JP6259557B2 - Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same - Google Patents
Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same Download PDFInfo
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- JP6259557B2 JP6259557B2 JP2012149847A JP2012149847A JP6259557B2 JP 6259557 B2 JP6259557 B2 JP 6259557B2 JP 2012149847 A JP2012149847 A JP 2012149847A JP 2012149847 A JP2012149847 A JP 2012149847A JP 6259557 B2 JP6259557 B2 JP 6259557B2
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- Japan
- Prior art keywords
- thermosetting resin
- group
- resin composition
- printed wiring
- component
- 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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- 229920001187 thermosetting polymer Polymers 0.000 title claims description 47
- 239000011342 resin composition Substances 0.000 title claims description 43
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 33
- -1 maleimide compound Chemical class 0.000 claims description 25
- 229920001296 polysiloxane Polymers 0.000 claims description 22
- 125000003277 amino group Chemical group 0.000 claims description 21
- 150000001412 amines Chemical class 0.000 claims description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 31
- 239000003822 epoxy resin Substances 0.000 description 28
- 229920000647 polyepoxide Polymers 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 239000011889 copper foil Substances 0.000 description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 239000000758 substrate Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 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 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- 229940018563 3-aminophenol Drugs 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- ODRWPDDLSGNZMY-UHFFFAOYSA-N 1-[3-(4-ethylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1=CC(CC)=CC=C1OC1=CC=CC(N2C(C=CC2=O)=O)=C1 ODRWPDDLSGNZMY-UHFFFAOYSA-N 0.000 description 2
- IKFPAKYBSYICFK-UHFFFAOYSA-N 1-[4-(4-propylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 IKFPAKYBSYICFK-UHFFFAOYSA-N 0.000 description 2
- GUIACFHOZIQGKX-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenyl]sulfonylphenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=C1 GUIACFHOZIQGKX-UHFFFAOYSA-N 0.000 description 2
- MPLHZTWRCINWPX-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]disulfanyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1SSC1=CC=C(N2C(C=CC2=O)=O)C=C1 MPLHZTWRCINWPX-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 2
- PDCMTKJRBAZZHL-UHFFFAOYSA-N 5-aminobenzene-1,3-diol Chemical compound NC1=CC(O)=CC(O)=C1 PDCMTKJRBAZZHL-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229920005992 thermoplastic resin Polymers 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 125000006839 xylylene group Chemical group 0.000 description 2
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- KFBZIELKVXTTIX-UHFFFAOYSA-N 1-[3-(4-propylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1(C=CC(N1C=1C=C(OC2=CC=C(C=C2)CCC)C=CC=1)=O)=O KFBZIELKVXTTIX-UHFFFAOYSA-N 0.000 description 1
- MBNMVPPPCZKPIJ-UHFFFAOYSA-N 1-[3-[3-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(OC=2C=C(OC=3C=C(C=CC=3)N3C(C=CC3=O)=O)C=CC=2)=C1 MBNMVPPPCZKPIJ-UHFFFAOYSA-N 0.000 description 1
- JATBSJBWOJWDLM-UHFFFAOYSA-N 1-[3-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C1(C=CC(N1C=1C=C(OC2=CC=C(C=C2)C(C(F)(F)F)C(F)(F)F)C=CC=1)=O)=O JATBSJBWOJWDLM-UHFFFAOYSA-N 0.000 description 1
- FKHUSFNOGXJJRH-UHFFFAOYSA-N 1-[3-[4-[2-[4-[2-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(C(C)(C)C=2C=CC(OC=3C=C(C=CC=3)N3C(C=CC3=O)=O)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=1)=CC=CC=1N1C(=O)C=CC1=O FKHUSFNOGXJJRH-UHFFFAOYSA-N 0.000 description 1
- DAHSSGJLGBHPBZ-UHFFFAOYSA-N 1-[3-[4-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(C=CC=3)N3C(C=CC3=O)=O)=CC=2)=C1 DAHSSGJLGBHPBZ-UHFFFAOYSA-N 0.000 description 1
- DWJYMIWBPJIVFF-UHFFFAOYSA-N 1-[3-[4-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]sulfanylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(OC=2C=CC(SC=3C=CC(OC=4C=C(C=CC=4)N4C(C=CC4=O)=O)=CC=3)=CC=2)=C1 DWJYMIWBPJIVFF-UHFFFAOYSA-N 0.000 description 1
- PYEMBNRNLTZWBY-UHFFFAOYSA-N 1-[3-[4-[4-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]sulfinylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(OC=2C=CC(=CC=2)S(=O)C=2C=CC(OC=3C=C(C=CC=3)N3C(C=CC3=O)=O)=CC=2)=C1 PYEMBNRNLTZWBY-UHFFFAOYSA-N 0.000 description 1
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- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、絶縁性や耐熱性、低熱膨張性等を有するとともに、特に耐薬品性に優れ、電子部品等に用いられる熱硬化性樹脂組成物、及びこれを用いたプリプレグ、積層板、プリント配線板に関する。 The present invention has an insulating property, heat resistance, low thermal expansion property, etc., and is particularly excellent in chemical resistance, and is a thermosetting resin composition used for electronic parts and the like, and a prepreg, a laminate, and a printed wiring using the same. Regarding the board.
近年の電子機器の小型化・高性能化の流れに伴い、プリント配線板では配線密度の高度化、高集積化が進展し、これにともなって、プリント配線板用積層板の耐熱性の向上による信頼性向上への要求が強まっている。このような用途においては、優れた耐熱性、低線膨張係数を兼備することが要求されている。 Along with the recent trend toward miniaturization and higher performance of electronic devices, the wiring density of printed wiring boards has become increasingly sophisticated and highly integrated. With this, the heat resistance of laminated boards for printed wiring boards has been improved. There is an increasing demand for improved reliability. In such applications, it is required to combine excellent heat resistance and a low linear expansion coefficient.
プリント配線板用積層板としては、エポキシ樹脂を主剤とした樹脂組成物とガラス織布とを硬化・一体成形したものが一般的である。一般にエポキシ樹脂は、絶縁性や耐熱性、コスト等のバランスに優れるが、近年のプリント配線板の高密度実装、高多層化構成にともなう耐熱性向上への要求に対応するには、どうしてもその耐熱性の上昇には限界がある。さらに、熱膨張率が大きいため、芳香環を有するエポキシ樹脂の選択やシリカ等の無機充填材を高充填化することで低熱膨張化を図っている(特許文献1参照)。 As a laminated board for a printed wiring board, one obtained by curing and integrally molding a resin composition mainly composed of an epoxy resin and a glass woven fabric is generally used. In general, epoxy resins have a good balance of insulation, heat resistance, cost, etc. However, in order to meet the demands for improved heat resistance due to recent high-density mounting of printed wiring boards and multi-layered structures, the heat resistance is unavoidable. There is a limit to the increase in sex. Furthermore, since the coefficient of thermal expansion is large, low thermal expansion is achieved by selecting an epoxy resin having an aromatic ring or by highly filling an inorganic filler such as silica (see Patent Document 1).
特に近年、半導体用パッケージ基板では、小型化、薄型化に伴い、部品実装時やパッケージ組み立て時において、チップと基板との熱膨張係数の差に起因した反りが大きな課題となっており、低熱膨張化が求められているが、充填量を増やすことは吸湿による絶縁信頼性の低下や樹脂−配線層の密着不足、プレス成形不良を起こすことが知られている。 Particularly in recent years, with semiconductor package substrates, warping due to the difference in coefficient of thermal expansion between the chip and the substrate has become a major issue at the time of component mounting and package assembly due to downsizing and thinning. However, increasing the filling amount is known to cause a decrease in insulation reliability due to moisture absorption, insufficient adhesion of the resin-wiring layer, and poor press molding.
さらに、基板の薄型化により微細な回路形成に適応できる材料が求められており、ドリル加工あるいはレーザ加工後にめっきを行なった際のショート不良やオープン不良が生じているため、樹脂の耐薬品性向上が強く求められている。 In addition, there is a need for materials that can be applied to fine circuit formation by reducing the thickness of the substrate, and there is a short-circuit failure or open failure when plating is performed after drilling or laser processing, which improves the chemical resistance of the resin. Is strongly demanded.
本発明の目的は、こうした現状に鑑み、特に銅箔接着強度、高耐薬品性、はんだ耐熱性、高耐熱性、低熱膨張性に優れる樹脂組成物、及びこれを用いたプリプレグ、積層板、プリント配線板を提供することである。 In view of the current situation, the object of the present invention is to provide a resin composition excellent in copper foil adhesive strength, high chemical resistance, solder heat resistance, high heat resistance, low thermal expansion, and a prepreg, laminate, and print using the same. It is to provide a wiring board.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、ポリビスマレイミド樹脂とアミノ基を有するアミン当量500以上2300以下のシリコーン樹脂を含有する樹脂組成物が上記目的に沿うものであることを見出した。
すなわち、本発明は、以下の熱硬化性樹脂組成物、プリプレグ積層板及びプリント配線板を提供する。
As a result of intensive studies to achieve the above object, the present inventors have found that a resin composition containing a polybismaleimide resin and a silicone resin having an amino group with an amine equivalent of 500 to 2300 meets the above object. I found out.
That is, the present invention provides the following thermosetting resin composition, prepreg laminate, and printed wiring board.
1.(a)1分子構造中に少なくとも2個のN−置換マレイミド基を有するマレイミド化合物と、(b)1分子構造中に少なくとも1個のアミノ基を有する、アミン当量500以上2300以下のシリコーン化合物を含有することを特徴とする熱硬化性樹脂組成物。
2.さらに、(c)分子構造中にフェノール性水酸基を有する化合物を含有する上記1に記載の熱硬化性樹脂組成物。
3.さらに、(d)熱硬化性樹脂を含有する上記1又は2に記載の熱硬化性樹脂組成物。
4.(b)成分が、アミン当量600以上1600以下のシリコーン化合物である上記1〜3のいずれかに記載の熱硬化性樹脂組成物。
5.(b)成分が、1分子構造中に少なくとも2個のアミノ基を有するシリコーン化合物である上記1〜4のいずれかに記載の熱硬化性樹脂組成物。
6.(b)成分が、両末端にアミノ基を有するシリコーン化合物である上記1〜4のいずれかに記載の熱硬化性樹脂組成物。
7.(b)成分が、どちらか一方の末端にアミノ基を有するシリコーン化合物である上記1〜4のいずれかに記載の熱硬化性樹脂組成物。
8.(c)成分が、分子構造中にアミノ基とフェノール性水酸基を有する化合物である上記2〜7のいずれかに記載の熱硬化性樹脂組成物。
9.(c)成分が、多官能フェノール性樹脂である上記2〜8のいずれかに記載の熱硬化性樹脂組成物。
10.(d)成分が、分子構造中にエポキシ基および/又はシアネート基を有する熱硬化性樹脂である上記3〜9のいずれかに記載の熱硬化性樹脂組成物。
11.さらに、下記一般式(1)又は(2)で表される(e)硬化促進剤を含有する上記1〜10のいずれかに記載の熱硬化性樹脂組成物。
1. (A) a maleimide compound having at least two N-substituted maleimide groups in one molecular structure; and (b) a silicone compound having an amine equivalent of 500 to 2300 having at least one amino group in one molecular structure. A thermosetting resin composition characterized by containing.
2. Furthermore, (c) The thermosetting resin composition of said 1 containing the compound which has a phenolic hydroxyl group in molecular structure.
3. Furthermore, (d) The thermosetting resin composition according to the above 1 or 2, which contains a thermosetting resin.
4). (B) The thermosetting resin composition according to any one of 1 to 3, wherein the component is a silicone compound having an amine equivalent of 600 to 1600.
5. (B) The thermosetting resin composition according to any one of the above 1 to 4, wherein the component is a silicone compound having at least two amino groups in one molecular structure.
6). (B) The thermosetting resin composition according to any one of 1 to 4, wherein the component is a silicone compound having amino groups at both ends.
7). (B) The thermosetting resin composition according to any one of the above 1 to 4, wherein the component is a silicone compound having an amino group at one terminal.
8). (C) The thermosetting resin composition according to any one of 2 to 7 above, wherein the component is a compound having an amino group and a phenolic hydroxyl group in the molecular structure.
9. (C) The thermosetting resin composition in any one of said 2-8 whose component is polyfunctional phenolic resin.
10. (D) The thermosetting resin composition according to any one of 3 to 9, wherein the component is a thermosetting resin having an epoxy group and / or a cyanate group in the molecular structure.
11. Furthermore, the thermosetting resin composition in any one of said 1-10 containing the (e) hardening accelerator represented by the following general formula (1) or (2).
12.さらに、(f)無機充填材を含有する上記1〜11のいずれかに記載の熱硬化性樹脂組成物。
13.上記1〜12のいずれかに記載の熱硬化性樹脂組成物を用いたプリプレグ。
14.上記13に記載のプリプレグを用いて積層成形して得られた積層板。
15.上記14に記載の積層板を用いて製造されたプリント配線板。
12 Furthermore, (f) The thermosetting resin composition in any one of said 1-11 containing an inorganic filler.
13. The prepreg using the thermosetting resin composition in any one of said 1-12.
14 14. A laminate obtained by laminate molding using the prepreg as described in 13 above.
15. 15. A printed wiring board produced using the laminate as described in 14 above.
本発明の熱硬化性樹脂組成物を基材に含浸又は塗工して得たプリプレグ、及び該プリプレグを積層形成することにより製造した積層板、及び該積層板を用いて製造した多層プリント配線板は、銅箔接着強度、高ガラス転移温度、低熱膨張性、はんだ耐熱性、耐薬品性に優れ、電子機器用プリント配線板として有用である。 Prepreg obtained by impregnating or coating base material with thermosetting resin composition of the present invention, laminate produced by laminating the prepreg, and multilayer printed wiring board produced using the laminate Is excellent in copper foil adhesive strength, high glass transition temperature, low thermal expansion, solder heat resistance, and chemical resistance, and is useful as a printed wiring board for electronic equipment.
以下、本発明について詳細に説明する。
本発明は、下記構成を有する熱硬化性樹脂組成物、プリプレグ、積層板、及びプリント配線板に関する。
Hereinafter, the present invention will be described in detail.
The present invention relates to a thermosetting resin composition, a prepreg, a laminate, and a printed wiring board having the following configurations.
本発明の熱硬化性樹脂組成物における(a)成分の1分子中に少なくとも2個のN−置換マレイミド基を有するマレイミド化合物としては、例えば、N,N'−エチレンビスマレイミド、N,N'−ヘキサメチレンビスマレイミド、N,N'−(1,3−フェニレン)ビスマレイミド、N,N'−[1,3−(2−メチルフェニレン)]ビスマレイミド、N,N'−[1,3−(4−メチルフェニレン)]ビスマレイミド、N,N'−(1,4−フェニレン)ビスマレイミド、ビス(4−マレイミドフェニル)メタン、ビス(3−メチル−4−マレイミドフェニル)メタン、3,3'−ジメチル−5,5'−ジエチル−4,4'−ジフェニルメタンビスマレイミド、ビス(4−マレイミドフェニル)エーテル、ビス(4−マレイミドフェニル)スルホン、ビス(4−マレイミドフェニル)スルフィド、ビス(4−マレイミドフェニル)ケトン、ビス(4−マレイミドシクロヘキシル)メタン、1,4−ビス(4−マレイミドフェニル)シクロヘキサン、1,4−ビス(マレイミドメチル)シクロヘキサン、1,4−ビス(マレイミドメチル)ベンゼン、1,3−ビス(4−マレイミドフェノキシ)ベンゼン、1,3-ビス(3−マレイミドフェノキシ)ベンゼン、ビス[4−(3−マレイミドフェノキシ)フェニル]メタン、ビス[4−(4−マレイミドフェノキシ)フェニル]メタン、1,1'−ビス[4−(3−マレイミドフェノキシ)フェニル]エタン、1,1'−ビス[4−(4−マレイミドフェノキシ)フェニル]エタン、1,2−ビス[4−(3−マレイミドフェノキシ)フェニル]エタン、1,2−ビス[4−(4−マレイミドフェノキシ)フェニル]エタン、2,2'-ビス[4−(3−マレイミドフェノキシ)フェニル]プロパン、2,2'−ビス[4−(4−マレイミドフェノキシ)フェニル]プロパン、2,2'−ビス[4−(3−マレイミドフェノキシ)フェニル]ブタン、2,2'−ビス[4−(4−マレイミドフェノキシ)フェニル]ブタン、2,2'−ビス[4−(3−マレイミドフェノキシ)フェニル]−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ビス[4−(4−マレイミドフェノキシ)フェニル]−1,1,1,3,3,3−ヘキサフルオロプロパン、 Examples of the maleimide compound having at least two N-substituted maleimide groups in one molecule of the component (a) in the thermosetting resin composition of the present invention include N, N′-ethylenebismaleimide and N, N ′. -Hexamethylene bismaleimide, N, N '-(1,3-phenylene) bismaleimide, N, N'-[1,3- (2-methylphenylene)] bismaleimide, N, N '-[1,3 -(4-methylphenylene)] bismaleimide, N, N '-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3, 3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimide) Enyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4- Bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4 -(4-maleimidophenoxy) phenyl] methane, 1,1'-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1'-bis [4- (4-maleimidophenoxy) phenyl] ethane, , 2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) Phenyl] ethane, 2,2'-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2'-bis [4 -(3-maleimidophenoxy) phenyl] butane, 2,2'-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2'-bis [4- (3-maleimidophenoxy) phenyl] -1, 1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,
4,4'−ビス(3−マレイミドフェノキシ)ビフェニル、4,4'−ビス(4−マレイミドフェノキシ)ビフェニル、ビス[4−(3−マレイミドフェノキシ)フェニル]ケトン、ビス[4−(4−マレイミドフェノキシ)フェニル]ケトン、2,2'−ビス(4−マレイミドフェニル)ジスルフィド、ビス(4−マレイミドフェニル)ジスルフィド、ビス[4−(3−マレイミドフェノキシ)フェニル]スルフィド、ビス[4−(4−マレイミドフェノキシ)フェニル]スルフィド、ビス[4−(3−マレイミドフェノキシ)フェニル]スルホキシド、ビス[4−(4−マレイミドフェノキシ)フェニル]スルホキシド、ビス[4−(3−マレイミドフェノキシ)フェニル]スルホン、ビス[4−(4−マレイミドフェノキシ)フェニル]スルホン、ビス[4−(3−マレイミドフェノキシ)フェニル]エーテル、ビス[4−(4−マレイミドフェノキシ)フェニル]エーテル、1,4−ビス[4−(4−マレイミドフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,3−ビス[4−(4−マレイミドフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,4−ビス[4−(3−マレイミドフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,3−ビス[4−(3−マレイミドフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,4−ビス[4−(4−マレイミドフェノキシ)−3,5−ジメチル−α,α−ジメチルベンジル]ベンゼン、1,3−ビス[4−(4−マレイミドフェノキシ)−3,5−ジメチル−α,α−ジメチルベンジル]ベンゼン、1,4−ビス[4−(3−マレイミドフェノキシ)−3,5−ジメチル−α,α−ジメチルベンジル]ベンゼン、1,3−ビス[4−(3−マレイミドフェノキシ)−3,5−ジメチル−α,α−ジメチルベンジル]ベンゼン、ポリフェニルメタンマレイミド(例えば大和化成(株)製、商品名:BMI−2300等)等が挙げられ、これらのマレイミド化合物は、単独で用いても2種類以上を混合して用いてもよい。 4,4′-bis (3-maleimidophenoxy) biphenyl, 4,4′-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimide) Phenoxy) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4- Maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-Maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophene) Xyl) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [ 4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3- Bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α -Dimethylbenzyl] be , 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmethanemaleimide (for example, manufactured by Daiwa Kasei Co., Ltd., trade name: BMI-) These maleimide compounds may be used alone or in admixture of two or more.
これらのマレイミド化合物の中で、反応率が高く、より高耐熱性化できるビス(4−マレイミドフェニル)メタン、ビス(4−マレイミドフェニル)スルホン、N,N'−(1,3−フェニレン)ビスマレイミド、2,2'−ビス(4−(4−マレイミドフェノキシ)フェニル)プロパン、ポリフェニルメタンマレイミドが好ましく、溶剤への溶解性の点から、ビス(4−マレイミドフェニル)メタンが特に好ましい。 Among these maleimide compounds, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, and N, N ′-(1,3-phenylene) bis, which have a high reaction rate and can have higher heat resistance. Maleimide, 2,2′-bis (4- (4-maleimidophenoxy) phenyl) propane and polyphenylmethanemaleimide are preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.
(b)成分の1分子構造中に少なくとも1個のアミノ基を有する、アミン当量500以上2300以下のシリコーン化合物としては、1分子構造中に少なくとも2個のアミノ基を有するシリコーン化合物が好適に用いられ、上記のようなシリコーン構造の両末端にアミノ基を有するシリコーン化合物、どちらか一方の末端にアミノ基を有するシリコーン化合物や、側鎖にアミノ基を有するシリコーン化合物、側鎖、及び少なくとも一方の末端にアミノ基を有するシリコーン化合物が用いられる。 (B) As a silicone compound having at least one amino group in one molecular structure of the component and having an amine equivalent of 500 to 2300, a silicone compound having at least two amino groups in one molecular structure is preferably used. A silicone compound having an amino group at both ends of the silicone structure as described above, a silicone compound having an amino group at one end, a silicone compound having an amino group at a side chain, a side chain, and at least one of A silicone compound having an amino group at the terminal is used.
本発明の成分(b)の1分子構造中に少なくとも1個のアミノ基を有する、アミン当量500以上2300以下のシリコーン化合物は、市販品を用いることができ、例えば、「X−22−161A」(アミン当量800)、「X−22−161B」(アミン当量1500)、「KF−8012」(アミン当量2200)、「X−22−9409」(アミン当量700)、「X−22−1660B−3」(アミン当量2200)(以上、信越化学工業(株)製)、「BY−16−853」(アミン当量650)、「BY−16−853B」(アミン当量2200)(以上、東レダウコーニング(株)製)等が挙げられ、これらは単独で、あるいは2種類以上を混合して用いてもよい。 A commercially available product can be used as the silicone compound having an amine equivalent of 500 or more and 2300 or less and having at least one amino group in one molecular structure of the component (b) of the present invention. For example, “X-22-161A” (Amine equivalent 800), "X-22-161B" (amine equivalent 1500), "KF-8012" (amine equivalent 2200), "X-22-9409" (amine equivalent 700), "X-22-1660B- 3 ”(amine equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd.),“ BY-16-853 ”(amine equivalent 650),“ BY-16-853B ”(amine equivalent 2200) (above, Toray Dow Corning) Etc.), and these may be used alone or in admixture of two or more.
シリコーン化合物のアミン当量は、550以上2300以下であることが好ましく、耐薬品性向上の点から600以上1600以下であることがより好ましい。さらに、銅箔接着強度の向上の点から600以上1000以下であることが特に好ましい。 The amine equivalent of the silicone compound is preferably 550 or more and 2300 or less, and more preferably 600 or more and 1600 or less from the viewpoint of improving chemical resistance. Furthermore, from the point of improvement of copper foil adhesive strength, it is especially preferable that it is 600-1000.
(b)成分の使用量は、(a)成分100質量部に対して5〜100質量部が好ましく、30〜50質量部がより好ましい。5質量部以上とすることにより低熱膨張性が向上する。100質量部以下とすることにより成形性が向上する。 (B) As for the usage-amount of a component, 5-100 mass parts is preferable with respect to 100 mass parts of (a) component, and 30-50 mass parts is more preferable. Low thermal expansion improves by setting it as 5 mass parts or more. Formability is improved by setting it to 100 parts by mass or less.
本発明の熱硬化性樹脂組成物には、さらに(c)成分の分子構造中にフェノール性水酸基を有する化合物を含有させることが好ましい。なかでも、多官能フェノール性樹脂が好ましい。
(c)成分の分子構造中にフェノール性水酸基を有する化合物は、例えば、ビスフェノールA、ビスフェノールF、ビスフェノールS、4,4'−ビフェニルフェノール、テトラメチルビスフェノールA、ジメチルビスフェノールA、テトラメチルビスフェノールF、ジメチルビスフェノールF、テトラメチルビスフェノールS、ジメチルビスフェノールS、テトラメチル4,4'−ビフェノール、ジメチル−4,4'−ビフェニルフェノール、1−(4−ヒドロキシフェニル)−2−[4−(1,1'−ビス−(4−ヒドロキシフェニル)エチル)フェニル]プロパン、2,2'−メチレン−ビス(4−メチル−6−tert−ブチルフェノール)、4,4'−ブチリデン−ビス(3−メチル−6−tertブチルフェノール)、トリスヒドロキシフェニルメタン、レゾルシノール、ハイドロキノン、ピロガロール、ジイソプロポリデン骨格を有するフェノール類、1,1'−ジ−4−ヒドロキシフェニルフルオレン等のフルオレン骨格を有するフェノール類、フェノール化ポリブタジエン、フェノール、クレゾール類、エチルフェノール類、ブチルフェノール類、オクチルフェノール類、ビスフェノールA、ビスフェノールF、ビスフェノールS、ナフトール類等の各種フェノールを原料とするノボラック樹脂、キシリレン骨格含有フェノールノボラック樹脂、ジシクロペンタジエン骨格含有フェノールノボラック樹脂、ビフェニル骨格含有フェノールノボラック樹脂、フルオレン骨格含有フェノールノボラック樹脂等の各種ノボラック樹脂等が挙げられる。
The thermosetting resin composition of the present invention preferably further contains a compound having a phenolic hydroxyl group in the molecular structure of the component (c). Of these, polyfunctional phenolic resins are preferred.
The compound having a phenolic hydroxyl group in the molecular structure of component (c) is, for example, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, Dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl 4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1 '-Bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6) -Tertbutylphenol), trishydroxy Phenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropolyden skeleton, phenols having a fluorene skeleton such as 1,1′-di-4-hydroxyphenylfluorene, phenolized polybutadiene, phenol, cresols, ethylphenol , Butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, novolak resins made from various phenols, xylylene skeleton-containing phenol novolac resins, dicyclopentadiene skeleton-containing phenol novolac resins, biphenyl skeleton-containing phenols Various novolak resins such as a novolak resin and a phenol novolak resin containing a fluorene skeleton may be used.
また、(c)成分の分子構造中にアミノ基とフェノール性水酸基を有する化合物としては、例えば、m−アミノフェノール、p−アミノフェノール、o−アミノフェノール、p−アミノ安息香酸、m−アミノ安息香酸、o−アミノ安息香酸、o−アミノベンゼンスルホン酸、m−アミノベンゼンスルホン酸、p−アミノベンゼンスルホン酸、3,5−ジヒドロキシアニリン、3,5−ジカルボキシアニリン等が挙げられる。これらは単独で、あるいは2種類以上を混合して用いてもよい。これらの中で、溶解性や合成の収率の点からm−アミノフェノール、p−アミノフェノール、o−アミノフェノール、p−アミノ安息香酸、m−アミノ安息香酸、及び3,5−ジヒドロキシアニリンが好ましく、耐熱性の点からm−アミノフェノール及びp−アミノフェノールがより好ましく、低熱膨張性の点からp−アミノフェノールが特に好ましい。 Examples of the compound having an amino group and a phenolic hydroxyl group in the molecular structure of component (c) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, and m-aminobenzoic acid. Examples include acids, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like. These may be used alone or in admixture of two or more. Among these, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are used in terms of solubility and synthesis yield. Preferably, m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance, and p-aminophenol is particularly preferable from the viewpoint of low thermal expansion.
(c)成分が分子構造中にアミノ基とフェノール性水酸基を有する化合物である場合、(a)成分の1分子構造中に少なくとも2個のN−置換マレイミド基を有するマレイミド化合物と有機溶媒中で、必要により加熱・保温しながら0.1〜10時間撹拌し、あらかじめ反応させておくことができる。 When the component (c) is a compound having an amino group and a phenolic hydroxyl group in the molecular structure, the maleimide compound having at least two N-substituted maleimide groups in one molecular structure of the component (a) in an organic solvent If necessary, the mixture can be stirred for 0.1 to 10 hours while being heated and kept warm, and reacted in advance.
この場合、(c)成分のアミノ基とフェノール性水酸基を有する化合物は、低熱膨張性の点からp−アミノフェノールが好ましい。ここで、(b)成分のシリコーン化合物と(c)成分のフェノール性水酸基を有するアミン化合物の使用量は、それらの−NH2基当量の総和と(a)成分のマレイミド化合物のマレイミド基当量との関係が、次式:
2.0≦(マレイミド基当量)/(−NH2基換算の当量)≦10.0
に示す範囲であることが望ましい。当量比が10.0を超えると溶剤への溶解性が不足したり熱硬化性樹脂の耐熱性が低下する場合があり、2.0未満であるとゲル化を起こしたり、熱硬化性樹脂の耐熱性が低下する場合がある。
In this case, the compound (c) having an amino group and a phenolic hydroxyl group is preferably p-aminophenol from the viewpoint of low thermal expansion. Here, the use amount of the silicone compound of component (b) and the amine compound having a phenolic hydroxyl group of component (c) is the sum of the —NH 2 group equivalents and the maleimide group equivalent of the maleimide compound of component (a). The relationship is:
2.0 ≦ (maleimide group equivalent) / (-NH 2 group equivalent) ≦ 10.0
It is desirable to be in the range shown in. If the equivalent ratio exceeds 10.0, the solubility in the solvent may be insufficient or the heat resistance of the thermosetting resin may decrease, and if it is less than 2.0, gelation may occur, Heat resistance may decrease.
(c)成分の使用量は、上記関係式を満たした上で(a)成分100質量部に対して1〜50質量部が好ましく、5〜20質量部がより好ましい。1質量部以上とすることにより耐薬品性が向上する。50質量部以下とすることにより耐熱性が向上する。 (C) As for the usage-amount of a component, 1-50 mass parts is preferable with respect to 100 mass parts of (a) component after satisfy | filling the said relational expression, and 5-20 mass parts is more preferable. Chemical resistance improves by setting it as 1 mass part or more. Heat resistance improves by setting it as 50 mass parts or less.
この際の有機溶媒の使用量は、(a)成分と(c)成分の総和100質量部当たり、10〜1000質量部とすることが好ましく、100〜500質量部とすることがより好ましく、200〜500質量部とすることが特に好ましい。有機溶剤の配合量が少ないと溶解性が不足し、また1000質量部を超えると合成に長時間を要する。 The amount of the organic solvent used in this case is preferably 10 to 1000 parts by mass, more preferably 100 to 500 parts by mass, per 100 parts by mass of the sum of the components (a) and (c). It is especially preferable to set it as -500 mass parts. If the amount of the organic solvent is small, the solubility is insufficient, and if it exceeds 1000 parts by mass, a long time is required for synthesis.
この反応で使用される有機溶媒は特に制限されないが、例えばエタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、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系溶剤、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系溶剤、テトラヒドロフラン等のエーテル系溶剤、トルエン、キシレン、メシチレン等の芳香族系溶剤、ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドン等の窒素原子含有溶剤、ジメチルスルホキシド等の硫黄原子含有溶剤等が挙げられ、これらは単独で、あるいは2種類以上を混合して使用してもよい。これらの中で、溶解性の点からシクロヘキサノン、プロピレングリコールモノメチルエーテル、メチルセロソルブが好ましく、低毒性である点からシクロヘキサノン、プロピレングリコールモノメチルエーテルがより好ましく、揮発性が高くプリプレグの製造時に残溶剤として残りにくいプロピレングリコールモノメチルエーテルが特に好ましい。 The organic solvent used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, nitrogen atom containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfur atom containing solvents such as dimethyl sulfoxide, etc. These may be used alone or in admixture of two or more. Among these, cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity, and they remain as residual solvents when producing prepreg because of their high volatility. The difficult propylene glycol monomethyl ether is particularly preferred.
また、この反応には、必要により任意に反応触媒を使用することができ、特に限定されない。反応触媒の例としては、トリエチルアミン、ピリジン、トリブチルアミン等のアミン類、メチルイミダゾール、フェニルイミダゾール等のイミダゾール類、トリフェニルホスフィン等のリン系触媒等が挙げられ、これらは単独で、あるいは2種類以上を混合して使用してもよい。 In this reaction, a reaction catalyst can be optionally used as necessary, and is not particularly limited. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more. May be used in combination.
上記の(a)成分と(c)成分を有機溶媒中で反応させる際、反応温度は70〜150℃であることが好ましく、100〜130℃であることがさらに好ましい。反応時間は0.1〜10時間であることが好ましく、1〜6時間であることがさらに好ましい。 When the above components (a) and (c) are reacted in an organic solvent, the reaction temperature is preferably 70 to 150 ° C, more preferably 100 to 130 ° C. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
本発明の熱硬化性樹脂組成物には、さらに(d)熱硬化性樹脂を含有させることが好ましい。なかでも、分子構造中にエポキシ基および/又はシアネート基を有する熱硬化性樹脂が好ましい。
(d)成分の熱硬化性樹脂は、特に制限されないが、例えば、エポキシ樹脂、フェノール樹脂、不飽和イミド樹脂、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、オキセタン樹脂、アミノ樹脂、不飽和ポリエステル樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂、メラミン樹脂等が挙げられ、これらは単独で、あるいは2種類以上を混合して使用してもよい。これらの中で、成形性や電気絶縁性の点からエポキシ樹脂、シアネート樹脂が好ましい。
The thermosetting resin composition of the present invention preferably further contains (d) a thermosetting resin. Especially, the thermosetting resin which has an epoxy group and / or cyanate group in molecular structure is preferable.
The thermosetting resin as the component (d) is not particularly limited, and examples thereof include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, Examples include allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, and the like. These may be used alone or in admixture of two or more. Among these, epoxy resins and cyanate resins are preferable from the viewpoint of moldability and electrical insulation.
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、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、ビスフェノールFノボラック型エポキシ樹脂、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、トリフェノールフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、キシリレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、脂環式エポキシ樹脂、多官能フェノール類及びアントラセン等の多環芳香族類のジグリシジルエーテル化合物およびこれらにリン化合物を導入したリン含有エポキシ樹脂等が挙げられ、これらは単独で、あるいは2種類以上を混合して使用してよい。これらの中で、耐熱性、難燃性の点からビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂が好ましい。 Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene type epoxy resin, Triazine skeleton containing epoxy resin, Fluorene skeleton containing epoxy resin, Triphenolphenol methane type epoxy resin, Biphenyl type epoxy resin, Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin, Naphthalene type epoxy resin, Dicyclopentadiene -Type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl ether compounds of polycyclic aromatics such as anthracene And these phosphorus-containing epoxy resin obtained by introducing a phosphorus compound are mentioned, these alone, or two or more kinds may be used in admixture. Among these, biphenylaralkyl type epoxy resins and naphthalene type epoxy resins are preferred from the viewpoint of heat resistance and flame retardancy.
また、シアネート樹脂としては、例えば、ノボラック型シアネート樹脂、ビスフェノールA型シアネート樹脂、ビスフェノールE型シアネート樹脂、テトラメチルビスフェノールF型シアネート樹脂等のビスフェノール型シアネート樹脂およびこれらが一部トリアジン化したプレポリマー等を挙げることができ、これらは単独で、あるいは2種類以上を混合して使用してもよい。これらの中で耐熱性、難燃性の点からノボラック型シアネート樹脂が好ましい。 Examples of cyanate resins include novolak-type cyanate resins, bisphenol A-type cyanate resins, bisphenol E-type cyanate resins, and tetramethylbisphenol F-type cyanate resins, and prepolymers in which these are partially triazines. These may be used alone or in admixture of two or more. Among these, a novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy.
(d)成分の使用量は、(a)成分100質量部に対して20〜300質量部が好ましく、50〜150質量部がより好ましい。20質量部以上とすることにより耐熱性が向上し、300質量部以下とすることにより耐薬品性が向上する。 (D) As for the usage-amount of a component, 20-300 mass parts is preferable with respect to 100 mass parts of (a) component, and 50-150 mass parts is more preferable. Heat resistance improves by setting it as 20 mass parts or more, and chemical resistance improves by setting it as 300 mass parts or less.
本発明の熱硬化性樹脂には、耐熱性や難燃性、銅箔接着強度等の向上化のため、(e)硬化促進剤を用いることが望ましく、硬化促進剤の例としては、イミダゾール類及びその誘導体、第三級アミン類、第四級アンモニウム塩、ホスフィン類及びホスホニウム塩等の有機リン系化合物等が挙げられる。その中でもイミダゾール類及びその誘導体が耐熱性や難燃性、銅箔接着強度等の点から好ましく、さらに下記一般式(1)で表される、イソシアネート樹脂との反応により得られるイミダゾール誘導体や、下記一般式(2)で表される、イミダゾール基がエポキシ樹脂と反応することにより得られるイミダゾール誘導体が200℃以下での比較的低温での硬化成形性とワニスやプリプレグの経日安定性に優れるためより好ましく、下記式(3)又は(4)で表される化合物が少量配合されてもよく、また商業的にも安価であることから特に好ましい。 For the thermosetting resin of the present invention, it is desirable to use (e) a curing accelerator in order to improve heat resistance, flame retardancy, copper foil adhesion strength, etc. Examples of the curing accelerator include imidazoles And organic phosphorus compounds such as derivatives thereof, tertiary amines, quaternary ammonium salts, phosphines and phosphonium salts. Among them, imidazoles and derivatives thereof are preferable in terms of heat resistance, flame retardancy, copper foil adhesive strength, and the like, and further represented by the following general formula (1), imidazole derivatives obtained by reaction with isocyanate resins, The imidazole derivative represented by the general formula (2) obtained by reacting an imidazole group with an epoxy resin is excellent in curing moldability at a relatively low temperature at 200 ° C. or less and the aging stability of varnish and prepreg. More preferably, a small amount of the compound represented by the following formula (3) or (4) may be blended, and it is particularly preferable because it is commercially inexpensive.
(式中、R6、R7、R8、R9は各々独立に水素原子、又は炭素数1〜5の脂肪族炭化水素基、フェニル基を示し、Dはアルキレン基、芳香族炭化水素基である)
(In the formula, R 6 , R 7 , R 8 and R 9 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, and D represents an alkylene group or an aromatic hydrocarbon group. Is)
(式中、R6、R7、R8、R9は各々独立に水素原子、又は炭素数1〜5の脂肪族炭化水素基、フェニル基を示し、Bは存在しないか(Bは単結合)、又はアルキレン基、アルキリデン基、エーテル基、スルフォニル基のいずれかである)
(Wherein R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a phenyl group, and B is not present (B is a single bond) Or an alkylene group, an alkylidene group, an ether group or a sulfonyl group)
(e)硬化促進剤の使用量は、固形分換算の該成分(a)〜(d)の総和100質量部当たり、0.1質量部以上10質量部以下とすることが好ましく、0.1質量部以上5質量部以下とすることがより好ましく、0.1質量部以上1質量部以下とすることが特に好ましい。硬化促進剤の使用量を0.1質量部以上とすることにより優れた耐熱性や難燃性、銅箔接着強度が得られ、また10質量部以下とすることにより耐熱性、経日安定性及びプレス成形性が低下しない。 (E) It is preferable that the usage-amount of a hardening accelerator shall be 0.1 to 10 mass parts per 100 mass parts of total of this component (a)-(d) of solid content conversion, 0.1 It is more preferable to set it as 5 to 5 mass parts, and it is especially preferable to set it as 0.1 to 1 mass part. Excellent heat resistance and flame retardancy and copper foil adhesion strength can be obtained by setting the amount of the curing accelerator used to 0.1 parts by mass or more, and heat resistance and stability over time by setting it to 10 parts by mass or less. And press formability does not deteriorate.
本発明の熱硬化性樹脂には、任意に(f)無機充填材の併用ができる。無機充填材としては、シリカ、アルミナ、タルク、マイカ、カオリン、水酸化アルミニウム、ベーマイト、水酸化マグネシウム、ホウ酸亜鉛、スズ酸亜鉛、酸化亜鉛、酸化チタン、窒化ホウ素、炭酸カルシウム、硫酸バリウム、ホウ酸アルミニウム、チタン酸カリウム、EガラスやTガラス、Dガラス等のガラス粉や中空ガラスビーズ等が挙げられ、これらは単独で、あるいは2種類以上を混合して使用してもよい。
これらの(f)成分の無機充填材中で、誘電特性、耐熱性、低熱膨張性の点からシリカが特に好ましい。シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカと、乾式法で製造され結合水等をほとんど含まない乾式法シリカが挙げられ、乾式法シリカとしてはさらに、製造法の違いにより破砕シリカ、フュームドシリカ、溶融球状シリカが挙げられる。これらの中で、低熱膨張性及び樹脂に充填した際の高流動性から溶融球状シリカが好ましい。
In the thermosetting resin of the present invention, (f) an inorganic filler can be optionally used in combination. Inorganic fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, and boron. Examples include aluminum oxide, potassium titanate, glass powder such as E glass, T glass, and D glass, and hollow glass beads. These may be used alone or in admixture of two or more.
Among these inorganic fillers of component (f), silica is particularly preferable from the viewpoint of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include a precipitated silica produced by a wet method and having a high water content, and a dry method silica produced by a dry method and containing almost no bound water. The dry method silica further includes differences in production methods. Examples include crushed silica, fumed silica, and fused spherical silica. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.
(f)成分の無機充填材として溶融球状シリカを用いる場合、その平均粒子径は0.1〜10μmであることが好ましく、0.3〜8μmであることがより好ましい。該溶融球状シリカの平均粒子径を0.1μm以上にすることで、樹脂に高充填した際の流動性を良好に保つことができ、さらに10μm以下にすることで、粗大粒子の混入確率を減らし粗大粒子起因の不良の発生を抑えることができる。ここで、平均粒子径とは、粒子の全体積を100%として粒子径による累積度数分布曲線を求めた時、ちょうど体積50%に相当する点の粒子径のことであり、レーザ回折散乱法を用いた粒度分布測定装置等で測定することができる。 When fused spherical silica is used as the inorganic filler of component (f), the average particle size is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced. Generation of defects due to coarse particles can be suppressed. Here, the average particle size is a particle size at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.
(f)無機充填材の含有量は、固形分換算の(a)〜(d)成分の総和100質量部当たり10〜70質量部であることが好ましく、30〜55質量部であることがより好ましい。無機充填材の含有量を樹脂成分の総和100質量部当たり10〜70質量部にすることで、樹脂組成物の成形性と低熱膨張性を良好に保つことが出来る。 (F) The content of the inorganic filler is preferably 10 to 70 parts by mass and more preferably 30 to 55 parts by mass per 100 parts by mass of the total of components (a) to (d) in terms of solid content. preferable. By making content of an inorganic filler into 10-70 mass parts per 100 mass parts of sum total of a resin component, the moldability and low thermal expansibility of a resin composition can be kept favorable.
本発明では、その目的に反しない範囲内で、任意に公知の熱可塑性樹脂、エラストマー、難燃剤、有機充填材等の併用ができる。
熱可塑性樹脂の例としては、テトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、ポリフェニレンエーテル樹脂、フェノキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、キシレン樹脂、石油樹脂及びシリコーン樹脂等が挙げられる。
エラストマーの例としては、ポリブタジエン、アクリロニトリル、エポキシ変性ポリブタジエン、無水マレイン酸変性ポリブタジエン、フェノール変性ポリブタジエン及びカルボキシ変性アクリロニトリル等が挙げられる。
有機充填材の例としては、シリコーンパウダー、テトラフルオロエチレン、ポリエチレン、ポリプロピレン、ポリスチレン、並びにポリフェニレンエーテル等の有機物粉末等が挙げられる。
In the present invention, known thermoplastic resins, elastomers, flame retardants, organic fillers, and the like can be used in combination as long as they do not contradict the purpose.
Examples of the thermoplastic resin include tetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.
Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.
Examples of organic fillers include organic powders such as silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.
本発明において、任意に該樹脂組成物に対して、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤及び密着性向上剤等の添加も可能であり、特に限定されない。これらの例としては、ベンゾトリアゾール系等の紫外線吸収剤、ヒンダードフェノール系やスチレン化フェノール等の酸化防止剤、ベンゾフェノン類、ベンジルケタール類、チオキサントン系等の光重合開始剤、スチルベン誘導体等の蛍光増白剤、尿素シラン等の尿素化合物やシランカップリング剤等の密着性向上剤等が挙げられる。 In the present invention, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like can be arbitrarily added to the resin composition, and the resin composition is not particularly limited. Examples of these include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescence such as stilbene derivatives. Examples include brighteners, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.
本発明の熱硬化性樹脂組成物はワニスとして用いられる。ワニスを製造する際に使用される有機溶媒は特に制限されないが、例えばエタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、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系溶剤、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系溶剤、テトラヒドロフラン等のエーテル系溶剤、トルエン、キシレン、メシチレン等の芳香族系溶剤、ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドン等の窒素原子含有溶剤、ジメチルスルホキシド等の硫黄原子含有溶剤等が挙げられ、これらは単独で、あるいは2種類以上を混合して使用してもよい。これらの中で、溶解性の点からシクロヘキサノン、プロピレングリコールモノメチルエーテル、メチルセロソルブが好ましく、低毒性である点からシクロヘキサノン、プロピレングリコールモノメチルエーテルがより好ましく、揮発性が高くプリプレグの製造時に残溶剤として残りにくいプロピレングリコールモノメチルエーテルが特に好ましい。
ワニスは固形分濃度として40〜80質量%として使用することが好ましい。
The thermosetting resin composition of the present invention is used as a varnish. The organic solvent used in the production of the varnish is not particularly limited. Ketone solvents, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, nitrogen atom containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfur atom containing solvents such as dimethyl sulfoxide, etc. These may be used alone or in admixture of two or more. Among these, cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity. The difficult propylene glycol monomethyl ether is particularly preferred.
The varnish is preferably used as a solid concentration of 40 to 80% by mass.
本発明のプリプレグは、前記した本発明の熱硬化性樹脂組成物を、基材に含浸又は塗工してなるものである。以下、本発明のプリプレグについて詳述する。
本発明のプリプレグは、本発明の熱硬化性樹脂組成物を、基材に含浸又は塗工し、加熱等により半硬化(Bステージ化)して本発明のプリプレグを製造することができる。本発明の基材として、各種の電気絶縁材料用積層板に用いられている周知のものが使用できる。その材質の例としては、Eガラス、Dガラス、Sガラス及びQガラス等の無機物繊維、ポリイミド、ポリエステル及びテトラフルオロエチレン等の有機繊維、並びにそれらの混合物等が挙げられる。
これらの基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット及びサーフェシングマット等の形状を有するが、材質及び形状は、目的とする成形物の用途や性能により選択され、必要により、単独又は2種類以上の材質及び形状を組み合わせることができる。基材の厚さは、特に制限されず、例えば、約0.03〜0.5mmを使用することができ、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性や耐湿性、加工性の面から好適である。
The prepreg of the present invention is obtained by impregnating or coating the base material with the above-described thermosetting resin composition of the present invention. Hereinafter, the prepreg of the present invention will be described in detail.
The prepreg of the present invention can be produced by impregnating or coating the base material with the thermosetting resin composition of the present invention and semi-curing (B-stage) by heating or the like. As the base material of the present invention, known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and tetrafluoroethylene, and mixtures thereof.
These base materials have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined. The thickness of the substrate is not particularly limited, and can be, for example, about 0.03 to 0.5 mm, and is surface-treated with a silane coupling agent or the like or mechanically subjected to fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability.
本発明のプリプレグは、該基材に対する樹脂組成物の付着量が、乾燥後のプリプレグの樹脂含有率で、20〜90重量%となるように、基材に含浸又は塗工した後、通常、100〜200℃の温度で1〜30分加熱乾燥し、半硬化(Bステージ化)させて得ることができる。
本発明の積層板は、前述の本発明のプリプレグを用いて、積層成形して、形成することができる。本発明のプリプレグを、例えば、1〜20枚重ね、その片面又は両面に銅及びアルミニウム等の金属箔を配置した構成で積層成形することにより製造することができる。金属箔は、電気絶縁材料用途で用いるものであれば特に制限されない。
積層板を製造する際の成形条件は、例えば、電気絶縁材料用積層板及び多層板の手法が適用でき、例えば多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用し、温度100〜250℃、圧力0.2〜10MPa、加熱時間0.1〜5時間の範囲で成形することができる。また、本発明のプリプレグと内層用配線板とを組合せ、積層成形して、多層板を製造することもできる。
The prepreg of the present invention is usually impregnated or coated on the base material so that the amount of the resin composition attached to the base material is 20 to 90% by weight with the resin content of the prepreg after drying. It can be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).
The laminate of the present invention can be formed by laminate molding using the prepreg of the present invention described above. The prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications.
The molding conditions for producing the laminate can be applied, for example, to the method of laminates for electrical insulation materials and multilayer plates, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. Molding can be performed at 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.
本発明に係るプリント配線板は、前記積層板の表面に回路を形成して製造される。すなわち、本発明に係る積層板の導体層を通常のエッチング法によって配線加工し、前述のプリプレグを介して配線加工した積層板を複数積層し、加熱プレス加工することによって一括して多層化する。その後、ドリル加工またはレーザ加工によるスルーホール又はブラインドビアホールの形成と、めっき又は導電性ペーストによる層間配線の形成を経て多層プリント配線板を製造することができる。 The printed wiring board according to the present invention is manufactured by forming a circuit on the surface of the laminated board. That is, the conductor layer of the laminated board according to the present invention is subjected to wiring processing by a normal etching method, and a plurality of laminated boards subjected to wiring processing through the above-described prepreg are laminated and subjected to hot press processing to be multilayered at once. Then, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.
次に、下記の実施例により本発明をさらに詳しく説明するが、これらの実施例は本発明を制限するものではない。
なお、各実施例および比較例から得られた銅張積層板を用いて、銅箔接着強度(銅箔ピール強度)、ガラス転移温度(Tg)、熱膨張率、はんだ耐熱性、耐薬品性について以下の方法で測定・評価した。
Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
In addition, about the copper foil adhesive strength (copper foil peel strength), glass transition temperature (Tg), thermal expansion coefficient, solder heat resistance, chemical resistance, using the copper clad laminate obtained from each example and comparative example Measurement and evaluation were carried out by the following methods.
(1)銅箔接着強度(銅箔ピール強度)の評価
銅張積層板を銅エッチング液に浸漬することにより1cm幅の銅箔(12μm箔)を形成して評価基板を作製し、引張り試験機を用いて銅箔の接着強度(銅箔ピール強度)を測定した。
(1) Evaluation of copper foil adhesive strength (copper foil peel strength) A copper-clad laminate is immersed in a copper etching solution to form a 1 cm wide copper foil (12 μm foil) to produce an evaluation substrate, and a tensile tester Was used to measure the adhesive strength (copper foil peel strength) of the copper foil.
(2)ガラス転移温度(Tg)の測定
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた5mm角の評価基板を作製し、TMA試験装置(デュポン社製、TMA2940)を用いて圧縮法で熱機械分析をおこなった。評価基板を前記装置にZ方向に装着後、荷重5g、昇温速度10℃/分の測定条件にて連続して2回測定した。2回目の測定における熱膨張曲線の異なる接線の交点で示されるTgを求め、耐熱性を評価した。
(2) Measurement of glass transition temperature (Tg) A 5-mm square evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (manufactured by DuPont, TMA2940) was used. The thermomechanical analysis was performed by the compression method. After mounting the evaluation substrate on the apparatus in the Z direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined, and the heat resistance was evaluated.
(3)熱膨張率の測定
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた5mm角の評価基板を作製し、TMA試験装置(デュポン社製、TMA2940)を用いて圧縮法で熱機械分析をおこなった。評価基板を前記装置にX方向に装着後、荷重5g、昇温速度10℃/分の測定条件にて連続して2回測定した。2回目の測定における30℃から100℃の平均熱膨張率を算出し、これを熱膨張率の値とした。
(3) Measurement of coefficient of thermal expansion A 5 mm square evaluation board from which copper foil has been removed by immersing a copper clad laminate in a copper etching solution is prepared, and a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940) A thermomechanical analysis was performed. After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of the coefficient of thermal expansion.
(4)はんだ耐熱性の評価
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた5cm角の評価基板を作製し、平山製作所(株)製プレッシャー・クッカー試験装置を用いて、121℃、2気圧の条件で4時間までプレッシャー・クッカー処理を行った後、温度288℃のはんだ浴に、評価基板を20秒間浸漬した後、外観を観察することによりはんだ耐熱性を評価した。
(4) Evaluation of solder heat resistance A 5 cm square evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared using a pressure cooker test apparatus manufactured by Hirayama Seisakusho Co., Ltd. After performing the pressure-cooker treatment up to 4 hours under the conditions of 121 ° C. and 2 atm, the evaluation substrate was immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the solder heat resistance was evaluated by observing the appearance.
(5)耐薬品性の評価
得られた銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた5cm角の評価基板を作製し、重量を測定したのち、膨潤液としてジエチレングリコールモノブチルエーテル:200ml/L、NaOH:5g/Lの水溶液を作製し、70℃に加温して5分間浸漬処理した。次に、粗化液として、KMnO4:60g/L、NaOH:40g/Lの水溶液を作製し、80℃に加温して10分間浸漬処理した。引き続き、中和液(SnCl2:30g/L、HCl:30ml/L)の水溶液に室温で5分間浸漬処理して中和した。処理した評価基板を乾燥、重量測定し、処理前後の重量を比較することで耐薬品性を評価した。
(5) Evaluation of chemical resistance The obtained copper-clad laminate was immersed in a copper etching solution to prepare a 5 cm square evaluation substrate from which the copper foil was removed, and after measuring the weight, diethylene glycol monobutyl ether as a swelling solution : 200 ml / L, NaOH: 5 g / L aqueous solution was prepared, heated to 70 ° C. and immersed for 5 minutes. Next, an aqueous solution of KMnO4: 60 g / L and NaOH: 40 g / L was prepared as a roughening solution, heated to 80 ° C. and immersed for 10 minutes. Subsequently, it was neutralized by immersing it in an aqueous solution of a neutralizing solution (SnCl2: 30 g / L, HCl: 30 ml / L) at room temperature for 5 minutes. The treated evaluation substrate was dried and weighed, and the chemical resistance was evaluated by comparing the weight before and after the treatment.
実施例1〜10、比較例1〜3
以下に示す(a)〜(d)成分と、(e)硬化促進剤、(f)無機充填材、及び希釈溶剤にメチルエチルケトンを使用して、第1表〜第3表に示した配合割合(質量部)で混合して樹脂分65質量%の均一なワニスを得た。
次に、上記ワニスを厚さ0.1mmのEガラスクロスに含浸塗工し、160℃で10分加熱乾燥して樹脂含有量50質量%のプリプレグを得た。
このプリプレグを4枚重ね、18μmの電解銅箔を上下に配置し、圧力2.5MPa、温度230℃で90分間プレスを行って、銅張積層板を得た。
得られた銅張積層板の測定・評価結果を第1表〜第3表に示す。
Examples 1-10, Comparative Examples 1-3
Components (a) to (d) shown below, (e) a curing accelerator, (f) an inorganic filler, and a blending ratio shown in Tables 1 to 3 using methyl ethyl ketone as a diluent solvent ( To obtain a uniform varnish having a resin content of 65% by mass.
Next, the varnish was impregnated and applied to an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 50 mass%.
Four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 230 ° C. for 90 minutes to obtain a copper-clad laminate.
The measurement and evaluation results of the obtained copper-clad laminate are shown in Tables 1 to 3.
(a)マレイミド化合物
ビス(4−マレイミドフェニル)メタン
3,3'−ジメチル−5,5'−ジエチル−4,4'−ジフェニルメタンビスマレイミド
(A) Maleimide compound bis (4-maleimidophenyl) methane 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide
(b)シリコーン化合物
X−22−161A(信越化学工業(株)製、アミン当量800)
X−22−161B(信越化学工業(株)製、アミン当量1500)
KF−8012(信越化学工業(株)製、アミン当量2200)
(B) Silicone compound X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 800)
X-22-161B (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 1500)
KF-8012 (Shin-Etsu Chemical Co., Ltd., amine equivalent 2200)
(c)フェノール性水酸基を有する化合物
ビスフェノールA
p−アミノフェノール
(C) Compound having phenolic hydroxyl group Bisphenol A
p-aminophenol
(d)熱硬化性樹脂
ビフェニルアラルキル型エポキシ樹脂(日本化薬(株)製、商品名:NC−3000 −H)
ノボラック型シアネート樹脂(ロンザジャパン(株)製、商品名:PT−30)
(D) Thermosetting resin Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000-H)
Novolac-type cyanate resin (Lonza Japan Co., Ltd., trade name: PT-30)
(e)硬化促進剤:G−8009L(ヘキサメチレンジイソシアネート樹脂と2−エチ ル−4−メチルイミダゾールの付加反応物:前記の式(4)で表される化合物)
(f)無機充填材:溶融シリカ(アドマテックス(株)製、商品名:SC−2050K NK)
(g)その他のシリコーン化合物
KF−8010(信越化学工業(株)製、アミン当量430)(比較例)
KF−8008(信越化学工業(株)製、アミン当量5700)(比較例)
(E) Curing accelerator: G-8809L (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole: compound represented by the above formula (4))
(F) Inorganic filler: fused silica (manufactured by Admatechs Co., Ltd., trade name: SC-2050K NK)
(G) Other silicone compounds KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 430) (comparative example)
KF-8008 (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 5700) (comparative example)
表から明らかなように、本発明の実施例は、銅箔接着強度、ガラス転移温度、低熱膨張性、はんだ耐熱性、耐薬品性の全ての項目において優れている。一方、比較例は、銅箔接着強度、ガラス転移温度、低熱膨張性、はんだ耐熱性、耐薬品性の全てを満たすものは無く、いずれかの特性に劣っている。 As is apparent from the table, the examples of the present invention are excellent in all items of copper foil adhesive strength, glass transition temperature, low thermal expansion, solder heat resistance, and chemical resistance. On the other hand, none of the comparative examples satisfy all of the copper foil adhesive strength, glass transition temperature, low thermal expansion property, solder heat resistance, and chemical resistance, and are inferior in any of the characteristics.
本発明の熱硬化性樹脂組成物より得られるプリプレグを積層形成した積層板を用いて製造されるプリント配線板は、銅箔密着強度、ガラス転移温度、低熱膨張性、はんだ耐熱性、耐薬品性に優れ、高集積化された電子機器用プリント配線板として有用である。 A printed wiring board manufactured using a laminate obtained by laminating a prepreg obtained from the thermosetting resin composition of the present invention has copper foil adhesion strength, glass transition temperature, low thermal expansion, solder heat resistance, chemical resistance. And is useful as a highly integrated printed wiring board for electronic equipment.
Claims (13)
(式中、R6、R7、R8、R9はそれぞれ独立に、水素原子、炭素数1〜5の脂肪族炭化水素基、又はフェニル基を示し、Dはアルキレン基又は芳香族炭化水素基である。)
(式中、R6、R7、R8、R9はそれぞれ独立に、水素原子、炭素数1〜5の脂肪族炭化水素基、又はフェニル基を示し、Bは単結合、又はアルキレン基、アルキリデン基、エーテル基、スルフォニル基のいずれかである。) Furthermore, the thermosetting resin composition for printed wiring boards in any one of Claims 1-8 containing (e) hardening accelerator represented by the following general formula (1) or (2).
(Wherein R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, and D represents an alkylene group or an aromatic hydrocarbon. Group.)
(Wherein R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, and B represents a single bond or an alkylene group, It is either an alkylidene group, an ether group or a sulfonyl group.)
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