and unreacted epichlorohydrin were distilled off from the organic layer by heating under reduced pressure to obtain 230 g of the desired epoxy resin. This epoxy resin is referred to as “epoxy resin I”.
The analytical value of the epoxy resin I was epoxy equivalent: 705 g / equivalent, softening point: 97 ° C., total chlorine content: 360 mass ppm.
＜製造例２＞
攪拌機、滴下ロート及び温度計を備えた２Ｌ容ガラス製フラスコに、ビスフェノール（１）（セントラル硝子社 商品名：Ｂｉｓ−ＡＦ（Ｈ））２００ｇ、エピクロルヒドリン９９．１ｇ（ビスフェノール（１）１モル当たり１．８０モル）、水３１６．９ｇを仕込み、予め４０℃に加熱した後２５質量％水酸化ナトリウム水溶液１９３．６ｇを０．２５時間かけて滴下しながら、１００℃まで昇温した。その後、１００℃に保ちながら０．４５時間保持し反応を完了させ、次いでメチルイソブチルケトン４７６．５ｇを加えた後、水洗により副生塩及び過剰の水酸化ナトリウムを除去した。有機層から加熱減圧によりメチルイソブチルケトンと未反応のエピクロルヒドリンを留去して、目的のエポキシ樹脂２３０ｇを得た。このエポキシ樹脂を「エポキシ樹脂II」とする。
エポキシ樹脂IIの分析値は、エポキシ当量；４６１ｇ／当量、軟化点；７０℃、全塩素含有量；６００質量ｐｐｍであった。
<Production Example 2>
In a 2 L glass flask equipped with a stirrer, a dropping funnel and a thermometer, 200 g of bisphenol (1) (Central Glass Co., Ltd., trade name: Bis-AF (H)), 99.1 g of epichlorohydrin (1 per mol of bisphenol (1 )) .80 mol) and 316.9 g of water were charged and heated in advance to 40 ° C., and then the temperature was raised to 100 ° C. while 193.6 g of 25 mass% sodium hydroxide aqueous solution was added dropwise over 0.25 hours. Thereafter, the reaction was completed by maintaining the temperature at 100 ° C. for 0.45 hours, and then 476.5 g of methyl isobutyl ketone was added, and then by-product salt and excess sodium hydroxide were removed by washing with water. Methyl isobutyl ketone and unreacted epichlorohydrin were distilled off from the organic layer by heating under reduced pressure to obtain 230 g of the desired epoxy resin. This epoxy resin is referred to as “epoxy resin II”.
The analytical value of the epoxy resin II was epoxy equivalent: 461 g / equivalent, softening point: 70 ° C., total chlorine content: 600 mass ppm.
＜製造例３＞
攪拌機、滴下ロート及び温度計を備えた５Ｌ容ガラス製フラスコに、ビスフェノール（１）（セントラル硝子社 商品名：Ｂｉｓ−ＡＦ（Ｈ））６５０ｇ、エピクロルヒドリン３７５．９ｇ（ビスフェノール（１）１モル当たり２．１モル）、水１０２９．９ｇを仕込み、予め４０℃に加熱した後２５質量％水酸化ナトリウム水溶液７３４．４ｇを０．２５時間かけて滴下しながら、１００℃まで昇温した。その後、１００℃に保ちながら０．４５時間保持し反応を完了させ、水洗により副生塩及び過剰の水酸化ナトリウムを除去した。有機層から加熱減圧により未反応のエピクロルヒドリンを留去して、粗製エポキシ樹脂を得た。この粗製エポキシ樹脂を、メチルイソブチルケトンを１３１７ｇに溶解させ、４８質量％水酸化ナトリウム水溶液１２．４ｇを加え、６５℃の温度で１時間反応させた。その後、メチルイソブチルケトン７３１．７ｇと、反応液に第一リン酸ナトリウム水溶液と水を加えて、過剰の水酸化ナトリウムを中和し、水洗して副生塩を除去した。ついで減圧下でメチルイソブチルケトンを完全に除去して、目的のエポキシ樹脂６００ｇを得た。このエポキシ樹脂を「エポキシ樹脂III」とする。
エポキシ樹脂IIIの分析値は、エポキシ当量；４０７ｇ／当量、軟化点；６５℃、全塩素含有量；６１０質量ｐｐｍであった。
<Production Example 3>
In a 5 L glass flask equipped with a stirrer, a dropping funnel and a thermometer, 650 g of bisphenol (1) (Central Glass Co., Ltd .: Bis-AF (H)), 375.9 g of epichlorohydrin (2 per mol of bisphenol (1 )) 0.1 mol) and 1029.9 g of water were charged and heated in advance to 40 ° C., and then the temperature was raised to 100 ° C. while adding 734.4 g of a 25% by mass aqueous sodium hydroxide solution over 0.25 hours. Thereafter, the reaction was completed by maintaining the temperature at 100 ° C. for 0.45 hours, and the by-product salt and excess sodium hydroxide were removed by washing with water. Unreacted epichlorohydrin was distilled off from the organic layer by heating under reduced pressure to obtain a crude epoxy resin. This crude epoxy resin was dissolved in 1317 g of methyl isobutyl ketone, 12.4 g of 48 mass% sodium hydroxide aqueous solution was added, and the mixture was reacted at a temperature of 65 ° C. for 1 hour. Thereafter, 731.7 g of methyl isobutyl ketone and an aqueous sodium phosphate solution and water were added to the reaction solution to neutralize excess sodium hydroxide and washed with water to remove by-product salts. Subsequently, methyl isobutyl ketone was completely removed under reduced pressure to obtain 600 g of the desired epoxy resin. This epoxy resin is referred to as “epoxy resin III”.
The analytical value of the epoxy resin III was epoxy equivalent: 407 g / equivalent, softening point: 65 ° C., total chlorine content: 610 mass ppm.
＜製造例４＞
攪拌機、滴下ロート及び温度計を備えた５Ｌ容ガラス製フラスコに、予め４０℃に加熱したビスフェノール（１）（セントラル硝子社 商品名：Ｂｉｓ−ＡＦ（Ｈ））２１０ｇ、イソプロピルアルコール２７０ｇ、エピクロルヒドリン６９３．８ｇ（ビスフェノール（１）１モル当たり１２．０モル）、水９６．４ｇを仕込み、４０℃に昇温して均一に溶解させた後、４８％水酸化ナトリウム水溶液１１９．８ｇを１．５時間かけて滴下した。その間に徐々に昇温し、滴下終了後には系内が６５℃になるようにした。その後、６５℃で０．５時間保持し反応を完了させ、水洗により副生塩及び過剰の水酸化ナトリウムを除去した。ついで、生成物から減圧下で過剰のエピクロルヒドリンとイソプロパノールを留去して、粗製エポキシ樹脂を得た。この粗製エポキシ樹脂を、メチルイソブチルケトンを４２０ｇに溶解させ、４８質量％水酸化ナトリウム水溶液５．９２ｇを加え、６５℃の温度で１時間反応させた。その後、反応液に第一リン酸ナトリウム水溶液を加えて、過剰の水酸化ナトリウムを中和し、水洗して副生塩を除去した。ついで減圧下でメチルイソブチルケトンを完全に除去して、目的のエポキシ樹脂２７０ｇを得た。このエポキシ樹脂を「エポキシ樹脂IV」とする。
エポキシ樹脂IVの分析値は、エポキシ当量；２３８ｇ／当量、全塩素含有量；６８０質量ｐｐｍであった。なお、エポキシ樹脂IVは常温（２５℃）で液体であったため、軟化点は測定しなかった。
<Production Example 4>
In a 5 L glass flask equipped with a stirrer, a dropping funnel and a thermometer, 210 g of bisphenol (1) (Central Glass Co., Ltd., trade name: Bis-AF (H)) preheated to 40 ° C., 270 g of isopropyl alcohol, epichlorohydrin 693. 8 g ( 12.0 mol per 1 mol of bisphenol (1 ) ) and 96.4 g of water were charged, and the mixture was heated to 40 ° C. and dissolved uniformly. Then, 119.8 g of 48% sodium hydroxide aqueous solution was added for 1.5 hours. It was dripped over. During this time, the temperature was gradually raised, and the temperature inside the system was adjusted to 65 ° C. after the dropping was completed. Thereafter, the reaction was completed by maintaining at 65 ° C. for 0.5 hour, and by-product salt and excess sodium hydroxide were removed by washing with water. Subsequently, excess epichlorohydrin and isopropanol were distilled off from the product under reduced pressure to obtain a crude epoxy resin. This crude epoxy resin was dissolved in 420 g of methyl isobutyl ketone, added with 5.92 g of a 48 mass% aqueous sodium hydroxide solution, and reacted at a temperature of 65 ° C. for 1 hour. Thereafter, an aqueous sodium phosphate solution was added to the reaction solution to neutralize excess sodium hydroxide and washed with water to remove by-product salts. Subsequently, methyl isobutyl ketone was completely removed under reduced pressure to obtain 270 g of the desired epoxy resin. This epoxy resin is referred to as “epoxy resin IV”.
The analytical value of the epoxy resin IV was epoxy equivalent: 238 g / equivalent, total chlorine content: 680 mass ppm. In addition, since the epoxy resin IV was liquid at normal temperature (25 degreeC), the softening point was not measured.
［エポキシ樹脂組成物の調製及び評価］
＜実施例１〜４、比較例１〜３＞
成分（Ａ）のエポキシ樹脂又はその他のエポキシ樹脂と成分（Ｂ）のエポキシ樹脂硬化剤（Ｂ）を表−１に示す組成で配合して、表−１に示す温度で均一になるまで混合し、続いて硬化促進剤を添加し、撹拌、溶解してエポキシ樹脂組成物を得、前述の評価を行った。結果を表−１に示す。
[Preparation and Evaluation of Epoxy Resin Composition]
<Examples 1-4, Comparative Examples 1-3>
Blend the epoxy resin of component (A) or other epoxy resin and the epoxy resin curing agent (B) of component (B) in the composition shown in Table-1 and mix until uniform at the temperature shown in Table-1. Subsequently, a curing accelerator was added, stirred and dissolved to obtain an epoxy resin composition, and the above-described evaluation was performed. The results are shown in Table-1.
［考察］
表−１の結果から次のことが分かる。
実施例１〜４は、ビスフェノール（１）を原料としないエポキシ樹脂を用いた比較例１と比べて、誘電率が低く、誘電正接が小さいことから誘電特性が良好であり、吸水率も低く、更にＴｇが高いことから耐熱性に優れることが分かる。
ビスフェノール（１）を原料としても、エピハロヒドリン／ビスフェノール（１）比が大きく、低エポキシ当量のエポキシ樹脂であるエポキシ樹脂IVを用いた比較例２は、Ｔｇは高かったものの、誘電率が高く、吸水率もやや高かった。また、エポキシ樹脂IVはエポキシ当量が小さいので、完全硬化させるためには実施例１〜４と比べて硬化剤が多く必要であるため、エポキシ樹脂の配合比率が低下し、本発明のエポキシ樹脂が本来有する低誘電率、低誘電正接の性能を十分に発揮できない。
比較例３は比較例２と同程度のエポキシ当量を有するビスフェノールＡ型エポキシ樹脂を用いたものであるが、誘電正接が非常に高かった。このため、架橋密度は実施例１〜４より高いものと考えられるが、Ｔｇは実施例１〜４の方が高かった。
[Discussion]
The following can be understood from the results of Table-1.
Examples 1 to 4 have a low dielectric constant and a low dielectric loss tangent compared to Comparative Example 1 using an epoxy resin that does not use bisphenol (1) as a raw material. Furthermore, since Tg is high, it turns out that it is excellent in heat resistance.
Comparative Example 2 using Epoxy Resin IV which is an epoxy resin having a large epihalohydrin / bisphenol (1) and having a low epoxy equivalent even when bisphenol (1) is used as a raw material has a high dielectric constant and water absorption although it has a high Tg. The rate was also slightly higher. Moreover, since epoxy resin IV has a small epoxy equivalent, it requires a larger amount of curing agent than Examples 1 to 4 for complete curing, so the blending ratio of the epoxy resin is reduced and the epoxy resin of the present invention is reduced. The inherent low dielectric constant and low dielectric loss tangent performance cannot be fully exhibited.
In Comparative Example 3, a bisphenol A type epoxy resin having an epoxy equivalent to that of Comparative Example 2 was used, but the dielectric loss tangent was very high. For this reason, although it is thought that a crosslinking density is higher than Examples 1-4, Tg was higher in Examples 1-4.
以上より、本発明のエポキシ樹脂組成物は、Ｔｇをある程度高温に保持しながら、非常に優れた誘電特性と低い吸水率を実現できることが分かる。 From the above, it can be seen that the epoxy resin composition of the present invention can achieve very good dielectric properties and low water absorption while maintaining Tg at a certain high temperature.
Claims (4)
成分（Ａ）：下記式（１）で表されるビスフェノール化合物とエピハロヒドリンとを反応して得られるエポキシ樹脂であって、式（１）で表されるビスフェノール化合物１モルに対して、エピハロヒドリン１．２５〜４．８０モルを反応させてなるエポキシ樹脂
成分（Ｂ）：フェノール系エポキシ樹脂硬化剤及び／又はジシアンジアミド系エポキシ樹脂硬化剤
Component (A): An epoxy resin obtained by reacting a bisphenol compound represented by the following formula (1) with an epihalohydrin, and an epihalohydrin 1 per mole of the bisphenol compound represented by the formula (1) Epoxy resin component (B) obtained by reacting .25 to 4.80 mol: phenolic epoxy resin curing agent and / or dicyandiamide epoxy resin curing agent
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