JP6596811B2 - Thermosetting resin composition, prepreg using the same, film with resin, laminated board, multilayer printed wiring board, and semiconductor package - Google Patents
Thermosetting resin composition, prepreg using the same, film with resin, laminated board, multilayer printed wiring board, and semiconductor package Download PDFInfo
- Publication number
- JP6596811B2 JP6596811B2 JP2014151955A JP2014151955A JP6596811B2 JP 6596811 B2 JP6596811 B2 JP 6596811B2 JP 2014151955 A JP2014151955 A JP 2014151955A JP 2014151955 A JP2014151955 A JP 2014151955A JP 6596811 B2 JP6596811 B2 JP 6596811B2
- Authority
- JP
- Japan
- Prior art keywords
- molecule
- resin composition
- group
- compound
- resin
- 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.)
- Active
Links
- 229920005989 resin Polymers 0.000 title claims description 164
- 239000011347 resin Substances 0.000 title claims description 164
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 79
- 239000011342 resin composition Substances 0.000 title claims description 77
- 239000004065 semiconductor Substances 0.000 title claims description 16
- -1 siloxane compound Chemical class 0.000 claims description 234
- 230000002378 acidificating effect Effects 0.000 claims description 37
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 37
- 125000001424 substituent group Chemical group 0.000 claims description 34
- 239000003822 epoxy resin Substances 0.000 claims description 32
- 229920000647 polyepoxide Polymers 0.000 claims description 32
- 125000000524 functional group Chemical group 0.000 claims description 29
- 150000003949 imides Chemical class 0.000 claims description 27
- 125000003700 epoxy group Chemical group 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 17
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 11
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000003475 lamination Methods 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 33
- 238000000034 method Methods 0.000 description 33
- 239000010410 layer Substances 0.000 description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 239000003960 organic solvent Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 239000000758 substrate Substances 0.000 description 20
- 239000011889 copper foil Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 19
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 238000010030 laminating Methods 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 239000002966 varnish Substances 0.000 description 13
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 12
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 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 10
- 229920003986 novolac Polymers 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000004020 conductor Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 239000000806 elastomer Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 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 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 150000004982 aromatic amines Chemical class 0.000 description 6
- 239000007809 chemical reaction catalyst Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 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 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 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 6
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-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
- 229920000877 Melamine resin Polymers 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- 239000005456 alcohol based solvent Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 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
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000005553 drilling Methods 0.000 description 4
- 239000004210 ether based solvent Substances 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 3
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 3
- BWAPJIHJXDYDPW-UHFFFAOYSA-N 2,5-dimethyl-p-phenylenediamine Chemical compound CC1=CC(N)=C(C)C=C1N BWAPJIHJXDYDPW-UHFFFAOYSA-N 0.000 description 3
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 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 3
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 3
- 229940018563 3-aminophenol Drugs 0.000 description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 3
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 2
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 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
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 2
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 description 2
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent 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
- 238000009835 boiling Methods 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012772 electrical insulation material Substances 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 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
- 238000003860 storage Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- YTCGLFCOUJIOQH-UHFFFAOYSA-N 1,3,4-oxadiazole-2,5-diamine Chemical compound NC1=NN=C(N)O1 YTCGLFCOUJIOQH-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-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
- XOJRVZIYCCJCRD-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 XOJRVZIYCCJCRD-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XGKKWUNSNDTGDS-UHFFFAOYSA-N 2,5-dimethylheptane-1,7-diamine Chemical compound NCC(C)CCC(C)CCN XGKKWUNSNDTGDS-UHFFFAOYSA-N 0.000 description 1
- HHOJVZAEHZGDRB-UHFFFAOYSA-N 2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=NC(N)=NC(N)=N1 HHOJVZAEHZGDRB-UHFFFAOYSA-N 0.000 description 1
- PWTLARNDEIPZOG-UHFFFAOYSA-N 2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl prop-2-enoate Chemical compound NC1=NC(N)=NC(CCOC(=O)C=C)=N1 PWTLARNDEIPZOG-UHFFFAOYSA-N 0.000 description 1
- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- YEEIWUUBRYZFEH-UHFFFAOYSA-N 3-methoxyhexane-1,6-diamine Chemical compound NCCC(OC)CCCN YEEIWUUBRYZFEH-UHFFFAOYSA-N 0.000 description 1
- SGEWZUYVXQESSB-UHFFFAOYSA-N 3-methylheptane-1,7-diamine Chemical compound NCCC(C)CCCCN SGEWZUYVXQESSB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZWIBGDOHXGXHEV-UHFFFAOYSA-N 4,4-dimethylheptane-1,7-diamine Chemical compound NCCCC(C)(C)CCCN ZWIBGDOHXGXHEV-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-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
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- NOHQTLHHNIKWBA-UHFFFAOYSA-N [SiH4].NC(=O)N Chemical compound [SiH4].NC(=O)N NOHQTLHHNIKWBA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920006285 olefinic elastomer Polymers 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、半導体パッケージやプリント配線板用に好適な熱硬化性樹脂組成物、並びに、これを用いたプリプレグ、樹脂付フィルム、積層板、多層プリント配線板及び半導体パッケージに関する。 The present invention relates to a thermosetting resin composition suitable for a semiconductor package or a printed wiring board, and a prepreg, a resin-coated film, a laminate, a multilayer printed wiring board, and a semiconductor package using the same.
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、これに伴って、配線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、低熱膨張性を兼備することが要求されている。
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する樹脂組成物をガラスクロスに含浸したプリプレグを硬化し、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、高多層化構成に伴う耐熱性向上への要請に対応するには、どうしてもその耐熱性には限界がある。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）。
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。しかし、無機充填材の充填量を増やすことで低熱膨張化する手法では、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場合がある。
With the trend toward smaller and higher performance electronic devices in recent years, printed wiring boards have become increasingly dense and highly integrated, and with this, reliability has been improved by improving the heat resistance of laminated boards for wiring. There is an increasing demand for improvement. In such applications, it is required to have both excellent heat resistance and low thermal expansion.
As a laminated board for printed wiring boards, a prepreg in which a glass cloth is impregnated with a resin composition mainly composed of an epoxy resin is cured and molded. In general, epoxy resin has a good balance of insulation, heat resistance, cost, etc. However, in order to respond to the demand for improved heat resistance due to recent high-density mounting of printed wiring boards and multi-layered structures, it is inevitably necessary. There is a limit to 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).
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. Is required. However, in the method of reducing the thermal expansion by increasing the filling amount of the inorganic filler, there are cases where the insulation reliability is lowered due to moisture absorption, the resin-wiring layer is insufficiently adhered, and the press molding is poor.
また、高密度実装、高多層化積層板に広く使用されているポリビスマレイミド樹脂は、その耐熱性は非常に優れているものの、吸湿性が高く、接着性に難点がある。さらに、積層時にエポキシ樹脂に比べ高温、長時間を必要とするため、生産性が悪いという欠点もあった。一般的に、エポキシ樹脂の場合１８０℃以下の温度で硬化可能であるが、ポリビスマレイミド樹脂を積層する場合は２２０℃以上の高温で且つ長時間の処理が必要である。特許文献２に記載の変性イミド樹脂組成物では、耐湿性や接着性が改良されるものの、メチルエチルケトン等の汎用性溶剤への可溶性を確保するために、水酸基とエポキシ基を含有する低分子化合物で変性している。このため、得られる変性イミド樹脂の耐熱性はポリビスマレイミド樹脂と比較して、大幅に劣るという問題があった。 In addition, polybismaleimide resins widely used for high-density packaging and highly multilayered laminates are very excellent in heat resistance, but have high hygroscopicity and have difficulty in adhesion. Furthermore, since a high temperature and a long time are required compared with an epoxy resin at the time of lamination | stacking, there also existed a fault that productivity was bad. In general, an epoxy resin can be cured at a temperature of 180 ° C. or lower, but in the case of laminating a polybismaleimide resin, a treatment at a high temperature of 220 ° C. or higher and a long time is required. In the modified imide resin composition described in Patent Document 2, although moisture resistance and adhesion are improved, in order to ensure solubility in general-purpose solvents such as methyl ethyl ketone, a low molecular compound containing a hydroxyl group and an epoxy group is used. Denatured. For this reason, there existed a problem that the heat resistance of the modified imide resin obtained was significantly inferior compared with poly bismaleimide resin.
本発明の目的は、こうした現状に鑑み、優れた低硬化収縮性、低熱膨張性、良好な銅箔接着性、及び高弾性率を有する熱硬化性樹脂組成物、これを用いたプリプレグ、樹脂付フィルム、積層板、多層プリント配線板及び半導体パッケージ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 thermosetting resin composition having excellent low curing shrinkage, low thermal expansion, good copper foil adhesion, and high elastic modulus, a prepreg using the same, and a resin-attached resin. It is to provide a film, a laminated board, a multilayer printed wiring board, and a semiconductor package.
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、１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）と、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（Ｂ）を含有する、或いは前記アミノ変性シロキサン化合物（Ａ）とマレイミド化合物（Ｂ）を反応させて得られる変性イミド樹脂を含有する熱硬化性樹脂組成物を用いることで上記の目的を達成し得ることを見出し、本発明を完成するに至った。本発明は、かかる知見にもとづいて完成したものである。 As a result of intensive studies to achieve the above object, the inventors of the present invention have an amino-modified siloxane compound (A) having at least one primary amino group in one molecule and at least two in one molecule. A thermosetting resin composition containing a maleimide compound (B) having an N-substituted maleimide group or containing a modified imide resin obtained by reacting the amino-modified siloxane compound (A) and the maleimide compound (B). It has been found that the above-mentioned purpose can be achieved by using it, and the present invention has been completed. The present invention has been completed based on such knowledge.
すなわち、本発明は、以下の熱硬化性樹脂組成物、これを用いたプリプレグ、樹脂付フィルム、積層板、多層プリント配線板及び半導体パッケージを提供するものである。 That is, this invention provides the following thermosetting resin compositions, a prepreg using the same, a film with resin, a laminated board, a multilayer printed wiring board, and a semiconductor package.
１．１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）と、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（Ｂ）を含有する熱硬化性樹脂組成物。
２．１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）と、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（Ｂ）を反応させて得られる変性イミド樹脂を含有する熱硬化性樹脂組成物。
３．さらに、下記一般式（１）に示す酸性置換基を有するアミン化合物（Ｃ）を含有する上記１又は２に記載の熱硬化性樹脂組成物。
４．１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）と、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（Ｂ）と、下記一般式（１）酸性置換基を有するアミン化合物（Ｃ）を反応させて得られる、酸性置換基を有する変性イミド樹脂を含有する熱硬化性樹脂組成物。
５．１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）が、１分子中に少なくとも１個のエポキシ基を有するシロキサン化合物（i）と、１分子中に少なくとも２個の一級アミノ基を有するアミン化合物（ii）を反応させて得られる、上記１〜４のいずれかに記載の熱硬化性樹脂組成物。
６．さらに、熱可塑性エラストマー（Ｄ）を含有する上記１〜５のいずれかに記載の熱硬化性樹脂組成物。
７．さらに、エポキシ樹脂及びシアネート樹脂から選ばれる少なくとも一種の熱硬化性樹脂（Ｅ）を含有する上記１〜６のいずれかに記載の熱硬化性樹脂組成物。
８．さらに、無機充填材（Ｆ）を含有する上記１〜７のいずれかに記載の熱硬化性樹脂組成物。
９．さらに、硬化促進剤（Ｇ）を含有する上記１〜８のいずれかに記載の熱硬化性樹脂組成物。
１０．上記１〜９のいずれかに記載の熱硬化性樹脂組成物を基材に含浸してなるプリプレグ。
１１．上記１〜９のいずれかに記載の熱硬化性樹脂組成物を支持体上に層形成してなる樹脂付フィルム。
１２．上記１０に記載のプリプレグを積層成形して得られる積層板。
１３．上記１１に記載の樹脂付フィルムを積層成形して得られる積層板。
１４．上記１２又は１３に記載の積層板を用いて製造された多層プリント配線板。
１５．上記１４に記載の多層プリント配線板に半導体素子を搭載してなる半導体パッケージ。
1.1 Thermosetting containing an amino-modified siloxane compound (A) having at least one primary amino group in a molecule and a maleimide compound (B) having at least two N-substituted maleimide groups in one molecule Resin composition.
2. Obtained by reacting an amino-modified siloxane compound (A) having at least one primary amino group in a molecule with a maleimide compound (B) having at least two N-substituted maleimide groups in one molecule. A thermosetting resin composition containing a modified imide resin.
3. Furthermore, the thermosetting resin composition of said 1 or 2 containing the amine compound (C) which has an acidic substituent shown to following General formula (1).
4.1 Amino-modified siloxane compound (A) having at least one primary amino group in one molecule, a maleimide compound (B) having at least two N-substituted maleimide groups in one molecule, and the following general formula ( 1) The thermosetting resin composition containing the modified imide resin which has an acidic substituent obtained by making the amine compound (C) which has an acidic substituent react.
5. An amino-modified siloxane compound (A) having at least one primary amino group in one molecule is a siloxane compound (i) having at least one epoxy group in one molecule and at least two in one molecule. The thermosetting resin composition according to any one of the above 1 to 4, obtained by reacting an amine compound (ii) having a primary amino group.
6). Furthermore, the thermosetting resin composition in any one of said 1-5 containing a thermoplastic elastomer (D).
7). Furthermore, the thermosetting resin composition in any one of said 1-6 containing at least 1 type of thermosetting resin (E) chosen from an epoxy resin and cyanate resin.
8). Furthermore, the thermosetting resin composition in any one of said 1-7 containing an inorganic filler (F).
9. Furthermore, the thermosetting resin composition in any one of said 1-8 containing a hardening accelerator (G).
10. A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of 1 to 9 above.
11. The film with a resin formed by carrying out the layer formation of the thermosetting resin composition in any one of said 1-9 on a support body.
12 A laminate obtained by laminating the prepreg as described in 10 above.
13. A laminate obtained by laminating the film with resin as described in 11 above.
14 14. A multilayer printed wiring board produced using the laminate as described in 12 or 13 above.
15. 15. A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board described in 14 above.
本発明によれば、優れた低硬化収縮性、低熱膨張性、良好な銅箔接着性、及び高弾性率を有する熱硬化性樹脂組成物、これを用いたプリプレグ、樹脂付フィルム、積層板、多層プリント配線板及び半導体パッケージを提供することができる。
特に、本発明の熱硬化性樹脂組成物を、基材に含浸してなるプリプレグ、支持体上に層形成してなる樹脂付フィルム、及び該プリプレグ又は該樹脂付フィルムを積層成形することにより製造した積層板は、低硬化収縮性、低熱膨張性、優れた銅箔接着性、及び高弾性率を有し、多層プリント配線板、半導体パッケージとして有用である。
According to the present invention, a thermosetting resin composition having excellent low curing shrinkage, low thermal expansibility, good copper foil adhesion, and high elastic modulus, a prepreg using the same, a film with resin, a laminate, A multilayer printed wiring board and a semiconductor package can be provided.
In particular, a prepreg obtained by impregnating a base material with the thermosetting resin composition of the present invention, a resin-coated film formed on a support, and the prepreg or the resin-coated film are produced by lamination molding. The laminated board has low curing shrinkage, low thermal expansion, excellent copper foil adhesion, and high elastic modulus, and is useful as a multilayer printed wiring board and a semiconductor package.
以下、本発明について詳細に説明する。
本発明の熱硬化性樹脂組成物は、１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）（以下、アミノ変性シロキサン化合物（Ａ）と呼ぶことがある）と、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（Ｂ）（以下、マレイミド化合物（Ｂ）と呼ぶことがある）を含有するものである。
Hereinafter, the present invention will be described in detail.
The thermosetting resin composition of the present invention comprises an amino-modified siloxane compound (A) having at least one primary amino group in one molecule (hereinafter sometimes referred to as amino-modified siloxane compound (A)), 1 It contains a maleimide compound (B) having at least two N-substituted maleimide groups in the molecule (hereinafter sometimes referred to as maleimide compound (B)).
本発明に用いられる１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）は、特に限定されるものではないが、例えば、１分子中に少なくとも１個のエポキシ基を有するシロキサン化合物（i）（以下、シロキサン化合物（i）と呼ぶことがある）と、１分子中に少なくとも２個の一級アミノ基を有するアミン化合物（ii）（以下、アミン化合物（ii）と呼ぶことがある）を反応させて得ることが好ましい。
１分子中に少なくとも１個のエポキシ基を有するシロキサン化合物（i）は、１分子中に少なくとも２個のエポキシ基を有するシロキサン化合物が好ましく、１分子中に２個のエポキシ基を有するシロキサン化合物がより好ましい。
The amino-modified siloxane compound (A) having at least one primary amino group in one molecule used in the present invention is not particularly limited. For example, it has at least one epoxy group in one molecule. Siloxane compound (i) (hereinafter sometimes referred to as siloxane compound (i)) and amine compound (ii) having at least two primary amino groups in one molecule (hereinafter referred to as amine compound (ii)) Is preferably obtained by reacting.
The siloxane compound (i) having at least one epoxy group in one molecule is preferably a siloxane compound having at least two epoxy groups in one molecule, and is preferably a siloxane compound having two epoxy groups in one molecule. More preferred.
本発明に用いられる１分子中に少なくとも１個のエポキシ基を有するシロキサン化合物（i）としては、市販品を用いてもよい。市販品としては、例えば、両末端にエポキシ基を有する「Ｘ−２２−１６３」（官能基当量２００）、「ＫＦ−１０５」（官能基当量４９０）、「Ｘ−２２−１６３Ａ」（官能基当量１０００）、「Ｘ−２２−１６３Ｂ」（官能基当量１７５０）、「Ｘ−２２−１６３Ｃ」（官能基当量２７００）、両末端に脂環式エポキシ基を有する「Ｘ−２２−１６９ＡＳ」（官能基当量５００）、「Ｘ−２２−１６９Ｂ」（官能基当量１７００）、一方の末端にエポキシ基を有する「Ｘ−２２−１７３０Ｘ」（官能基当量４５００）、側鎖及び両末端にエポキシ基を有する「Ｘ−２２−９００２」（官能基当量５０００）、側鎖にエポキシ基を有する「Ｘ−２２−３４３」（官能基当量５２５）、「ＫＦ−１０１」（官能基当量３５０）、「ＫＦ−１００１」（官能基当量３５００）、「Ｘ−２２−２０００」（官能基当量６２０）、「Ｘ−２２−４７４１」（官能基当量２５００）、「ＫＦ−１００２」（官能基当量４３００）、側鎖に脂環式エポキシ樹脂を有する「Ｘ−２２−２０４６」（官能基当量６００）、「ＫＦ−１０２」（官能基当量３６００）等が挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。さらには各種エポキシ樹脂と混合して使用することができる。これらの中で、例えば、耐熱性の点から「Ｘ−２２−１６３Ａ」、「Ｘ−２２−１６３Ｂ」、「Ｘ−２２−１６３Ｃ」、「Ｘ−２２−３４３」、「Ｘ−２２−９００２」、「ＫＦ−１０１」が好ましく、「Ｘ−２２−１６３Ａ」、「Ｘ−２２−１６３Ｂ」がより好ましく、低熱膨張率の点から「Ｘ−２２−１６３Ｂ」が特に好ましい。（いずれも、信越化学工業株式会社の商品名であり、官能基当量の単位はｇ／ｍｏｌである。） A commercially available product may be used as the siloxane compound (i) having at least one epoxy group in one molecule used in the present invention. Examples of commercially available products include “X-22-163” (functional group equivalent 200), “KF-105” (functional group equivalent 490), and “X-22-163A” (functional group) having epoxy groups at both ends. Equivalent 1000), “X-22-163B” (functional group equivalent 1750), “X-22-163C” (functional group equivalent 2700), “X-22-169AS” having an alicyclic epoxy group at both ends ( Functional group equivalent 500), “X-22-169B” (functional group equivalent 1700), “X-22-1730X” (functional group equivalent 4500) having an epoxy group at one terminal, side chain and epoxy group at both terminals “X-22-9002” (functional group equivalent 5000), “X-22-343” (functional group equivalent 525) having an epoxy group in the side chain, “KF-101” (functional group equivalent 350), “ KF-10 1 ”(functional group equivalent 3500),“ X-22-2000 ”(functional group equivalent 620),“ X-22-4741 ”(functional group equivalent 2500),“ KF-1002 ”(functional group equivalent 4300), side Examples include “X-22-2046” (functional group equivalent 600) and “KF-102” (functional group equivalent 3600) having an alicyclic epoxy resin in the chain. These may be used alone or in combination of two or more. Furthermore, it can be used by mixing with various epoxy resins. Among these, from the viewpoint of heat resistance, for example, “X-22-163A”, “X-22-163B”, “X-22-163C”, “X-22-343”, “X-22-9002” "," KF-101 "are preferable," X-22-163A "and" X-22-163B "are more preferable, and" X-22-163B "is particularly preferable from the viewpoint of a low thermal expansion coefficient. (All are trade names of Shin-Etsu Chemical Co., Ltd., and the unit of functional group equivalent is g / mol.)
本発明に用いられる１分子中に少なくとも２個の一級アミノ基を有するアミン化合物（ii）は、１分子中に２個の一級アミノ基を有するアミン化合物が好ましい。
本発明に用いられる１分子中に少なくとも２個の一級アミノ基を有するアミン化合物（ii）としては、例えば、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、ｏ−フェニレンジアミン、３−メチル−１，４−ジアミノベンゼン、２，５−ジメチル−１，４−ジアミノベンゼン、４，４'−ジアミノジフェニルメタン、３，３'−ジメチル−４，４'−ジアミノ−ジフェニルメタン、３，３'−ジエチル−４，４'−ジアミノ−ジフェニルメタン、４，４'−ジアミノジフェニルエーテル、４，４'−ジアミノジフェニルスルホン、３，３'−ジアミノジフェニルスルホン、４，４'−ジアミノジフェニルケトン、ベンジジン、３，３'−ジメチル−４，４'−ジアミノビフェニル、２，２'−ジメチル−４，４'−ジアミノビフェニル、３，３'−ジヒドロキシベンジジン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、３，３−ジメチル−５，５−ジエチル−４，４−ジフェニルメタンジアミン、２，２−ビス（４−アミノフェニル）プロパン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４，４'−ビス（４−アミノフェノキシ）ビフェニル、ビス（４−（４−アミノフェノキシ）フェニル）スルホン、ビス（４−（３−アミノフェノキシ）フェニル）スルホン、９，９−ビス（４−アミノフェニル）フルオレン等の芳香族アミン類、エチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、２，５−ジメチルヘキサメチレンジアミン、３−メトキシヘキサメチレンジアミン、２，５−ジメチルヘプタメチレンジアミン、３−メチルヘプタメチレンジアミン、４，４−ジメチルヘプタメチレンジアミン、５−メチルノナメチレンジアミン、１，４−ジアミノシクロヘキサン、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン、ジアミノポリシロキサン、２，５−ジアミノ−１，３，４−オキサジアゾ−ル、ビス（４−アミノシクロヘキシル）メタン等の脂肪族アミン類、メラミン、ベンゾグアナミン、アセトグアナミン、２，４−ジアミノ−６−ビニル−ｓ−トリアジン、２，４−ジアミノ−６−アリル−ｓ−トリアジン、２，４−ジアミノ−６−アクリロイルオキシエチル−ｓ−トリアジン、２，４−ジアミノ−６−メタクリロイルオキシエチル−ｓ−トリアジン等のグアナミン化合物類などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。
The amine compound (ii) having at least two primary amino groups in one molecule used in the present invention is preferably an amine compound having two primary amino groups in one molecule.
Examples of the amine compound (ii) having at least two primary amino groups in one molecule used in the present invention include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, and 3-methyl-1,4. -Diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamino-diphenylmethane, 3,3'-diethyl-4, 4'-diamino-diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl -4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydro Xibenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) Propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone , Aromatic amines such as 9,9-bis (4-aminophenyl) fluorene, ethylenediamine, tetramethylenediamine, pentamethylene Diamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methyl Heptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, diaminopolysiloxane, 2,5 -Aliphatic amines such as diamino-1,3,4-oxadiazol and bis (4-aminocyclohexyl) methane, melamine, benzoguanamine, acetoguanamine, 2,4-diamino-6-vinyl-s-triazine, 2 , And guanamine compounds such as 2-diamino-6-allyl-s-triazine, 2,4-diamino-6-acryloyloxyethyl-s-triazine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, and the like. It is done. These may be used alone or in combination of two or more.
これらの中で、例えば、反応時の反応性が高く、より高耐熱性化できる芳香族アミン類である４，４'−ジアミノジフェニルメタン、３，３'−ジメチル−４，４'−ジアミノビフェニル、３，３'−ジメチル−４，４'−ジアミノ−ジフェニルメタン、３，３'−ジエチル−４，４'−ジアミノ−ジフェニルメタン、４，４'−ビス（４−アミノフェノキシ）ビフェニル、ビス（４−（４−アミノフェノキシ）フェニル）プロパンがより好ましく、安価であることや溶剤への溶解性の点から４，４'−ジアミノジフェニルメタン、３，３'−ジメチル−４，４'−ジアミノビフェニル、３，３'−ジエチル−４，４'−ジアミノ−ジフェニルメタン、ビス（４−（４−アミノフェノキシ）フェニル）プロパンが好ましく、低熱膨張性や誘電特性の点から、３，３'−ジエチル−４，４'−ジアミノ−ジフェニルメタン、ビス（４−（４−アミノフェノキシ）フェニル）プロパンが特に好ましい。また、高弾性率化できる点から、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、３−メチル−１，４−ジアミノベンゼン、２，５−ジメチル−１，４−ジアミノベンゼンも好ましい。 Among these, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, which are aromatic amines that are highly reactive at the time of reaction and can be further improved in heat resistance, 3,3′-dimethyl-4,4′-diamino-diphenylmethane, 3,3′-diethyl-4,4′-diamino-diphenylmethane, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (4-Aminophenoxy) phenyl) propane is more preferable, and 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3 is inexpensive in view of solubility in a solvent. , 3′-diethyl-4,4′-diamino-diphenylmethane and bis (4- (4-aminophenoxy) phenyl) propane are preferred, and from the viewpoint of low thermal expansion and dielectric properties, 3, 3′-diethyl-4,4′-diamino-diphenylmethane, bis (4- (4-aminophenoxy) phenyl) propane are particularly preferred. Moreover, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene are also preferable from the viewpoint of increasing the elastic modulus.
本発明において、１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）を得るための反応としては、特に限定されるものではないが、例えば、１分子中に少なくとも１個のエポキシ基を有するシロキサン化合物（i）と、１分子中に少なくとも２個の一級アミノ基を有するアミン化合物（ii）を有機溶媒中で反応させることにより、１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）を得ることが好ましい。 In the present invention, the reaction for obtaining the amino-modified siloxane compound (A) having at least one primary amino group in one molecule is not particularly limited, but for example, at least one in one molecule. By reacting the siloxane compound (i) having an epoxy group with an amine compound (ii) having at least two primary amino groups in one molecule in an organic solvent, at least one primary amino group in one molecule is reacted. It is preferable to obtain an amino-modified siloxane compound (A) having a group.
本反応に使用される有機溶媒としては、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、γ−ブチロラクトン等のエステル系溶剤などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。これらの中で、例えば、溶解性の点からプロピレングリコールモノメチルエーテル、シクロヘキサノン、トルエン、ジメチルホルムアミド、ジメチルアセトアミド、γ−ブチロラクトン等が好ましく、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、トルエンがより好ましい。 Examples of the organic solvent used in this reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, tetrahydrofuran Ether solvents such as toluene, xylene, mesitylene and other aromatic solvents, dimethylformamide, dimethylacetamide, nitrogen atom-containing solvents such as N-methylpyrrolidone, sulfur atom-containing solvents such as dimethylsulfoxide, and esters such as γ-butyrolactone. System solvents and the like. These may be used alone or in combination of two or more. Among these, for example, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, γ-butyrolactone and the like are preferable from the viewpoint of solubility, and propylene glycol monomethyl which is highly volatile and hardly remains as a residual solvent at the time of manufacturing a prepreg Ether and toluene are more preferable.
本反応には、必要により任意に反応触媒を使用することができ、反応触媒の例としては、ｐ−トルエンスルホン酸等の酸性触媒、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などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。 In this reaction, a reaction catalyst can be optionally used as necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid, amines such as triethylamine, pyridine and tributylamine, methylimidazole, phenyl Examples thereof include imidazoles such as imidazole and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more.
ここで、１分子中に少なくとも１個のエポキシ基を有するシロキサン化合物（i）と、１分子中に２個の一級アミノ基を有するアミン化合物（ii）の使用量は、例えば、アミン化合物（ii）の一級アミノ基数〔アミン化合物（ii）の使用量（ｇ）／アミン化合物（ii）の一級アミノ基の官能基当量（ｇ／ｍｏｌ）〕が、シロキサン化合物（i）のエポキシ基数〔シロキサン化合物（i）の使用量（ｇ）／シロキサン化合物（i）のエポキシ基の官能基当量（ｇ／ｍｏｌ）〕の１．０〜１０．０倍の範囲になるように使用することが好ましく、１．５〜５倍がより好ましい。１．０倍以上とすることにより、銅箔接着性や弾性率の低下が抑制され、また、１０．０倍以下とすることにより、低熱膨張性や耐熱性の低下が抑制される。 Here, the amount of the siloxane compound (i) having at least one epoxy group in one molecule and the amine compound (ii) having two primary amino groups in one molecule is, for example, an amine compound (ii) The number of primary amino groups [amount of amine compound (ii) used (g) / functional equivalent (g / mol) of primary amino group of amine compound (ii)] is the number of epoxy groups [siloxane compound of siloxane compound (i)] The amount of (i) used (g) / the functional group equivalent (g / mol) of the epoxy group of the siloxane compound (i)] is preferably 1.0 to 10.0 times the range. More preferably 5 to 5 times. By setting it as 1.0 times or more, the fall of copper foil adhesiveness and an elastic modulus is suppressed, and by making it 10.0 times or less, the fall of low thermal expansibility and heat resistance is suppressed.
また、有機溶媒の使用量は、例えば、シロキサン化合物（i）、及びアミン化合物（ii）の総和１００質量部に対して、２５〜２０００質量部とすることが好ましく、４０〜１０００質量部とすることがより好ましく、４０〜５００質量部とすることが特に好ましい。有機溶媒の使用量を２５質量部以上とすることにより、溶解性が不足することが少なく、また２０００質量部以下とすることにより、反応に長時間を要さない傾向がある。 Moreover, it is preferable to set it as 25-2000 mass parts with respect to 100 mass parts of sum total of a siloxane compound (i) and an amine compound (ii), for example, and the usage-amount of an organic solvent is 40-1000 mass parts. It is more preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, the solubility is rarely insufficient, and when it is 2000 parts by mass or less, there is a tendency that the reaction does not require a long time.
上記の原料、有機溶媒、必要により反応触媒を反応釜に仕込み、必要により加熱、保温しながら０．１時間から１０時間攪拌し反応させることにより、アミノ変性シロキサン化合物（Ａ）が得られる。
反応温度は、例えば、７０〜１５０℃が好ましく、１００〜１３０℃がより好ましい。温度を７０℃以上とすることにより、反応速度が遅くなりすぎることが少なく、温度を１５０℃以下とすることにより、反応溶媒に高沸点の溶媒を必要としないため、プリプレグを製造する際に、残溶剤が残りにくく、耐熱性の低下が抑制される。
The amino-modified siloxane compound (A) is obtained by charging the above raw materials, organic solvent, and if necessary, a reaction catalyst in a reaction kettle and stirring and reacting for 0.1 to 10 hours while heating and keeping warm as necessary.
For example, the reaction temperature is preferably 70 to 150 ° C, and more preferably 100 to 130 ° C. When the temperature is set to 70 ° C. or higher, the reaction rate is less likely to be too slow, and when the temperature is set to 150 ° C. or lower, the reaction solvent does not require a high boiling point solvent. Residual solvent hardly remains and heat resistance is prevented from lowering.
また、アミノ変性シロキサン化合物（Ａ）の重量平均分子量（Ｍｗ）は、例えば、１０００〜３０００００が好ましく、特に６０００〜１５００００が好ましい。重量平均分子量（Ｍｗ）が前記下限値以上であると低熱膨張性が優れ、前記上限値以下であると相溶性に優れる。なお、重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定を行い、標準ポリスチレンを用いて作製した検量線により換算したものである。
重量平均分子量（Ｍｗ）の測定は、例えば、以下条件で行うことが出来る。
測定装置としては、オートサンプラー（東ソー株式会社製ＡＳ−８０２０）、カラムオーブン（日本分光株式会社製８６０−Ｃ０）、ＲＩ検出器（日本分光株式会社製８３０−ＲＩ）、ＵＶ／ＶＩＳ検出器（日本分光株式会社製８７０−ＵＶ）、ＨＰＬＣポンプ（日本分光株式会社製８８０−ＰＵ）を使用することが可能である。
また、使用カラムとしては、東ソー株式会社製 ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２０００，２３００を使用でき、測定条件としては、測定温度４０℃、流量０．５ｍｌ/ｍｉｎ、溶媒をテトラヒドロフランとすることで測定可能である。
In addition, the weight average molecular weight (Mw) of the amino-modified siloxane compound (A) is preferably, for example, 1000 to 300000, and particularly preferably 6000 to 150,000. When the weight average molecular weight (Mw) is not less than the lower limit, the low thermal expansion property is excellent, and when it is not more than the upper limit, the compatibility is excellent. The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve produced using standard polystyrene.
The weight average molecular weight (Mw) can be measured, for example, under the following conditions.
As a measuring device, an auto sampler (AS-8020 manufactured by Tosoh Corporation), a column oven (860-C0 manufactured by JASCO Corporation), an RI detector (830-RI manufactured by JASCO Corporation), a UV / VIS detector ( JASCO Corporation 870-UV) and HPLC pump (JASCO Corporation 880-PU) can be used.
Further, TSKgel SuperHZ2000, 2300 manufactured by Tosoh Corporation can be used as the column used, and measurement can be performed by using a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent of tetrahydrofuran.
本発明に用いられる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（Ｂ）は、１分子中に２個のＮ-置換マレイミド基を有するマレイミド化合物が好ましい。
本発明の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（Ｂ）は、例えば、ビス（４−マレイミドフェニル）メタン、ポリフェニルメタンマレイミド、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、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、４−メチル−１，３−フェニレンビスマレイミド、ｍ−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）プロパン等が挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。
The maleimide compound (B) having at least two N-substituted maleimide groups in one molecule used in the present invention is preferably a maleimide compound having two N-substituted maleimide groups in one molecule.
The maleimide compound (B) having at least two N-substituted maleimide groups in one molecule of the present invention includes, for example, bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, Bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2 -Bis (4- (4-maleimidophenoxy) phenyl) propane and the like. These may be used alone or in combination of two or more.
これらの中で、例えば、反応性が高く、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、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパンが好ましく、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、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパンがより好ましく、安価である点からビス（４−マレイミドフェニル）メタンが特に好ましい。 Among these, for example, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, and 2,2-bis (4- (4-maleimidophenoxy), which have high reactivity and can have higher heat resistance. Phenyl) propane is preferable, and from the viewpoint of solubility in a solvent, bis (4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are more preferable and inexpensive. Bis (4-maleimidophenyl) methane is particularly preferred.
本発明の熱硬化性樹脂組成物において、アミノ変性シロキサン化合物（Ａ）の使用量は、例えば、樹脂成分の総和１００質量部当たり、１〜３０質量部とすることが好ましく、５〜２０質量部とすることが、低硬化収縮性、銅箔接着性、耐薬品性の点からより好ましい。
マレイミド化合物（Ｂ）の使用量は、例えば、樹脂成分の総和１００質量部当たり、３０〜９９質量部とすることが好ましく、４０〜８０質量部とすることがより好ましい。
In the thermosetting resin composition of the present invention, the use amount of the amino-modified siloxane compound (A) is preferably 1 to 30 parts by mass, for example, 5 to 20 parts by mass per 100 parts by mass of the total resin components. Is more preferable from the viewpoint of low curing shrinkage, copper foil adhesion, and chemical resistance.
The amount of the maleimide compound (B) used is preferably, for example, 30 to 99 parts by mass, and more preferably 40 to 80 parts by mass, per 100 parts by mass of the total resin components.
本発明の熱硬化性樹脂組成物は、１分子中に少なくとも１個の一級アミノ基を有するアミノ変性シロキサン化合物（Ａ）と、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（Ｂ）を反応させて得られる変性イミド樹脂を含有するものも包含する（以下、該反応を「プレ反応」とも称する）。このようなプレ反応を行うことにより、分子量を制御することができ、更なる低硬化収縮性、低熱膨張性、弾性率向上を行うことができる。 The thermosetting resin composition of the present invention comprises an amino-modified siloxane compound (A) having at least one primary amino group in one molecule and a maleimide compound having at least two N-substituted maleimide groups in one molecule. Also included are those containing a modified imide resin obtained by reacting (B) (hereinafter, this reaction is also referred to as “pre-reaction”). By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage, low thermal expansion, and improvement in elastic modulus can be performed.
このプレ反応は、有機溶媒中で加熱保温しながらアミノ変性シロキサン化合物（Ａ）、マレイミド化合物（Ｂ）を反応させて変性イミド樹脂を合成することが好ましい。
有機溶媒中でアミノ変性シロキサン化合物（Ａ）、及びマレイミド化合物（Ｂ）を反応させる際の反応温度は、例えば、７０〜１５０℃であることが好ましく、１００〜１３０℃であることがより好ましい。反応時間は、例えば、０．１〜１０時間であることが好ましく、１〜６時間であることがより好ましい。
In this pre-reaction, it is preferable to synthesize a modified imide resin by reacting the amino-modified siloxane compound (A) and the maleimide compound (B) while heating and keeping in an organic solvent.
The reaction temperature when the amino-modified siloxane compound (A) and the maleimide compound (B) are reacted in an organic solvent is, for example, preferably 70 to 150 ° C, and more preferably 100 to 130 ° C. For example, the reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
このプレ反応において、アミノ変性シロキサン化合物（Ａ）とマレイミド化合物（Ｂ）の使用量は、例えば、マレイミド化合物（Ｂ）のマレイミド基数〔マレイミド化合物（Ｂ）の使用量（ｇ）／マレイミド化合物（Ｂ）のマレイミド基の官能基当量（ｇ／ｍｏｌ）〕が、アミノ変性シロキサン化合物（Ａ）の一級アミノ基数〔アミノ変性シロキサン化合物（Ａ）の使用量（ｇ）／アミノ変性シロキサン化合物（Ａ）の一級アミノ基の官能基当量（ｇ／ｍｏｌ）〕の２．０〜１５．０倍になる範囲であることが好ましい。２．０倍以上とすることによりゲル化及び耐熱性の低下が抑制され、また、１５．０倍以下とすることにより有機溶剤への溶解性、耐熱性の低下が抑制される。 In this pre-reaction, the amount of the amino-modified siloxane compound (A) and the maleimide compound (B) used is, for example, the number of maleimide groups in the maleimide compound (B) [the amount of maleimide compound (B) used (g) / maleimide compound (B). ) Is the number of primary amino groups of the amino-modified siloxane compound (A) [amount of amino-modified siloxane compound (A) used (g) / amino-modified siloxane compound (A) The functional group equivalent (g / mol) of the primary amino group is preferably in the range of 2.0 to 15.0 times. By setting it to 2.0 times or more, gelation and a decrease in heat resistance are suppressed, and by setting it to 15.0 times or less, solubility in an organic solvent and a decrease in heat resistance are suppressed.
プレ反応におけるマレイミド化合物（Ｂ）の使用量は、上記のような関係を維持しつつ、例えば、アミノ変性シロキサン化合物（Ａ）１００質量部に対して１０〜３０００質量部が好ましく、３０〜１５００質量部がより好ましく、４０〜３００質量部がより好ましい。１０質量部以上とすることにより良好な耐熱性が得られ、３０００質量部以下とすることにより低熱膨張性を良好に保つことができる傾向にある。 The amount of the maleimide compound (B) used in the pre-reaction is, for example, preferably 10 to 3000 parts by weight, and 30 to 1500 parts by weight with respect to 100 parts by weight of the amino-modified siloxane compound (A) while maintaining the above relationship. Part is more preferable, and 40 to 300 parts by mass is more preferable. When the amount is 10 parts by mass or more, good heat resistance is obtained, and when the amount is 3000 parts by mass or less, low thermal expansion tends to be kept good.
このプレ反応で使用される有機溶媒は、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、酢酸エチルエステルやγ−ブチロラクトン等のエステル系溶剤、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などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。 Examples of the organic solvent used in this pre-reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetic acid. Ester solvents such as ethyl ester and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide And sulfur atom-containing solvents such as These may be used alone or in combination of two or more.
これらの有機溶媒の中で、例えば、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、γ−ブチロラクトンが好ましく、低毒性であることや揮発性が高く残溶剤として残りにくい点から、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、ジメチルアセトアミドが特に好ましい。 Among these organic solvents, for example, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone has low toxicity and is highly volatile and hardly remains as a residual solvent. , Propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable.
有機溶媒の使用量は、例えば、アミノ変性シロキサン化合物（Ａ）、及びマレイミド化合物（Ｂ）の総和１００質量部に対して、２５〜２０００質量部とすることが好ましく、４０〜１０００質量部とすることがより好ましく、４０〜５００質量部とすることが特に好ましい。有機溶媒の使用量を２５質量部以上とすることにより、良好な溶解性が得られ、２０００質量部以下とすることにより、反応に長時間を要さない傾向にある。 The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass and 40 to 1000 parts by mass with respect to 100 parts by mass of the total of the amino-modified siloxane compound (A) and the maleimide compound (B). It is more preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, good solubility is obtained, and when it is 2000 parts by mass or less, the reaction does not require a long time.
また、このプレ反応には任意に反応触媒を使用することができる。例えば、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、リチウムアミド、ナトリウムアミド、カリウムアミド等のアルカリ金属アミドなどが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。 In addition, a reaction catalyst can be optionally used for this pre-reaction. Examples thereof include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and alkali metal amides such as lithium amide, sodium amide, and potassium amide. These may be used alone or in combination of two or more.
また、上記プレ反応より得られた変性イミド樹脂の使用量は、例えば、熱硬化性樹脂組成物の樹脂成分の総和１００質量部当たり、５０〜１００質量部とすることが好ましく、６０〜８０質量部とすることがより好ましい。変性イミド樹脂の使用量を５０質量部以上とすることにより低熱膨張性、高弾性率が得られる。 Moreover, it is preferable that the usage-amount of the modified imide resin obtained from the said pre reaction shall be 50-100 mass parts per 100 mass parts of sum total of the resin component of a thermosetting resin composition, for example, and 60-80 masses. More preferably, it is a part. By setting the amount of the modified imide resin used to be 50 parts by mass or more, low thermal expansion and high elastic modulus can be obtained.
本発明のアミノ変性シロキサン化合物（Ａ）と、マレイミド化合物（Ｂ）を含有する熱硬化性樹脂組成物及び前記化合物をプレ反応させて得られる変性イミド樹脂を含有する熱硬化性樹脂組成物は、単独で良好な熱硬化反応性を有するが、必要により、硬化剤及びラジカル開始剤を使用することで、耐熱性や接着性、機械強度を向上させることができる。
硬化剤としては、特に限定されるものではないが、例えば、ジシアンジアミドや、４，４’−ジアミノジフェニルメタン、４，４'−ジアミノ−３，３'−ジエチル−ジフェニルメタン、４，４’−ジアミノジフェニルスルホン、フェニレンジアミン、キシレンジアミン等の芳香族アミン類、ヘキサメチレンジアミン、２，５−ジメチルヘキサメチレンジアミン等の脂肪族アミン類、メラミン、ベンゾグアナミン等のグアナミン化合物類などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。
また、ラジカル開始剤としても、特に限定されるものではないが、例えば、アシル過酸化物、ハイドロパーオキサイド、ケトン過酸化物、ｔ−ブチル基を有する有機過酸化物、クミル基を有する過酸化物等の有機過酸化物が使用できる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。これらの中で、例えば、良好な反応性や耐熱性の点から、芳香族アミン類が好ましい。
A thermosetting resin composition containing the amino-modified siloxane compound (A) of the present invention and a maleimide compound (B) and a thermosetting resin composition containing a modified imide resin obtained by pre-reacting the compound, Although it has good thermosetting reactivity alone, if necessary, heat resistance, adhesiveness, and mechanical strength can be improved by using a curing agent and a radical initiator.
The curing agent is not particularly limited, and examples thereof include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, and 4,4′-diaminodiphenyl. Aromatic amines such as sulfone, phenylenediamine, and xylenediamine, aliphatic amines such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine, and guanamine compounds such as melamine and benzoguanamine. These may be used alone or in combination of two or more.
Further, the radical initiator is not particularly limited, but examples thereof include acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group. Organic peroxides such as products can be used. These may be used alone or in combination of two or more. Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.
さらに、本発明の熱硬化性樹脂組成物は、下記一般式（１）に示す酸性置換基を有するアミン化合物（Ｃ）を含有することができる。
酸性置換基を有するアミン化合物（Ｃ）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１種類のみを用いても、２種類以上を混合して用いてもよい。
これらの中で、例えば、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い。
Examples of the amine compound (C) having an acidic substituent include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o- Aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. These may be used alone or in combination of two or more.
Among these, for example, in terms of solubility and synthesis yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5- Dihydroxyaniline is preferred, and m-aminophenol and p-aminophenol are more preferred from the viewpoint of heat resistance.
酸性置換基を有するアミン化合物（Ｃ）の使用量は、例えば、樹脂成分の総和１００質量部当たり、０．５〜３０質量部とすることが好ましく、１〜２０質量部とすることが、低熱膨張性の点からより好ましい。 The amount of the amine compound (C) having an acidic substituent is, for example, preferably 0.5 to 30 parts by mass, and 1 to 20 parts by mass per 100 parts by mass of the total resin components. More preferable from the viewpoint of expansibility.
本発明の熱硬化性樹脂組成物は、アミノ変性シロキサン化合物（Ａ）と、マレイミド化合物（Ｂ）と、酸性置換基を有するアミン化合物（Ｃ）を反応させて得られる、酸性置換基を有する変性イミド樹脂を含有するものも包含する（以下、該反応を「プレ反応」とも称する）。このようなプレ反応を行うことにより、分子量を制御することができ、更なる低硬化収縮性、低熱膨張性、銅箔接着性向上を行うことができる。 The thermosetting resin composition of the present invention is modified with an acidic substituent obtained by reacting an amino-modified siloxane compound (A), a maleimide compound (B), and an amine compound (C) having an acidic substituent. Those containing an imide resin are also included (hereinafter, this reaction is also referred to as “pre-reaction”). By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage, low thermal expansion, and copper foil adhesion can be improved.
このプレ反応は、有機溶媒中で加熱保温しながらアミノ変性シロキサン化合物（Ａ）と、マレイミド化合物（Ｂ）と、酸性置換基を有するアミン化合物（Ｃ）を反応させて酸性置換基を有する変性イミド樹脂を合成することが好ましい。
有機溶媒中でアミノ変性シロキサン化合物（Ａ）と、マレイミド化合物（Ｂ）と、酸性置換基を有するアミン化合物（Ｃ）を反応させる際の反応温度は、例えば、７０〜１５０℃であることが好ましく、１００〜１３０℃であることがより好ましい。反応時間は、例えば、０．１〜１０時間であることが好ましく、１〜６時間であることがより好ましい。
In this pre-reaction, a modified imide having an acidic substituent by reacting an amino-modified siloxane compound (A), a maleimide compound (B), and an amine compound (C) having an acidic substituent while being heated and kept in an organic solvent. It is preferable to synthesize the resin.
The reaction temperature when the amino-modified siloxane compound (A), the maleimide compound (B), and the amine compound (C) having an acidic substituent are reacted in an organic solvent is preferably 70 to 150 ° C., for example. 100 to 130 ° C. is more preferable. For example, the reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
このプレ反応において、アミノ変性シロキサン化合物（Ａ）と、マレイミド化合物（Ｂ）と、酸性置換基を有するアミン化合物（Ｃ）の使用量は、例えば、マレイミド化合物（Ｂ）のマレイミド基数〔マレイミド化合物（Ｂ）の使用量（ｇ）／マレイミド化合物（Ｂ）のマレイミド基の官能基当量（ｇ／ｍｏｌ）〕が、アミノ変性シロキサン化合物（Ａ）と酸性置換基を有するアミン化合物（Ｃ）の一級アミノ基数〔アミノ変性シロキサン化合物（Ａ）の使用量（ｇ）／アミノ変性シロキサン化合物（Ａ）の一級アミノ基の官能基当量（ｇ／ｍｏｌ）＋酸性置換基を有するアミン化合物（Ｃ）の使用量（ｇ）／酸性置換基を有するアミン化合物（Ｃ）の一級アミノ基の官能基当量（ｇ／ｍｏｌ）〕の１．５〜１０．０倍になる範囲であることが好ましい。１．５倍以上とすることによりゲル化及び耐熱性の低下が抑制される。また、１０．０倍以下とすることにより有機溶剤への溶解性、耐熱性の低下が抑制される。 In this pre-reaction, the amount of the amino-modified siloxane compound (A), the maleimide compound (B), and the amine compound (C) having an acidic substituent is, for example, the number of maleimide groups of the maleimide compound (B) [maleimide compound ( B) used amount (g) / functional group equivalent of maleimide group (g / mol) of maleimide compound (B)] is amino-modified siloxane compound (A) and primary amino of amine compound (C) having acidic substituent Number of groups [Amount of amino-modified siloxane compound (A) used (g) / Amount of amine-functional siloxane compound (A) functional group equivalent of primary amino group (g / mol) + Amine compound (C) having an acidic substituent (G) / the functional group equivalent (g / mol) of the primary amino group of the amine compound (C) having an acidic substituent] is within a range of 1.5 to 10.0 times. Preferred. By setting it to 1.5 times or more, gelation and a decrease in heat resistance are suppressed. Moreover, the solubility to an organic solvent and a heat resistant fall are suppressed by setting it as 10.0 times or less.
プレ反応におけるマレイミド化合物（Ｂ）の使用量は、上記のような関係を維持しつつ、例えば、アミノ変性シロキサン化合物（Ａ）１００質量部に対して３０〜３０００質量部が好ましく、５０〜１５００質量部がより好ましく、５０〜３００質量部がより好ましい。３０質量部以上とすることにより耐熱性が低下しにくく、又、３０００質量部以下とすることにより低熱膨張性を良好に保つことができる。
また、プレ反応における酸性置換基を有するアミン化合物（Ｃ）の使用量は、例えば、アミノ変性シロキサン化合物（Ａ）１００質量部に対して１〜５００質量部が好ましく、１〜３００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熱性の低下が抑制され、又、５００質量部以下とすることにより低熱膨張性を良好に保つことができる。
The amount of the maleimide compound (B) used in the pre-reaction is, for example, preferably 30 to 3000 parts by weight, and 50 to 1500 parts by weight with respect to 100 parts by weight of the amino-modified siloxane compound (A) while maintaining the above relationship. Part is more preferable, and 50 to 300 parts by mass is more preferable. When the amount is 30 parts by mass or more, the heat resistance is not easily lowered, and when the amount is 3000 parts by mass or less, the low thermal expansion can be favorably maintained.
Moreover, 1-500 mass parts is preferable with respect to 100 mass parts of amino modified siloxane compounds (A), for example, and the usage-amount of the amine compound (C) which has an acidic substituent in pre-reaction is 1-300 mass parts. preferable. By setting it as 1 mass part or more, a heat resistant fall is suppressed, and low thermal expansion can be kept favorable by setting it as 500 mass parts or less.
このプレ反応で使用される有機溶媒は、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、酢酸エチルエステルやγ−ブチロラクトン等のエステル系溶剤、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などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。 Examples of the organic solvent used in this pre-reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetic acid. Ester solvents such as ethyl ester and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide And sulfur atom-containing solvents such as These may be used alone or in combination of two or more.
これらの有機溶媒の中で、例えば、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、γ−ブチロラクトン、ジメチルアセトアミドが好ましく、低毒性であることや揮発性が高く残溶剤として残りにくい点から、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、ジメチルアセトアミドが特に好ましい。 Among these organic solvents, for example, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, γ-butyrolactone, and dimethylacetamide are preferable from the viewpoint of solubility, and are low in toxicity and highly volatile and hardly remain as a residual solvent. To cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable.
有機溶媒の使用量は、例えば、アミノ変性シロキサン化合物（Ａ）、マレイミド化合物（Ｂ）、及び酸性置換基を有するアミン化合物（Ｃ）の総和１００質量部に対して、２５〜２０００質量部とすることが好ましく、４０〜１０００質量部とすることがより好ましく、４０〜５００質量部とすることが特に好ましい。有機溶媒の使用量を２５質量部以上とすることにより、溶解性が不足することが少なく、また２０００質量部以下とすることにより、反応に長時間を要さない傾向にある。 The amount of the organic solvent used is, for example, 25 to 2000 parts by mass with respect to 100 parts by mass in total of the amino-modified siloxane compound (A), the maleimide compound (B), and the amine compound (C) having an acidic substituent. It is preferably 40 to 1000 parts by mass, more preferably 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, the solubility is rarely insufficient, and when it is 2000 parts by mass or less, the reaction does not require a long time.
また、このプレ反応には任意に反応触媒を使用することができる。反応触媒は、例えば、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、リチウムアミド、ナトリウムアミド、カリウムアミド等のアルカリ金属アミドなどが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。 In addition, a reaction catalyst can be optionally used for this pre-reaction. Reaction catalysts include, for example, amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, alkali metal amides such as lithium amide, sodium amide and potassium amide Is mentioned. These may be used alone or in combination of two or more.
また、上記プレ反応より得られた酸性置換基を有する変性イミド樹脂の使用量は、例えば、熱硬化性樹脂組成物の樹脂成分の総和１００質量部当たり、５０〜１００質量部とすることが好ましく、６０〜８０質量部とすることがより好ましい。酸性置換基を有する変性イミド樹脂の使用量を５０質量部以上とすることにより低熱膨張性、高弾性率が得られる。 Moreover, it is preferable that the usage-amount of the modified imide resin which has an acidic substituent obtained from the said pre reaction shall be 50-100 mass parts per 100 mass parts of sum total of the resin component of a thermosetting resin composition, for example. 60 to 80 parts by mass is more preferable. By setting the amount of the modified imide resin having an acidic substituent to 50 parts by mass or more, low thermal expansion and high elastic modulus can be obtained.
本発明のアミノ変性シロキサン化合物（Ａ）と、マレイミド化合物（Ｂ）と、酸性置換基を有するアミン化合物（Ｃ）を含有してなる熱硬化性樹脂組成物及び前記化合物をプレ反応させて得られる酸性置換基を有する変性イミド樹脂を含有する熱硬化性樹脂組成物は、単独で良好な熱硬化反応性を有するが、必要により、硬化剤及びラジカル開始剤を使用することで、耐熱性や接着性、機械強度を向上させることができる。
硬化剤としては、特に限定されるものではないが、例えば、ジシアンジアミドや、４，４’−ジアミノジフェニルメタン、４，４'−ジアミノ−３，３'−ジエチル−ジフェニルメタン、４，４’−ジアミノジフェニルスルホン、フェニレンジアミン、キシレンジアミン等の芳香族アミン類、ヘキサメチレンジアミン、２，５−ジメチルヘキサメチレンジアミン等の脂肪族アミン類、メラミン、ベンゾグアナミン等のグアナミン化合物類などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。
また、ラジカル開始剤としても、特に限定されるものではないが、例えば、アシル過酸化物、ハイドロパーオキサイド、ケトン過酸化物、ｔ−ブチル基を有する有機過酸化物、クミル基を有する過酸化物などの有機過酸化物が使用できる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。これらの中で、例えば、良好な反応性や耐熱性の点から、芳香族アミン類が好ましい。
A thermosetting resin composition comprising the amino-modified siloxane compound (A) of the present invention, a maleimide compound (B), and an amine compound (C) having an acidic substituent, and obtained by pre-reacting the compound. A thermosetting resin composition containing a modified imide resin having an acidic substituent alone has good thermosetting reactivity, but if necessary, by using a curing agent and a radical initiator, heat resistance and adhesion Property and mechanical strength can be improved.
The curing agent is not particularly limited, and examples thereof include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, and 4,4′-diaminodiphenyl. Aromatic amines such as sulfone, phenylenediamine, and xylenediamine, aliphatic amines such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine, and guanamine compounds such as melamine and benzoguanamine. These may be used alone or in combination of two or more.
Further, the radical initiator is not particularly limited, but examples thereof include acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group. Organic peroxides such as products can be used. These may be used alone or in combination of two or more. Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.
さらに、本発明の熱硬化性樹脂組成物は、熱可塑性エラストマー（Ｄ）を含有することができる。
熱可塑性エラストマー（Ｄ）としては、例えば、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、アクリル系エラストマー、シリコーン系エラストマーやその誘導体等が挙げられる。これらは、ハードセグメント成分とソフトセグメント成分を有し、一般に前者が耐熱性及び強度に、後者が柔軟性及び強靭性に寄与している。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。
Furthermore, the thermosetting resin composition of the present invention can contain a thermoplastic elastomer (D).
Examples of the thermoplastic elastomer (D) include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers and derivatives thereof. These have a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These may be used alone or in combination of two or more.
また、これら熱可塑性エラストマーとしては、分子末端又は分子鎖中に反応性官能基を有するものを用いることができる。反応性官能基としては、例えば、エポキシ基、水酸基、カルボキシル基、アミノ基、アミド基、イソシアナト基、アクリル基、メタクリル基、ビニル基等が挙げられる。これら反応性官能基を分子末端又は分子鎖中に有することにより、樹脂への相溶性が向上し、本発明の熱硬化性樹脂組成物の硬化時に発生する内部応力をより効果的に低減することができ、結果として、基板の反りを顕著に低減することが可能となる。 Moreover, as these thermoplastic elastomers, those having a reactive functional group at the molecular end or molecular chain can be used. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acryl group, a methacryl group, and a vinyl group. By having these reactive functional groups in the molecular terminal or molecular chain, compatibility with the resin is improved, and internal stress generated during curing of the thermosetting resin composition of the present invention is more effectively reduced. As a result, it is possible to significantly reduce the warpage of the substrate.
これらの熱可塑性エラストマーの中で、例えば、耐熱性、絶縁信頼性の点で、スチレン系エラストマー、オレフィン系エラストマー、ポリアミド系エラストマー、及びシリコーン系エラストマーが好ましく、誘電特性の点から、スチレン系エラストマー及びオレフィン系エラストマーが特に好ましい。 Among these thermoplastic elastomers, for example, styrenic elastomers, olefinic elastomers, polyamide elastomers, and silicone elastomers are preferable in terms of heat resistance and insulation reliability. From the viewpoint of dielectric properties, styrenic elastomers and Olefin elastomers are particularly preferred.
また、これら熱可塑性エラストマーの分子末端又は分子鎖中に有する反応性官能基は、例えば、金属箔との密着性の点で、エポキシ基、水酸基、カルボキシル基、アミノ基、及びアミド基が好ましく、耐熱性、絶縁信頼性の点から、エポキシ基、水酸基、及びアミノ基が特に好ましい。 In addition, the reactive functional group possessed in the molecular terminal or molecular chain of these thermoplastic elastomers is preferably, for example, an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an amide group in terms of adhesion to the metal foil, From the viewpoint of heat resistance and insulation reliability, an epoxy group, a hydroxyl group, and an amino group are particularly preferable.
熱可塑性エラストマー（Ｄ）の使用量は、例えば、樹脂成分の総和１００質量部に対して、０．１〜５０質量部であることが好ましく、２〜３０質量部であることが、樹脂の相溶性が良く、硬化物の低硬化収縮性、低熱膨張性、優れた誘電特性を効果的に発現できる点からより好ましい。 The amount of the thermoplastic elastomer (D) used is, for example, preferably 0.1 to 50 parts by mass, and 2 to 30 parts by mass with respect to 100 parts by mass of the total resin components. It is more preferable from the viewpoint of good solubility, low cure shrinkage, low thermal expansion, and excellent dielectric properties of the cured product.
さらに、本発明の熱硬化性樹脂組成物は、エポキシ樹脂及びシアネート樹脂から選ばれる少なくとも一種の熱硬化性樹脂（Ｅ）を含有することができる。
エポキシ樹脂としては、特に限定されるものではないが、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノール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及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などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。これらの中で、例えば、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及びナフタレン型エポキシ樹脂が好ましい。
Furthermore, the thermosetting resin composition of the present invention can contain at least one thermosetting resin (E) selected from an epoxy resin and a cyanate resin.
The epoxy resin is not particularly limited. For example, 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 resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polyfunctional phenols and anthracene Such as diglycidyl ether compounds and phosphorus-containing epoxy resin obtained by introducing them into the phosphorus compounds. These may be used alone or in combination of two or more. Among these, for example, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable from the viewpoint of heat resistance and flame retardancy.
また、シアネート樹脂としても、特に限定されるものではないが、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及びこれらが一部トリアジン化したプレポリマーなどを挙げることができる。ここれらは１種類のみを用いても、２種類以上を混合して用いてもよい。これらの中で、例えば、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。 Further, the cyanate resin is not particularly limited. For example, bisphenol type cyanate resins such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, and the like. May be a prepolymer partially triazine. These may be used alone or in combination of two or more. Among these, for example, a novolac type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy.
これらの熱硬化性樹脂（Ｅ）には、必要に応じて硬化剤を使用することができる。硬化剤としては、例えば、フェノールノボラック、クレゾールノボラック、アミノトリアジンノボラック樹脂等の多官能フェノール化合物、ジシアンジアミド、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等のアミン化合物、無水フタル酸、無水ピロメリット酸、無水マレイン酸、無水マレイン酸共重合体等の酸無水物などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。 A curing agent can be used for these thermosetting resins (E) as necessary. As the curing agent, for example, polyfunctional phenol compounds such as phenol novolak, cresol novolak, aminotriazine novolak resin, amine compounds such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride, maleic anhydride, Examples thereof include acid anhydrides such as maleic anhydride copolymers. These may be used alone or in combination of two or more.
熱硬化性樹脂（Ｅ）の使用量としては、例えば、熱硬化性樹脂組成物の樹脂成分の総和１００質量部当たり、１〜５０質量部とすることが好ましく、耐熱性、耐薬品性の点から、１０〜３０質量部であることがより好ましい。 As a usage-amount of a thermosetting resin (E), it is preferable to set it as 1-50 mass parts per 100 mass parts of total of the resin component of a thermosetting resin composition, for example, and the point of heat resistance and chemical resistance From 10 to 30 parts by mass is more preferable.
本発明の熱硬化性樹脂組成物は、無機充填剤（Ｆ）を含有することができる。無機充填剤（Ｆ）としては，例えば、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、Ｔガラス、Ｄガラス等のガラス粉や中空ガラスビーズなどが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。 The thermosetting resin composition of the present invention can contain an inorganic filler (F). Examples of the inorganic filler (F) include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate. And glass powder such as barium sulfate, aluminum borate, potassium titanate, E glass, T glass, and D glass, and hollow glass beads. These may be used alone or in combination of two or more.
これらの中で、例えば、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などが挙げられる。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、溶融球状シリカ等が挙げられる。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。 Among these, for example, silica is particularly preferable from the viewpoint of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water. Further, examples of the dry process silica include crushed silica, fumed silica, fused spherical silica and the like depending on the production method. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.
無機充填剤（Ｆ）として溶融球状シリカを用いる場合、例えば、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、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 (F), for example, 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 diameter is a particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the particles as 100%, and a laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.
無機充填剤（Ｆ）の含有量は、例えば、熱硬化性樹脂組成物の樹脂成分の総和１００質量部に対して２０〜３００質量部であることが好ましく、５０〜２００質量部であることがより好ましい。無機充填剤（Ｆ）の含有量を樹脂成分の総和１００質量部に対して２０〜３００質量部にすることで、熱硬化性樹脂組成物の成形性と低熱膨張性を良好に保つことができる。
また、熱硬化性樹脂組成物に無機充填剤を配合するに際しては、例えば、該無機充填剤（Ｆ）をシラン系、チタネート系等のカップリング剤、シリコーンオリゴマー等の表面処理剤などで前処理、又はインテグラルブレンド処理することも好ましい。
The content of the inorganic filler (F) is, for example, preferably 20 to 300 parts by mass, and 50 to 200 parts by mass with respect to 100 parts by mass of the total resin components of the thermosetting resin composition. More preferred. By setting the content of the inorganic filler (F) to 20 to 300 parts by mass with respect to 100 parts by mass of the total of the resin components, the moldability and low thermal expansion of the thermosetting resin composition can be kept good. .
In addition, when an inorganic filler is blended in the thermosetting resin composition, for example, the inorganic filler (F) is pretreated with a coupling agent such as silane or titanate, or a surface treatment agent such as silicone oligomer. Alternatively, an integral blend treatment is also preferable.
本発明の熱硬化性樹脂組成物は、硬化促進剤（Ｇ）を含有することができる。硬化促進剤（Ｇ）としては、特に限定されるものではないが、例えば、ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸スズ、オクチル酸コバルト、ビスアセチルアセトナートコバルト（ＩＩ）、トリスアセチルアセトナートコバルト（ＩＩＩ）等の有機金属塩、イミダゾール類及びその誘導体、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、第二級アミン類、第三級アミン類、及び第四級アンモニウム塩などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。 これらの中で、例えば、促進効果と保存安定性の点から、ナフテン酸亜鉛、イミダゾール誘導体、ホスホニウム塩が好ましい。 The thermosetting resin composition of the present invention can contain a curing accelerator (G). The curing accelerator (G) is not particularly limited. For example, zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt And organic metal salts such as (III), imidazoles and derivatives thereof, organophosphorus compounds such as phosphines and phosphonium salts, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more. Among these, for example, zinc naphthenate, imidazole derivatives, and phosphonium salts are preferable from the viewpoint of the promoting effect and the storage stability.
硬化促進剤（Ｇ）の含有量は、例えば、熱硬化性樹脂組成物の樹脂成分の総和１００質量部に対して０．０１〜３．０質量部であることが好ましく、０．０５〜１．５質量部であることがより好ましい。硬化促進剤（Ｇ）の含有量を当該範囲にすることで、促進効果と保存安定性を良好に保つことができる。 It is preferable that content of a hardening accelerator (G) is 0.01-3.0 mass parts with respect to 100 mass parts of total of the resin component of a thermosetting resin composition, for example, 0.05-1 More preferably, it is 5 parts by mass. By making content of a hardening accelerator (G) into the said range, a promotion effect and storage stability 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、有機充填剤、難燃剤、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤及び接着性向上剤等を使用できる。 In the present invention, any known thermoplastic resins, organic fillers, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, and adhesion improvers may be used without departing from the object. Etc. can be used.
熱可塑性樹脂としては、例えば、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。 Examples of the thermoplastic resin include polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.
有機充填剤としては、例えば、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、シリコーン樹脂、テトラフルオロエチレン樹脂等よりなる樹脂フィラー、アクリル酸エステル系樹脂、メタクリル酸エステル系樹脂、共役ジエン系樹脂等よりなるゴム状態のコア層と、アクリル酸エステル系樹脂、メタクリル酸エステル系樹脂、芳香族ビニル系樹脂、シアン化ビニル系樹脂等よりなるガラス状態のシェル層を持つコアシェル構造の樹脂フィラーなどが挙げられる。 Examples of the organic filler include a resin filler made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, acrylate ester resin, methacrylate ester resin, conjugated diene resin, and the like. Examples thereof include a resin filler having a core-shell structure having a rubbery core layer and a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like.
難燃剤としては、例えば、臭素や塩素を含有する含ハロゲン系難燃剤、トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、リン酸エステル系化合物、赤リン等のリン系難燃剤スルファミン酸グアニジン、硫酸メラミン、ポリリン酸メラミン、メラミンシアヌレート等の窒素系難燃剤、シクロホスファゼン、ポリホスファゼン等のホスファゼン系難燃剤、三酸化アンチモン等の無機系難燃剤などが挙げられる。 Examples of the flame retardant include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphorous flame retardants such as red phosphorus, and guanidine sulfamate. And nitrogen flame retardants such as melamine sulfate, melamine polyphosphate, and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.
その他、紫外線吸収剤の例としてはベンゾトリアゾール系紫外線吸収剤、酸化防止剤の例としてはヒンダードフェノール系やヒンダードアミン系酸化防止剤、光重合開始剤の例としてはベンゾフェノン類、ベンジルケタール類、チオキサントン系の光重合開始剤、蛍光増白剤の例としてはスチルベン誘導体の蛍光増白剤、接着性向上剤の例としては尿素シラン等の尿素化合物やシラン系、チタネート系、アルミネート系等のカップリング剤が挙げられる。 Other examples of UV absorbers include benzotriazole UV absorbers, examples of antioxidants include hindered phenols and hindered amines, and examples of photopolymerization initiators include benzophenones, benzyl ketals, and thioxanthone. Examples of photopolymerization initiators and fluorescent brighteners include stilbene derivative fluorescent brighteners, and adhesion improvers such as urea compounds such as urea silane and silane, titanate and aluminate cups. A ring agent is mentioned.
本発明の熱硬化性樹脂組成物は、プリプレグに用いられるため、各成分が有機溶媒中に溶解又は分散されたワニスの状態とすることが好ましい。 Since the thermosetting resin composition of the present invention is used for a prepreg, it is preferable to have a varnish in which each component is dissolved or dispersed in an organic solvent.
ワニスを製造する際に用いる有機溶媒としては、例えば、メタノール、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媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶媒、テトラヒドロフラン等のエーテル系溶媒、トルエン、キシレン、メシチレン等の芳香族系溶媒、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媒、ジメチルスルホキシド等の硫黄原子含有溶媒などが挙げられる。これらは１種類のみを用いても、２種類以上を混合して用いてもよい。 これらの中で、例えば、溶解性の点から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、メチルセロソルブ、プロピレングリコールモノメチルエーテルが好ましく、低毒性である点からメチルイソブチルケトン、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い。 Examples of the organic solvent used for producing the varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents, ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atoms such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Examples thereof include solvents and sulfur atom-containing solvents such as dimethyl sulfoxide. These may be used alone or in combination of two or more. Among these, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.
ワニス中の熱硬化性樹脂組成物は、例えば、ワニス全体の４０〜９０質量％であることが好ましく、５０〜８０質量％であることがより好ましい。ワニス中の熱硬化性樹脂組成物の含有量を４０〜９０質量％にすることで、塗工性を良好に保ち、適切な樹脂組成物付着量のプリプレグを得ることができる。
なお、本明細書において、樹脂成分とは、主に、アミノ変性シロキサン化合物（Ａ）及びマレイミド化合物（Ｂ）であり、アミン化合物（Ｃ）、熱可塑性エラストマー（Ｄ）、熱硬化性樹脂（Ｅ）、無機充填剤（Ｆ）、及び硬化促進剤（Ｇ）の少なくともいずれかが配合されている場合は、これら配合物をも含むものである。
The thermosetting resin composition in the varnish is, for example, preferably 40 to 90% by mass, and more preferably 50 to 80% by mass with respect to the entire varnish. By setting the content of the thermosetting resin composition in the varnish to 40 to 90% by mass, it is possible to maintain good coating properties and obtain a prepreg having an appropriate resin composition adhesion amount.
In this specification, the resin component is mainly an amino-modified siloxane compound (A) and a maleimide compound (B), and an amine compound (C), a thermoplastic elastomer (D), a thermosetting resin (E ), An inorganic filler (F), and a curing accelerator (G) are included, these compounds are also included.
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、基材に含浸し、加熱等により半硬化（Ｂステージ化）して製造することができる。本発明の熱硬化性樹脂組成物を基材に含浸させる方法として特に限定されないが、例えば、基材を樹脂ワニスに浸漬する方法、各種コーターにより塗布する方法、スプレーによる吹き付ける方法等が挙げられる。これらの中でも、基材を樹脂ワニスに浸漬する方法が好ましい。これにより、基材に対する樹脂組成物の含浸性を向上することができる。
本発明の基材としては、例えば、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が挙げられる。他の用途では、例えば、繊維強化基材であれば、炭素繊維を用いることが可能である。
The prepreg of the present invention is obtained by impregnating a 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 the thermosetting resin composition of the present invention into a substrate and semi-curing (B-stage) by heating or the like. Although it does not specifically limit as a method to make a base material impregnate the thermosetting resin composition of this invention, For example, the method of immersing a base material in a resin varnish, the method of apply | coating with various coaters, the method of spraying, etc. are mentioned. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved.
As a base material of this invention, the well-known thing used for the laminated board for various electrical insulation materials can be used, for example. 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. In other applications, for example, carbon fibers can be used for fiber reinforced substrates.
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が挙げられる。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、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や、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。 Examples of these base materials include shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat. The material and shape are selected depending on the intended use and performance of the molded product, and if necessary, two or more kinds of materials and shapes can be combined. The thickness of the substrate can be, for example, about 0.03 to 0.5 mm, and the surface treated with a silane coupling agent or the like, or the one subjected to mechanical opening treatment is heat resistant. And from the viewpoint of moisture resistance and workability.
本発明のプリプレグは、例えば、該基材に対する熱硬化性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質量％となるように、基材に含浸した後、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。 The prepreg of the present invention, for example, after impregnating the base material so that the adhesion amount of the thermosetting resin composition to the base material is 20 to 90% by mass with the resin content of the prepreg after drying, Usually, 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).
本発明の樹脂付フィルムは、本発明の熱硬化性樹脂組成物を支持体上に層形成してなるものである。
本発明の樹脂付フィルムは、前記した本発明の熱硬化性樹脂組成物を支持体上に層形成し、加熱等により半硬化（Ｂステージ化）して製造することができる。この半硬化状態は、本発明の樹脂付きフィルムの樹脂組成物層を回路基板にラミネートし、硬化する際に、樹脂組成物層が硬化した絶縁樹脂層と回路パターン基板との接着力が確保される状態、また、回路基板への埋めこみ性（流動性）が確保される状態であることが好ましい。本発明の熱硬化性樹脂組成物を支持体上に層形成する方法として特に限定されないが、例えば、樹脂ワニスを、各種コーターを用いて支持体であるフィルムに塗布し、更に加熱、あるいは熱風吹きつけ等により乾燥させて樹脂組成物層を形成させることにより製造することができる。
The film with a resin of the present invention is obtained by forming a layer of the thermosetting resin composition of the present invention on a support.
The film with resin of the present invention can be produced by forming a layer of the above-described thermosetting resin composition of the present invention on a support and semi-curing (B-stage) by heating or the like. In this semi-cured state, when the resin composition layer of the resin-coated film of the present invention is laminated on a circuit board and cured, the adhesive force between the insulating resin layer cured by the resin composition layer and the circuit pattern board is ensured. In addition, it is preferable to be in a state in which embedding (fluidity) in a circuit board is ensured. The method for forming a layer of the thermosetting resin composition of the present invention on the support is not particularly limited. For example, a resin varnish is applied to a film as a support using various coaters, and further heated or blown with hot air. It can be produced by drying to form a resin composition layer.
熱硬化性樹脂組成物を支持体に塗布した後の乾燥条件は、例えば、該樹脂組成物層への有機溶剤の含有量が１０質量％以下、好ましくは５質量％以下となるように乾燥させる。ワニス中の有機溶剤量、有機溶剤の沸点によっても異なるが、例えば３０〜６０質量％の有機溶剤を含むワニスを５０〜１５０℃で３〜１０分程度乾燥させることにより、樹脂組成物層が形成される。乾燥条件は、予め簡単な実験により適宜、好適な乾燥条件を設定することが好ましい。 The drying conditions after applying the thermosetting resin composition to the support are, for example, dried so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. . Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. Is done. It is preferable to set suitable drying conditions as appropriate by simple experiments in advance.
樹脂付フィルムの樹脂組成物層の厚さは、通常、回路基板が有する導体層の厚さ以上とすることが好ましい。導体層の厚さは、例えば、５〜７０μｍであることが好ましく、多層プリント配線板の軽薄短小化のために、５〜５０μｍであることがより好ましく、５〜３０μｍであることがより好ましい。 In general, the thickness of the resin composition layer of the film with resin is preferably equal to or greater than the thickness of the conductor layer of the circuit board. The thickness of the conductor layer is preferably, for example, 5 to 70 μm, more preferably 5 to 50 μm, and more preferably 5 to 30 μm in order to reduce the thickness of the multilayer printed wiring board.
樹脂付フィルムにおける支持体は、特に限定されるものではなく、例えば、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリイミドなどの有機フィルム、更には離型紙や銅箔、アルミニウム箔等の金属箔を挙げることができる。なお、支持体及び後述する保護フィルムには、マット処理、コロナ処理の他、離型処理を施してもよい。 The support in the resin-coated film is not particularly limited, and examples thereof include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene naphthalate, organic films such as polycarbonate and polyimide, and separation. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, you may give a mold release process to a support body and the protective film mentioned later other than a mat | matte process and a corona treatment.
支持体の厚さは、例えば、１０〜１５０μｍが好ましく、より好ましくは２５〜５０μｍである。樹脂組成物層の支持体が密着していない面に、保護フィルムをさらに積層することができる。保護フィルムの厚さは、例えば１〜４０μｍである。保護フィルムを積層することにより、異物混入を防止することができる。
樹脂付フィルムは、ロール状に巻き取って貯蔵することもできる。保護フィルムとしては、特に限定されるものではないが、前述の支持体として挙げたものを用いることができる。
For example, the thickness of the support is preferably 10 to 150 μm, more preferably 25 to 50 μm. A protective film can be further laminated on the surface of the resin composition layer on which the support is not in close contact. The thickness of the protective film is, for example, 1 to 40 μm. By laminating the protective film, foreign matter can be prevented from being mixed.
The film with resin can also be wound and stored in a roll shape. Although it does not specifically limit as a protective film, The thing quoted as the above-mentioned support body can be used.
本発明の積層板は、前述の樹脂付フィルムを積層成形して得られるものである。例えば、樹脂付フィルムを、真空ラミネーターを用いて、回路基板、プリプレグ及び基材等の片面又は両面にラミネートし、必要に応じ、加熱により硬化することで製造することができる。
回路基板に用いられる基板としては、例えば、ガラスエポキシ基板、金属基板、ポリエステル基板、ポリイミド基板、ＢＴレジン基板、熱硬化型ポリフェニレンエーテル基板等が挙げられる。なお、ここで回路基板とは、上記のような基板の片面又は両面に回路パターンが形成されたものをいう。また導体層と絶縁層とを交互に複数積層してなるプリント配線板において、該プリント配線板の最外層の片面又は両面に回路パターンが形成されたものも、ここでいう回路基板に含まれる。なお導体層表面には、黒化処理等により予め粗化処理が施されていてもよい。
The laminated board of the present invention is obtained by laminating the above-mentioned resin-coated film. For example, it can be manufactured by laminating a film with resin on one side or both sides of a circuit board, a prepreg, a base material and the like using a vacuum laminator and curing by heating as necessary.
Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the circuit pattern was formed in the one or both surfaces of the above boards. In addition, a printed wiring board in which a plurality of conductor layers and insulating layers are alternately laminated and having a circuit pattern formed on one side or both sides of the outermost layer of the printed wiring board is also included in the circuit board here. The surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.
上記ラミネートにおいて、樹脂付フィルムが保護フィルムを有している場合には該保護フィルムを除去した後、必要に応じて樹脂付フィルム及び回路基板をプレヒートし、樹脂付フィルムを加圧及び加熱しながら回路基板に圧着する。本発明の樹脂付フィルムにおいては、真空ラミネート法により減圧下で回路基板にラミネートする方法が好適に用いられる。ラミネート条件は、例えば、圧着温度（ラミネート温度）を好ましくは７０〜１４０℃、圧着圧力を好ましくは０．１〜１．１ＭＰａとし、空気圧２０ｍｍＨｇ（２６．７ｈＰａ）以下の減圧下でラミネートするのが好ましい。また、ラミネートの方法は、バッチ式であってもロールでの連続式であってもよい。 In the above laminate, if the film with resin has a protective film, after removing the protective film, preheat the film with resin and the circuit board as necessary, while pressing and heating the film with resin Crimp to circuit board. In the film with resin of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are, for example, that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the lamination is performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. preferable. The laminating method may be a batch method or a continuous method using a roll.
樹脂付フィルムを回路基板にラミネートした後、室温付近に冷却してから、支持体を剥離する場合は剥離し、熱硬化することにより回路基板に絶縁樹脂層を形成することができる。熱硬化の条件は、熱硬化性樹脂樹脂組成物中の樹脂成分の種類、含有量等
に応じて適宜選択すればよいが、好ましくは１５０〜２２０℃で２０〜１８０分、より好ましくは１６０〜２００℃で３０〜１２０分の範囲で選択される。
After laminating the resin-coated film on the circuit board, the insulating resin layer can be formed on the circuit board by cooling it to around room temperature and then peeling it off when the support is peeled off and thermosetting. The conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the thermosetting resin resin composition, but are preferably 150 to 220 ° C. for 20 to 180 minutes, more preferably 160 to It is selected in the range of 30 to 120 minutes at 200 ° C.
絶縁樹脂層を形成した後、硬化前に支持体を剥離しなかった場合は、ここで剥離する。次いで必要により、回路基板上に形成された絶縁樹脂層に穴開けを行ってビアホール、スルーホールを形成する。穴あけは、例えば、ドリル、レーザー、プラズマ等の公知の方法により、また必要によりこれらの方法を組み合わせて行うことができるが、炭酸ガスレーザー、ＹＡＧレーザー等のレーザーによる穴あけが最も一般的な方法である。 If the support is not peeled off after the insulating resin layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating resin layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.
次いで、乾式メッキ又は湿式メッキにより絶縁樹脂層上に導体層を形成する。乾式メッキとしては、蒸着、スパッタリング、イオンプレーティング等の公知の方法を使用することができる。湿式メッキの場合は、まず、絶縁樹脂層の表面を、過マンガン酸塩（過マンガン酸カリウム、過マンガン酸ナトリウム等）、重クロム酸塩、オゾン、過酸化水素／硫酸、硝酸等の酸化剤で粗化処理し、凸凹のアンカーを形成する。酸化剤としては、特に過マンガン酸カリウム、過マンガン酸ナトリウム等の水酸化ナトリウム水溶液（アルカリ性過マンガン酸水溶液）が好ましく用いられる。次いで、無電解メッキと電解メッキとを組み合わせた方法で導体層を形成する。また導体層とは逆パターンのメッキレジストを形成し、無電解メッキのみで導体層を形成することもできる。その後のパターン形成の方法として、例えば、公知のサブトラクティブ法、セミアディティブ法などを用いることができる。 Next, a conductor layer is formed on the insulating resin layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the insulating resin layer is coated with an oxidizing agent such as permanganate (potassium permanganate, sodium permanganate), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. A roughening process is carried out to form an uneven anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.
本発明の積層板は、前述の本発明のプリプレグを積層成形して得られるものである。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又は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。
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回路基板とを組合せ、積層成形して、積層板を製造することもできる。
The laminate of the present invention is obtained by laminating the above-described prepreg of the present invention. 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 or aluminum on one or both sides thereof.
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. Moreover, the prepreg of the present invention and a circuit board can be combined and laminated to produce a laminated board.
本発明の多層プリント配線板は、前記積層板を用いて製造されるものである。例えば、本発明の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回路基板を得ることが出来る。そして、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、レーザー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、メッキ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 multilayer printed wiring board of this invention is manufactured using the said laminated board. For example, the circuit board can be obtained by wiring processing the conductor layer of the laminate of the present invention by an ordinary etching method. Then, a plurality of laminated boards processed by wiring through the above-described prepreg are laminated and subjected to hot press processing to be multi-layered at once. Thereafter, 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.
本発明に係る半導体パッケージは、前記多層プリント配線板の所定の位置に半導体チップやメモリ等の半導体素子を搭載し製造される。 The semiconductor package according to the present invention is manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the multilayer printed wiring board.
次に、下記の実施例により本発明を更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、各実施例及び比較例で得られた樹脂板を用いて硬化収縮率、銅張積層板を用いて、ガラス転移温度、熱膨張率、銅箔接着性、銅付きはんだ耐熱性、曲げ弾性率について以下の方法で測定し、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, using resin plates obtained in each Example and Comparative Example, curing shrinkage rate, using copper-clad laminate, glass transition temperature, thermal expansion coefficient, copper foil adhesion, solder heat resistance with copper, bending elasticity The rate was measured and evaluated by the following method.
（１）樹脂板の硬化収縮率の測定
縦５ｍｍ（Ｘ方向）、横５ｍｍ（Ｙ方向）、厚み1ｍｍ（Ｚ方向）の樹脂板を作製し、ＴＭＡ試験装置（ＴＡインスツルメント社製、Ｑ４００）を用いて圧縮法で熱機械分析を行った。樹脂板を前記装置にＸ方向又はＹ方向に装着後、荷重５ｇ、昇温速度４５℃／分とし、２０℃（５分保持）〜２６０℃（２分保持）〜２０℃（５分保持）の温度プロファイルにて測定した。昇温開始前の２０℃及び昇温後の２０℃での寸法変化量から樹脂板の硬化収縮率（％）を評価した。
具体的には、以下の式を用いて、樹脂板の硬化収縮率を算出した。
硬化収縮率（％）＝｛（昇温開始前２０℃の寸法（ｍｍ）−昇温後２０℃の寸法（ｍｍ））／昇温開始前２０℃の寸法（ｍｍ）｝×１００
(1) Measurement of curing shrinkage rate of resin plate A resin plate having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness of 1 mm (Z direction) was prepared, and a TMA test apparatus (TA Instruments, Q400) was prepared. ) Was used for the thermomechanical analysis by the compression method. After mounting the resin plate in the X direction or Y direction on the device, the load is 5 g, the heating rate is 45 ° C./min, 20 ° C. (5 min hold) to 260 ° C. (2 min hold) to 20 ° C. (5 min hold) The temperature profile was measured. The cure shrinkage rate (%) of the resin plate was evaluated from the dimensional change at 20 ° C. before starting the temperature increase and at 20 ° C. after the temperature increase.
Specifically, the curing shrinkage rate of the resin plate was calculated using the following formula.
Curing shrinkage rate (%) = {(20 ° C. before starting temperature rise (mm) −20 ° C. after temperature rising (mm)) / 20 ° C. before temperature rising (mm)} × 100
（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縦５ｍｍ（Ｘ方向）、横５ｍｍ（Ｙ方向）、厚み（Ｚ方向）の評価基板を作製し、ＴＭＡ試験装置（ＴＡインスツルメント社製、Ｑ４００）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) Evaluation of 5 mm in length (X direction), 5 mm in width (Y direction), and thickness (Z direction) from which copper foil was removed by immersing a copper clad laminate in a copper etching solution The board | substrate was produced and the thermomechanical analysis was performed by the compression method using the TMA test apparatus (the TA instrument company make, Q400). 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縦５ｍｍ（Ｘ方向）、横５ｍｍ（Ｙ方向）、厚み（Ｚ方向）の評価基板を作製し、ＴＭＡ試験装置（ＴＡインスツルメント社製、Ｑ４００）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℃まで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 thermal expansion coefficient An evaluation board having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness (Z direction), in which a copper foil is removed by immersing a copper clad laminate in a copper etching solution, is produced. Then, a thermomechanical analysis was performed by a compression method using a TMA test apparatus (Q400, manufactured by TA Instruments). 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）銅箔接着性（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３ｍｍ幅の銅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性（ピール強度）を測定した。
(4) Evaluation of copper foil adhesion (copper foil peel strength) A copper-clad laminate is immersed in a copper etching solution to form a copper foil having a width of 3 mm to produce an evaluation substrate, and copper is tested using a tensile tester. The adhesion (peel strength) of the foil was measured.
（５）銅付きはんだ耐熱性の評価
銅張積層板から２５ｍｍ角の評価基板を作製し、温度２８８℃のはんだ浴に、１２０分間評価基板をフロートし、外観を観察することにより銅付きはんだ耐熱性を評価した。
(5) Evaluation of solder heat resistance with copper Solder heat resistance with copper by preparing a 25 mm square evaluation board from a copper clad laminate, floating the evaluation board in a solder bath at a temperature of 288 ° C. for 120 minutes, and observing the appearance Sex was evaluated.
（６）曲げ弾性率
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２５ｍｍ×５０ｍｍの評価基板を作製し、オリエンテック社製５トンテンシロンを用い、クロスヘッド速度１ｍｍ／ｍｉｎ、スパン間距離２０ｍｍで測定した。
(6) Flexural modulus A copper-clad laminate was immersed in a copper etching solution to produce a 25 mm × 50 mm evaluation board from which the copper foil was removed, using a 5-ton tensilon manufactured by Orientec Co., Ltd., and a crosshead speed of 1 mm / min. Measured at a span distance of 20 mm.
製造実施例１：アミノ変性シロキサン化合物（Ａ−１）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、Ｘ−２２−１６３Ａ：５８．０ｇ、３，３’−ジエチル−４，４’−ジアミノジフェニルメタン：２２．１ｇ、プロピレングリコールモノメチルエーテル：５３．３ｇを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮し、アミノ変性シロキサン化合物（Ａ−１）含有溶液（樹脂成分：８０質量％、重量平均分子量（Ｍｗ）：１００００）を得た。
Production Example 1: Production of amino-modified siloxane compound (A-1) X-22-163A was placed in a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 58.0 g, 3,3′-diethyl-4,4′-diaminodiphenylmethane: 22.1 g, propylene glycol monomethyl ether: 53.3 g, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. Then, it was concentrated under normal pressure to obtain an amino-modified siloxane compound (A-1) -containing solution (resin component: 80% by mass, weight average molecular weight (Mw): 10,000).
製造実施例２：アミノ変性シロキサン化合物（Ａ−２）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、Ｘ−２２−１６３Ｂ：６５．７ｇ、３，３’−ジエチル−４，４’−ジアミノジフェニルメタン：１４．３ｇ、プロピレングリコールモノメチルエーテル：５３．３ｇを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮し、アミノ変性シロキサン化合物（Ａ−２）含有溶液（樹脂成分：８０質量％、重量平均分子量（Ｍｗ）：７０００）を得た。
Production Example 2: Production of amino-modified siloxane compound (A-2) X-22-163B was placed in a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 65.7 g, 3,3′-diethyl-4,4′-diaminodiphenylmethane: 14.3 g, propylene glycol monomethyl ether: 53.3 g, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. Then, it was concentrated under normal pressure to obtain an amino-modified siloxane compound (A-2) -containing solution (resin component: 80% by mass, weight average molecular weight (Mw): 7000).
製造実施例３：アミノ変性シロキサン化合物（Ａ−３）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、Ｘ−２２−１６３Ｃ：７４．４ｇ、２，５−ジメチル−１，４−ジアミノベンゼン：５．６ｇ、プロピレングリコールモノメチルエーテル：５３．３ｇを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮し、アミノ変性シロキサン化合物（Ａ−３）含有溶液（樹脂成分：８０質量％、重量平均分子量（Ｍｗ）：２００００））を得た。
Production Example 3: Production of amino-modified siloxane compound (A-3) X-22-163C was placed in a 2 liter reaction vessel with a thermometer, a stirrer, and a water quantifier with a reflux condenser and capable of heating and cooling. : 74.4 g, 2,5-dimethyl-1,4-diaminobenzene: 5.6 g, propylene glycol monomethyl ether: 53.3 g, and after reacting at 115 ° C. for 4 hours, the temperature was raised to 130 ° C. The solution was concentrated under pressure to obtain an amino-modified siloxane compound (A-3) -containing solution (resin component: 80% by mass, weight average molecular weight (Mw): 20000).
製造実施例４：変性イミド樹脂（Ｈ−１）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、アミノ変性シロキサン化合物（Ａ−１）含有溶液（樹脂成分：８０質量％）：４６．７ｇ、ビス（４−マレイミドフェニル）メタン：２６２．６g、プロピレングリコールモノメチルエーテル：４４０．７ｇを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮し、変性イミド樹脂（Ｈ−１）含有溶液（樹脂成分：６０質量％）を得た。
Production Example 4: Production of Modified Imide Resin (H-1) An amino-modified siloxane compound (A) was placed in a 2 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling. -1) containing solution (resin component: 80% by mass): 46.7 g, bis (4-maleimidophenyl) methane: 262.6 g, propylene glycol monomethyl ether: 440.7 g, and reacting at 115 ° C. for 4 hours The solution was heated to 130 ° C. and concentrated at normal pressure to obtain a modified imide resin (H-1) -containing solution (resin component: 60% by mass).
製造実施例５：変性イミド樹脂（Ｈ−２）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、アミノ変性シロキサン化合物（Ａ−２）含有溶液（樹脂成分：８０質量％）：４６．８ｇ、ビス（４−マレイミドフェニル）メタン：２６２．５g、プロピレングリコールモノメチルエーテル：４４０．６ｇを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮し、変性イミド樹脂（Ｈ−２）含有溶液（樹脂成分：６０質量％）を得た。
Production Example 5 Production of Modified Imide Resin (H-2) An amino-modified siloxane compound (A) was placed in a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. -2) Containing solution (resin component: 80% by mass): 46.8 g, bis (4-maleimidophenyl) methane: 262.5 g, propylene glycol monomethyl ether: 440.6 g, and reacted at 115 ° C. for 4 hours The solution was heated to 130 ° C. and concentrated at normal pressure to obtain a modified imide resin (H-2) -containing solution (resin component: 60% by mass).
製造実施例６：酸性置換基を有する変性イミド樹脂（Ｉ−１）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、アミノ変性シロキサン化合物（Ａ−１）含有溶液（樹脂成分：８０質量％）：４６．７ｇ、ビス（４−マレイミドフェニル）メタン：２５３．０g、ｐ−アミノフェノール：９．６ｇ、プロピレングリコールモノメチルエーテル：４４０．７gを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮し、酸性置換基を有する変性イミド樹脂（Ｉ−１）含有溶液（樹脂成分：６０質量％）を得た。
Production Example 6 Production of Modified Imide Resin (I-1) Having Acidic Substituent Amino acid was placed in a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Modified siloxane compound (A-1) -containing solution (resin component: 80% by mass): 46.7 g, bis (4-maleimidophenyl) methane: 253.0 g, p-aminophenol: 9.6 g, propylene glycol monomethyl ether: 440.7 g was added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at normal pressure, and a modified imide resin (I-1) -containing solution having an acidic substituent (resin component: 60% by mass) Got.
製造実施例７：酸性置換基を有する変性イミド樹脂（Ｉ−２）の製造
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、アミノ変性シロキサン化合物（Ａ−２）含有溶液（樹脂成分：８０質量％）：４６．８ｇ、ビス（４−マレイミドフェニル）メタン：２５２．９g、ｐ−アミノフェノール：９．６ｇ、プロピレングリコールモノメチルエーテル：４４０．６gを入れ、１１５℃で４時間反応した後、１３０℃まで昇温して常圧濃縮し、酸性置換基を有する変性イミド樹脂（Ｉ−２）含有溶液（樹脂成分：６０質量％）を得た。
Production Example 7 Production of Modified Imide Resin (I-2) Having Acidic Substituent Amino acid was placed in a 2 liter reaction vessel with a thermometer, a stirrer, and a water quantifier with a reflux condenser and capable of heating and cooling. Modified siloxane compound (A-2) -containing solution (resin component: 80% by mass): 46.8 g, bis (4-maleimidophenyl) methane: 252.9 g, p-aminophenol: 9.6 g, propylene glycol monomethyl ether: 440.6 g was added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at normal pressure, and a modified imide resin (I-2) -containing solution having an acidic substituent (resin component: 60% by mass) Got.
実施例１〜１８及び比較例１〜６
製造実施例１〜３で得られたアミノ変性シロキサン化合物（Ａ−１、Ａ−２、Ａ−３）含有溶液、製造実施例４、５で得られた変性イミド樹脂（Ｈ−１、Ｈ−２）含有溶液及び製造実施例６、７で得られた酸性置換基を有する変性イミド樹脂（Ｉ−１、Ｉ−２）含有溶液と、以下に示すシロキサン化合物（i）、アミン化合物（ii）、マレイミド化合物（Ｂ）、酸性置換基を有するアミン化合物（Ｃ）、熱可塑性エラストマー（Ｄ）、熱硬化性樹脂（Ｅ）、無機充填剤（Ｆ）、硬化促進剤（Ｇ）、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４表に示した配合割合（質量部）で混合して樹脂分６５質量％のワニスを得た。
次に、上記ワニスを、１６μｍのポリエチレンテレフタレート製フィルムに、乾燥後の樹脂厚が３５μｍとなるようにフィルムアプリケーター（テスター産業株式会社製、ＰＩ−１２１０）を用いて塗布し、１６０℃で１０分加熱乾燥し、半硬化物の樹脂粉を得た。
この樹脂粉をテフロンシートの型枠に投入し、１２μｍの電解銅箔の光沢面を上下に配置し、圧力２．０ＭＰａ、温度２４０℃で６０分間プレスを行った後、電解銅箔を除去して樹脂板を得た。
また、上記ワニスを厚さ０．１ｍｍのＥガラスクロスに含浸し、１６０℃で１０分加熱乾燥して樹脂含有量４８質量％のプリプレグを得た。
このプリプレグを４枚重ね、１２μｍの電解銅箔を上下に配置し、圧力３．０ＭＰａ、温度２４０℃で６０分間プレスを行って、銅張積層板を得た。
得られた樹脂板及び銅張積層板の測定及び評価結果を第１表〜第４表に示す。
Examples 1-18 and Comparative Examples 1-6
Solutions containing amino-modified siloxane compounds (A-1, A-2, A-3) obtained in Production Examples 1 to 3, modified imide resins (H-1, H-) obtained in Production Examples 4 and 5 2) Containing solution and modified imide resin (I-1, I-2) -containing solution having an acidic substituent obtained in Production Examples 6 and 7, and the following siloxane compound (i) and amine compound (ii) , Maleimide compound (B), amine compound having acidic substituent (C), thermoplastic elastomer (D), thermosetting resin (E), inorganic filler (F), curing accelerator (G), and diluent solvent In addition, methyl ethyl ketone was used and mixed at a blending ratio (parts by mass) shown in Tables 1 to 4 to obtain a varnish having a resin content of 65% by mass.
Next, the varnish was applied to a 16 μm polyethylene terephthalate film using a film applicator (PI-1210, manufactured by Tester Sangyo Co., Ltd.) so that the resin thickness after drying was 35 μm, and then at 160 ° C. for 10 minutes. Heat drying was performed to obtain a semi-cured resin powder.
This resin powder is put into a form of Teflon sheet, the glossy surface of 12 μm electrolytic copper foil is placed up and down, pressed at a pressure of 2.0 MPa and a temperature of 240 ° C. for 60 minutes, and then the electrolytic copper foil is removed. A resin plate was obtained.
Further, an E glass cloth having a thickness of 0.1 mm was impregnated with the varnish and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 48 mass%.
Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 3.0 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate.
The measurement and evaluation results of the obtained resin plate and copper clad laminate are shown in Tables 1 to 4.
シロキサン化合物（i）
・Ｘ−２２−１６３Ａ：両末端エポキシ変性シロキサン〔信越化学工業株式会社製、商品名〕
・Ｘ−２２−１６３Ｂ：両末端エポキシ変性シロキサン〔信越化学工業株式会社製、商品名〕
・Ｘ−２２−１６３Ｃ：両末端エポキシ変性シロキサン〔信越化学工業株式会社製、商品名〕
Siloxane compound (i)
-X-22-163A: Both-ends epoxy-modified siloxane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name]
-X-22-163B: Both-ends epoxy-modified siloxane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name]
・ X-22-163C: Epoxy-modified siloxane at both ends [manufactured by Shin-Etsu Chemical Co., Ltd., trade name]
アミン化合物（ii）
・ＫＡＹＡＨＡＲＤ Ａ−Ａ：３，３’−ジエチル−４，４’−ジアミノジフェニルメタン〔日本化薬株式会社製、商品名〕
Amine compound (ii)
KAYAHARD AA: 3,3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name]
マレイミド化合物（Ｂ）
・ＢＭＩ：ビス（４−マレイミドフェニル）メタン〔ケイ・アイ化成株式会社製、商品名〕
・ＢＭＩ−４０００：２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン〔大和化成工業株式会社製、商品名〕
Maleimide compound (B)
-BMI: Bis (4-maleimidophenyl) methane (trade name, manufactured by Kay Kasei Co., Ltd.)
BMI-4000: 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
酸性置換基を有するアミン化合物（Ｃ）
・ｐ−アミノフェノール〔関東化学株式会社製〕
Amine compound having acidic substituent (C)
・ P-aminophenol (manufactured by Kanto Chemical Co., Inc.)
熱可塑性エラストマー（Ｄ）
・エポフレンドＣＴ−３１０：エポキシ変性スチレン−ブタジエン共重合樹脂〔株式会社ダイセル製、商品名〕
Thermoplastic elastomer (D)
・ Epofriend CT-310: Epoxy-modified styrene-butadiene copolymer resin (trade name, manufactured by Daicel Corporation)
熱硬化性樹脂（Ｅ）
・ＰＴ−３０：ノボラック型シアネート樹脂〔ロンザジャパン株式会社製、商品名〕
・ＮＣ−７０００Ｌ：α−ナフトール/クレゾールノボラック型エポキシ樹脂〔日本化薬株式会社製、商品名〕
Thermosetting resin (E)
PT-30: Novolac-type cyanate resin [Lonza Japan Co., Ltd., trade name]
NC-7000L: α-naphthol / cresol novolac type epoxy resin (product name, manufactured by Nippon Kayaku Co., Ltd.)
無機充填剤（Ｆ）
・ＳＣ２０５０−ＫＮＫ：溶融球状シリカ〔株式会社アドマテックス製、平均粒子径０．５μｍ、商品名〕
・ＫＥＭＧＡＲＤ１１００：モリブデン酸亜鉛〔シャーウィン・ウィリアムズ社製、商品名〕
Inorganic filler (F)
SC2050-KNK: fused spherical silica [manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, trade name]
・ KEMGARD1100: zinc molybdate [manufactured by Sherwin Williams, trade name]
硬化促進剤（Ｇ）
・ナフテン酸亜鉛（ＩＩ）８％ミネラルスピリット溶液〔東京化成工業株式会社製、商品名〕
・Ｇ−８００９Ｌ：イソシアネートマスクイミダゾール〔第一工業製薬株式会社製、商品名〕
・ＴＰＰ−ＭＫ：テトラフェニルホスホニウムテトラ-ｐ-トリルボレート〔北興化学工業株式会社製、商品名〕
Curing accelerator (G)
・ Zinc (II) naphthenate 8% mineral spirit solution [Tokyo Chemical Industry Co., Ltd., trade name]
G-8809L: Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name]
・ TPP-MK: Tetraphenylphosphonium tetra-p-tolylborate [made by Hokuko Chemical Co., Ltd., trade name]
第１表〜第４表から明らかなように、本発明の実施例では、樹脂板の硬化収縮率が小さく、低硬化収縮性に優れ、また、積層板の特性においても、熱膨張率、銅箔接着性、弾性率に優れている。
一方、比較例は、樹脂板の硬化収縮率が大きく、また、積層板の特性においても、熱膨張率、銅箔接着性、弾性率において実施例と比較し、いずれかの特性に劣っている。
As is apparent from Tables 1 to 4, in the examples of the present invention, the curing shrinkage rate of the resin plate is small and excellent in low cure shrinkage, and also in the characteristics of the laminated plate, the thermal expansion coefficient, copper Excellent foil adhesion and elastic modulus.
On the other hand, the comparative example has a large curing shrinkage rate of the resin plate, and also in the properties of the laminated plate, the thermal expansion coefficient, the copper foil adhesiveness, and the elastic modulus are inferior to any of the properties. .
本発明の熱硬化性樹脂組成物を、基材に含浸してなるプリプレグ、支持体上に層形成してなる樹脂付フィルム、及び該プリプレグ又は該樹脂付フィルムを積層成形することにより製造した積層板は、特に低硬化収縮性、低熱膨張性、銅箔接着性、高弾性率に優れ、高集積化された半導体パッケージや電子機器用多層プリント配線板として有用である。 A prepreg obtained by impregnating a base material with the thermosetting resin composition of the present invention, a film with a resin formed on a support, and a laminate produced by laminating the prepreg or the resin-coated film. The board is particularly excellent in low curing shrinkage, low thermal expansion, copper foil adhesion, and high elastic modulus, and is useful as a highly integrated semiconductor package and multilayer printed wiring board for electronic devices.
Claims (15)
（式（１）中、Ｒ1は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を、Ｒ2は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。） Furthermore, the thermosetting resin composition for insulating resin layers of the laminated board of Claim 1 or 2 containing the amine compound (C) which has an acidic substituent shown to following General formula (1).
(In formula (1), each R 1 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R 2 independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)
（式（１）中、Ｒ1は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を、Ｒ2は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。） An amino-modified siloxane compound (A) having at least one primary amino group in one molecule, a maleimide compound (B) having at least two N-substituted maleimide groups in one molecule, and the following general formula (1) A thermosetting resin composition for an insulating resin layer of a laminate, comprising a modified imide resin having an acidic substituent, obtained by reacting an amine compound (C) having an acidic substituent shown in An amino-modified siloxane compound (A) having at least one primary amino group in the siloxane compound (i) having at least one epoxy group in one molecule and at least two primary amino groups in one molecule A thermosetting resin composition for an insulating resin layer of a laminate , which is obtained by reacting an amine compound (ii) having
(In formula (1), each R 1 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R 2 independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014151955A JP6596811B2 (en) | 2014-07-25 | 2014-07-25 | Thermosetting resin composition, prepreg using the same, film with resin, laminated board, multilayer printed wiring board, and semiconductor package |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014151955A JP6596811B2 (en) | 2014-07-25 | 2014-07-25 | Thermosetting resin composition, prepreg using the same, film with resin, laminated board, multilayer printed wiring board, and semiconductor package |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016030757A JP2016030757A (en) | 2016-03-07 |
| JP6596811B2 true JP6596811B2 (en) | 2019-10-30 |
Family
ID=55441350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014151955A Active JP6596811B2 (en) | 2014-07-25 | 2014-07-25 | Thermosetting resin composition, prepreg using the same, film with resin, laminated board, multilayer printed wiring board, and semiconductor package |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6596811B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6922167B2 (en) * | 2016-07-20 | 2021-08-18 | 昭和電工マテリアルズ株式会社 | Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board and its manufacturing method |
| JP6750363B2 (en) * | 2016-07-20 | 2020-09-02 | 日立化成株式会社 | Laminates, metal-clad laminates and printed wiring boards |
| JP6955329B2 (en) * | 2016-10-28 | 2021-10-27 | 株式会社日本触媒 | Curable resin composition, encapsulant and semiconductor device using it |
| CN113088061B (en) * | 2019-12-23 | 2022-11-29 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same |
| JP7124898B2 (en) * | 2021-01-13 | 2022-08-24 | 昭和電工マテリアルズ株式会社 | Thermosetting resin compositions, prepregs, laminates, printed wiring boards and semiconductor packages |
| WO2023013709A1 (en) * | 2021-08-05 | 2023-02-09 | 三菱瓦斯化学株式会社 | Resin composition, resin sheet, prepreg, metal foil-clad laminate, and printed wiring board |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05109932A (en) * | 1991-10-15 | 1993-04-30 | Hitachi Chem Co Ltd | Semiconductor sealing resin composition |
| WO2012099134A1 (en) * | 2011-01-18 | 2012-07-26 | 日立化成工業株式会社 | Resin composition, and printed wiring board, laminated sheet, and prepreg using same |
| CN105504809A (en) * | 2011-01-18 | 2016-04-20 | 日立化成株式会社 | Resin composition, and printed wiring board, laminated sheet, and prepreg using same |
| CN103328543B (en) * | 2011-01-18 | 2015-07-15 | 日立化成株式会社 | Modified silicone compound, and thermosetting resin composition, prepreg, laminate plate and printed wiring board using same |
| JP5949249B2 (en) * | 2012-07-13 | 2016-07-06 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board using the same |
| JP6040605B2 (en) * | 2012-07-18 | 2016-12-07 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board using the same |
| JP6019883B2 (en) * | 2012-07-25 | 2016-11-02 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and multilayer printed wiring board using the same |
| JP6322919B2 (en) * | 2012-07-25 | 2018-05-16 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board using the same |
| JP6065437B2 (en) * | 2012-07-25 | 2017-01-25 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board using the same |
| JP6065438B2 (en) * | 2012-07-25 | 2017-01-25 | 日立化成株式会社 | Prepreg, laminated board using the same, and multilayer printed wiring board |
| KR102166235B1 (en) * | 2012-11-28 | 2020-10-15 | 히타치가세이가부시끼가이샤 | Siloxane compound, modified imide resin, thermosetting resin composition, prepreg, resin-equipped film, laminated plate, multilayer printed circuit board, and semiconductor package |
| JP6186712B2 (en) * | 2012-12-05 | 2017-08-30 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and multilayer printed wiring board using the same |
-
2014
- 2014-07-25 JP JP2014151955A patent/JP6596811B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016030757A (en) | 2016-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6372071B2 (en) | Amino-modified siloxane compounds, modified imide resins, thermosetting resin compositions, prepregs, films with resins, laminates, multilayer printed wiring boards, and semiconductor packages | |
| JP6330892B2 (en) | Maleimide resin composition, cured product thereof, prepreg, laminate and multilayer printed wiring board | |
| JP6167850B2 (en) | Thermosetting resin composition, prepreg using the same, film with resin, laminate, printed wiring board, and semiconductor package | |
| JP6379675B2 (en) | Thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package | |
| JP6357762B2 (en) | Modified siloxane compound, thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board and semiconductor package | |
| JP6596811B2 (en) | Thermosetting resin composition, prepreg using the same, film with resin, laminated board, multilayer printed wiring board, and semiconductor package | |
| JP5949249B2 (en) | Thermosetting resin composition, prepreg, laminate and printed wiring board using the same | |
| JP2016132738A (en) | Thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package | |
| JP6427959B2 (en) | Thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package | |
| JP5914988B2 (en) | Prepreg, laminate and printed wiring board using thermosetting resin composition | |
| JP2016033195A (en) | Thermosetting resin composition, and prepreg, laminate and multilayer printed wiring board using the same | |
| JP6299434B2 (en) | Thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package | |
| JP6299433B2 (en) | Thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package | |
| JP7130922B2 (en) | Printed wiring boards, prepregs, laminates and semiconductor packages | |
| JP6819062B2 (en) | Thermosetting resin composition, prepreg using it, film with resin, laminated board, printed wiring board and semiconductor package, and imide resin and its manufacturing method. | |
| WO2018151287A1 (en) | Prepreg, laminate, printed wiring board, coreless substrate, semiconductor package and method for producing coreless substrate | |
| JP6152246B2 (en) | Pre-preg for printed wiring board, laminated board and printed wiring board | |
| JP6369134B2 (en) | Thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package | |
| JP6597721B2 (en) | Thermosetting resin composition, prepreg using the same, film with resin, laminate, printed wiring board, and semiconductor package | |
| JP6164318B2 (en) | Pre-preg for printed wiring board, laminated board and printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170602 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180529 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20180730 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180927 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190205 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190402 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190903 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190916 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6596811 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |