JPS648648B2 - - Google Patents
Info
- Publication number
- JPS648648B2 JPS648648B2 JP13008982A JP13008982A JPS648648B2 JP S648648 B2 JPS648648 B2 JP S648648B2 JP 13008982 A JP13008982 A JP 13008982A JP 13008982 A JP13008982 A JP 13008982A JP S648648 B2 JPS648648 B2 JP S648648B2
- Authority
- JP
- Japan
- Prior art keywords
- bis
- resin
- prepolymer
- cyanate ester
- present
- 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.)
- Expired
Links
- 239000004643 cyanate ester Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
- 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 claims description 11
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 description 15
- -1 4-cyanatophenyl Chemical group 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 150000001913 cyanates Chemical class 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- UFKLQICEQCIWNE-UHFFFAOYSA-N (3,5-dicyanatophenyl) cyanate Chemical compound N#COC1=CC(OC#N)=CC(OC#N)=C1 UFKLQICEQCIWNE-UHFFFAOYSA-N 0.000 description 1
- GUGZCSAPOLLKNG-UHFFFAOYSA-N (4-cyanatophenyl) cyanate Chemical compound N#COC1=CC=C(OC#N)C=C1 GUGZCSAPOLLKNG-UHFFFAOYSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MEZJQXVOMGUAMP-UHFFFAOYSA-N 1-(2-methylnaphthalen-1-yl)pyrrole-2,5-dione Chemical group CC1=CC=C2C=CC=CC2=C1N1C(=O)C=CC1=O MEZJQXVOMGUAMP-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- GEEGPFGTMRWCID-UHFFFAOYSA-N 1-n,1-n,1-n',1-n'-tetramethylbutane-1,1-diamine Chemical compound CCCC(N(C)C)N(C)C GEEGPFGTMRWCID-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- HYVGFUIWHXLVNV-UHFFFAOYSA-N 2-(n-ethylanilino)ethanol Chemical compound OCCN(CC)C1=CC=CC=C1 HYVGFUIWHXLVNV-UHFFFAOYSA-N 0.000 description 1
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- SIQHSJOKAUDDLN-UHFFFAOYSA-N 2-methyl-1-propylimidazole Chemical compound CCCN1C=CN=C1C SIQHSJOKAUDDLN-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- UCNCZASVJWGNBZ-UHFFFAOYSA-N 3-(2-ethyl-5-methyl-1h-imidazol-4-yl)propanenitrile Chemical compound CCC1=NC(CCC#N)=C(C)N1 UCNCZASVJWGNBZ-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-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
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- XECVXFWNYNXCBN-UHFFFAOYSA-N 4-[(4-aminophenyl)-phenylmethyl]aniline Chemical compound C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)C1=CC=CC=C1 XECVXFWNYNXCBN-UHFFFAOYSA-N 0.000 description 1
- CJXRYVQHINFIKO-UHFFFAOYSA-N 4-[1-(4-aminophenyl)-1-phenylethyl]aniline Chemical compound C=1C=C(N)C=CC=1C(C=1C=CC(N)=CC=1)(C)C1=CC=CC=C1 CJXRYVQHINFIKO-UHFFFAOYSA-N 0.000 description 1
- ZSQIQUAKDNTQOI-UHFFFAOYSA-N 4-[1-(4-aminophenyl)cyclohexyl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)CCCCC1 ZSQIQUAKDNTQOI-UHFFFAOYSA-N 0.000 description 1
- KIMCSKCETOAMBU-UHFFFAOYSA-N 4-[2-(4-amino-3,5-dibromophenyl)propan-2-yl]-2,6-dibromoaniline Chemical compound C=1C(Br)=C(N)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(N)C(Br)=C1 KIMCSKCETOAMBU-UHFFFAOYSA-N 0.000 description 1
- UBKRDXUXTYBRHS-UHFFFAOYSA-N 4-[2-(4-amino-3-methylphenyl)propan-2-yl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC(C(C)(C)C=2C=C(C)C(N)=CC=2)=C1 UBKRDXUXTYBRHS-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
- ZTKDMNHEQMILPE-UHFFFAOYSA-N 4-methoxy-n,n-dimethylaniline Chemical compound COC1=CC=C(N(C)C)C=C1 ZTKDMNHEQMILPE-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- GXFRMDVUWJDFAI-UHFFFAOYSA-N [2,6-dibromo-4-[2-(3,5-dibromo-4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C(Br)=C(OC#N)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OC#N)C(Br)=C1 GXFRMDVUWJDFAI-UHFFFAOYSA-N 0.000 description 1
- YKONYNBAMHVIMF-UHFFFAOYSA-N [2,6-dichloro-4-[2-(3,5-dichloro-4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C(Cl)=C(OC#N)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(OC#N)C(Cl)=C1 YKONYNBAMHVIMF-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- SNYVZKMCGVGTKN-UHFFFAOYSA-N [4-(4-cyanatophenoxy)phenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1OC1=CC=C(OC#N)C=C1 SNYVZKMCGVGTKN-UHFFFAOYSA-N 0.000 description 1
- HEJGXMCFSSDPOA-UHFFFAOYSA-N [4-(4-cyanatophenyl)phenyl] cyanate Chemical group C1=CC(OC#N)=CC=C1C1=CC=C(OC#N)C=C1 HEJGXMCFSSDPOA-UHFFFAOYSA-N 0.000 description 1
- CNUHQZDDTLOZRY-UHFFFAOYSA-N [4-(4-cyanatophenyl)sulfanylphenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1SC1=CC=C(OC#N)C=C1 CNUHQZDDTLOZRY-UHFFFAOYSA-N 0.000 description 1
- BUPOATPDNYBPMR-UHFFFAOYSA-N [4-(4-cyanatophenyl)sulfonylphenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1S(=O)(=O)C1=CC=C(OC#N)C=C1 BUPOATPDNYBPMR-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- PPZSVSGWDQKBIW-UHFFFAOYSA-N [4-bis(4-cyanatophenoxy)phosphanyloxyphenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1OP(OC=1C=CC(OC#N)=CC=1)OC1=CC=C(OC#N)C=C1 PPZSVSGWDQKBIW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical class OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 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 1
- 238000013007 heat curing Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- DLAPQHBZCAAVPQ-UHFFFAOYSA-N iron;pentane-2,4-dione Chemical compound [Fe].CC(=O)CC(C)=O DLAPQHBZCAAVPQ-UHFFFAOYSA-N 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- JDEJGVSZUIJWBM-UHFFFAOYSA-N n,n,2-trimethylaniline Chemical compound CN(C)C1=CC=CC=C1C JDEJGVSZUIJWBM-UHFFFAOYSA-N 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
- 239000000025 natural resin Substances 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 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 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 125000005590 trimellitic acid group Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Description
本発明は、(a)多官能性シアン酸エステル、該シ
アン酸エステルプレポリマー或いは該シアン酸エ
ステルとアミンとのプレポリマー、(b)多官能性マ
レイミド、該マレイミドプレポリマー或いは該マ
レイミドとアミンとのプレポリマー、および(c)ジ
シクロペンタジエンあるいはジシクロペンタジエ
ン樹脂を必須成分としてなる硬化性樹脂組成物で
あり、耐衝撃性にすぐれ、かつ接着力、耐熱性、
耐薬品性などの物性にもすぐれた硬化物を与える
ものである。
従来、多官能性シアン酸エステル類と多官能性
マレイミド類を注型等によつて形成した場合、耐
衝撃強度が小さいという欠点があつた。又、シク
ロペンタジエン樹脂を同様に成形したものも脆い
という欠点があつた。
本発明者らは、多官能性シアン酸エステル類、
多官能性マレイミド類およびジシクロペンタジエ
ン類を混合または予備反応して得られた樹脂組成
物は、基材との密着性が良好で、かつ耐衝撃強度
の向上した硬化物を得ることができることを見い
出し、本発明を完成させた。
本発明の組成物のａ成物である多官能性シアン
酸エステルとは２個以上のシアン酸エステル基を
有する有機化合物であり、好適なシアン酸エステ
ルは下記一般式
Ｒ（−Ｏ−Ｃ≡Ｎ）ｍ ……(1)
〔式中のｍは２以上、通常５以下の整数であり
Ｒは芳香族性の有機基であつて、上記シアン酸エ
ステル基は該有機基Ｒの芳香環に結合しているも
の〕
で表わされる化合物である。具体的に例示すれば
１，３―または１，４―ジシアナートベンゼン、
１，３，５―トリシアナ―トベンゼン、１，３
―、１，４―、１，６―、１，８―、２，６―ま
たは２，７―ジシアナートナフレタン、１，３，
６―トリシアナートナフレタン、４，4′―ジシア
ナートビフエニル、ビス（４―ジアナートフエニ
ル）メタン、２，２―ビス（４―シアナートフエ
ニル）プロパン、２，２―ビス（３，５―ジクロ
ロ―４―シアナートフエニル）プロパン、２，２
―ビス（３，５―ジブロモ―４―シアナートフエ
ニル）プロパン、ビス（４―シアナートフエニ
ル）エーテル、ビス（４―シアナートフエニル）
チオエーテル、ビス（４―シアナートフエニル）
スルホン、トリス（４―シアナートフエニル）ホ
スフアイト、トリス（４―シアナートフエニル）
ホスフエート、およびノボラツクとハロゲン化シ
アンとの反応により得られるシアン酸エステルな
どである。これらの他に特公昭41−1928、等公昭
44−4791、特公昭45−11712、特公昭46−41112お
よび特開昭51−63149などに記載のシアン酸エス
テルも用いうる。
又、上述した多官能性シアン酸エステルを、鉱
酸、ルイス酸、炭酸ナトリウム或いは塩化リチウ
ム等の塩類、トリブチルホスフイン等のリン酸エ
ステル類等の触媒の存在下に重合させて得られる
プレポリマーとして用いることができる。これら
のプレポリマーは、前記シアン酸エステル中のシ
アン基が三量化することによつて形成されるsym
―トリアジン環を、一般に分子中に有している。
本発明においては、平均分子量400〜6000の前記
プレポリマーを用いるのが好ましい。
更に、上記した多官能性シアン酸エステルはア
ミンとのプレポリマーの形でも使用できる。好適
に用いうるアミンを例示すれば、メタまたはパラ
フエニレンジアミン、メタまたはパラキシリレン
ジアミン、１，４―または１，３―シクロヘキサ
ンジアミン、ヘキサヒドロキシリレンジアミン、
４，4′―ジアミノビフエニル、ビス（４―アミノ
フエニル）メタン、ビス（４―アミノフエニル）
エーテル、ビス（４―アミノフエニル）スルホ
ン、ビス（４―アミノ―３―メチルフエニル）メ
タン、ビス（４―アミノ―３，５―ジメチルフエ
ニル）メタン、ビス（４―アミノフエニル）シク
ロヘキサン、２，２―ビス（４―アミノフエニ
ル）プロパン、２，２―ビス（４―アミノ―３―
メチルフエニル）プロパン、２，２―ビス（３，
５―ジブロモ―４―アミノフエニル）プロパン、
ビス（４―アミノフエニル）フエニルメタン、
３，４―ジアミノフエニル―4′―アミノフエニル
メタン、１，１―ビス（４―アミノフエニル）―
１―フエニルエタン等である。
むろん、上述した多官能性シアン酸エステル、
そのプレポリマー、およびアミンとのプレポリマ
ーは混合物の形で使用できる。
本発明の組成物のｂ成分の多官能性マレイミド
とは分子中にＮ―マレイミド基を２個以上有する
化合物である。
本発明に好適に使用される多官能性マレイミド
は下記一般式
〔式中、Ｒは２価又は３価の芳香族又は脂環族
性有機基であり、X1、X2は水素、ハロゲン、ま
たはアルキル基であり、ｎは２または３である。〕
で表わされる化合物である。上式で表わされるマ
レイミド類は無水マレイン酸類と２価又は３価の
アミン類とを反応させてマレアミド酸を調製し、
次いでマレアミド酸を脱水環化させるそれ自体公
知の方法で製造することができる。用いる多価ア
ミン類は芳香族アミンであることが最終樹脂の耐
熱性等の点で好ましいが、樹脂の可撓性や柔軟性
が望ましい場合には、脂環族アミンを単独或いは
組合せで使用してもよい。また、多価アミン類は
第１級アミンであることが反応性の点で特に望ま
しいが、第２級アミンも使用できる。好適なアミ
ン類としては、前記の多官能性シアン酸エステル
とアミンとのプレポリマーの製造で例示したも
の、およびｓ―トリアジン環をもつたメラミン、
アニリンとホルマーリンとを反応させてベンゼン
環をメチレン結合で結んだポリアミンなどが示さ
れる。
本発明においては、上述した多官能性マレイミ
ドは、所謂モノマーの形で使用する代りにプレポ
リマーの形で用いることもできるし、更には、多
官能性マレイミド合成に用いたアミンとのプレポ
リマーの形でも好適に用いうる。
次に本発明の(c)成分のジシクロペンタジエンと
は、シクロペンタジエン（沸点41.5℃の液体）を
常温下無触媒で保存するのみで容易に生成する二
量体であり、融点33.6℃の物質である。これは、
常温もしくは減圧下の加熱によつてシクロペンタ
ジエンを生成するものであり、又加圧、加熱下で
は多量体を生成するものである。本発明において
は、ジシクロペンタジエンはそのままモノマーの
形で用いてもよいし、加圧、加熱下で、必要に応
じて他のモノマーを小量用いて、多量体としたも
の、すなわちジシクロペンタジエン樹脂として用
いてもよい。
以上のａ，ｂ，ｃからなる本発明の硬化性樹脂
組成物は、単に混合する方法およびあらかじめ予
備反応さす方法によつて製造される。
本発明の樹脂組成物はそれ自体加熱により結合
し網状化して耐熱性樹脂となる性質を有している
が、架橋網状化を促進する目的で、通常は触媒を
含有させて使用する。このような触媒としては、
２―メチルイミダゾール、２―ウンデシルイミダ
ゾール、２―ヘプタデシルイミダゾール、２―フ
エニルイミダゾール、２―エチル４―メチルイミ
ダゾール、１―ベンジル―２メチルイミダゾー
ル、１―プロピル―２―メチルイミダゾール、１
―シアノエチル―２―メチルイミダゾール、１―
シアノエチル―２エチル―４メチルイミダゾー
ル、１―シアノエチル―２―ウンデシルイミダゾ
ール、１―シアノエチル―２―フエニルイミダゾ
ール、１―グアナミノエチル２―メチルイミダゾ
ールで例示されるイミダゾール類、さらには、こ
れらのイミダゾール類のトリメリト酸付加体な
ど；Ｎ，Ｎ―ジメチルベンジルアミン、Ｎ，Ｎ―
ジメチルアニリン、Ｎ，Ｎ―ジメチルトルイジ
ン、Ｎ，Ｎ―ジメチル―ｐ―アニシジン、ｐ―ハ
ロゲノ―Ｎ，Ｎ―ジメチルアニリン、２―Ｎ―エ
チルアニリノエタノール、トリ―ｎ―ブチルアミ
ン、ピリジン、キノリン、Ｎ―メチルモルホリ
ン、トリエタノールアミン、トリエチレンジアミ
ン、Ｎ，Ｎ，N′，N′―テトラメチルブタンジア
ミン、Ｎ―メチルピペリジンなどの第３級アミン
類；フエノール、クレゾール、キシレノール、レ
ゾルシン、フロログルシン等のフエノール類；ナ
フテン酸鉛、ステアリン酸鉛、ナフテン酸亜鉛、
オクチル酸亜鉛、オレイン酸スズ、ジブチル錫マ
レエート、ナフテン酸マンガン、ナフテン酸コバ
ルト、アセチルアセトン鉄などの有機金属化合
物；SnCl4、ZnCl2、AlCl3などの無機金属化合
物；過酸化ベンゾイル、ラウロイルパーオキサイ
ド、カプリリルパーオキサイド、アセチルパーオ
キサイド、パラクロロベンゾイルパーオキサイ
ド、ジーターシヤリ―ブチルジーパ―フタレート
などの過酸化物が挙げられる。その他に一般にエ
ポキシ樹脂の硬化剤又は触媒として知られている
ものも併用できる。触媒の添加量は、一般的な意
味での触媒量の範囲で十分であり、たとえば全組
成物に対して５重量％以下の量で使用されればよ
い。
本発明の組成物には、組成物本来の特性が損な
われない範囲で、所望に応じて種々の添加物を配
合することができる。これらの添加物としては、
本発明の組成物に新たな性質を付与するための天
然または合成の樹脂類；繊維質補強材；充墳剤；
洗顔料；増粘剤；滑剤；難燃剤等公知の各種添加
剤が含まれ、所望に応じて適宜組合せて用いられ
る。
本発明の硬化性樹脂組成物を硬化させるための
温度は、硬化剤や触媒の有無、組成成分の種類な
どによつても変化するが、通常100〜250℃の範囲
で選ばれればよい。成形品、積層品、接着構造物
等の製造に用いられる場合には、加熱硬化に際し
て圧力を加えることが好ましく、一般的に言つて
10〜500Kg／cm2の範囲内で適宜選ばれる。
以上詳細に述べた本発明の硬化性樹脂組成物
は、硬化速度が比較的早く、しかも比較的温和な
条件で硬化し得るという利点を有しているため、
種々の用途に用いた場合に優れた作業性と生産性
とが得られ、更にこの組成物を硬化させることに
より得た硬化樹脂は、接着性乃至は密着性、耐熱
性及び電気特性等の各種特性の望ましい組合せを
有していると共に、機械的性質特に耐衝撃性にす
ぐれ、耐薬品性、耐湿性等にも優れている。かく
して、本発明の組成物は、防錆、防燃、防災及び
その他各種塗料；電気絶縁用ワニス、接着剤；家
具、建材、外装材、電気絶縁材等の用途に適した
積層材料；或いは各種成形用樹脂として有用であ
る。
以下、実施例および比較例によつて本発明をさ
らに具体的に説明する。
実施例１〜３及び比較例１，２
第１表に示す組成比率で本願発明の組成物及び
比較の為の組成物を調製し、金型に入れて硬化し
て厚さ４mm、直径10cmの注型板を得た。
これらの注型板の試験結果を第２表に示した。
尚、表中の組成成分の調製及び耐衝撃性の試験
方法は以下によつた。
Ａ―１：２，２―ビス（４―シアナトフエニル）
プロパンとビス（４―マレイミドフエニル）
エーテルとを７：３の重量比で用い、150℃
で180分間予備反応させて得たシアン酸エス
テル―マレイミド予備反応物
Ａ―２：２，２―ビス（４―シアナトフエニル）
とプロパンとビス（４―マレイミドフエニ
ル）メタンとを５：５の重量比で用い、160
℃で90分間予備反応させて得たシアン酸エス
テル―マレイミド予備反応物
Ｂ：軟化点100℃であるジシクロペンタジエン樹
脂
Ｃ：ノボラツク型エポキシ樹脂（商品名；ECN
―1280，チバガイギー社製）
耐衝撃性：55ｇの鉄球を70cmの高さから直径９cm
の枠に固定した注型板に落下させる。
Ｏ：割れない Ｘ：割れる。
The present invention provides (a) a polyfunctional cyanate ester, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, (b) a polyfunctional maleimide, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine. This is a curable resin composition comprising a prepolymer and (c) dicyclopentadiene or dicyclopentadiene resin as essential components.
It provides a cured product with excellent physical properties such as chemical resistance. Conventionally, when polyfunctional cyanate esters and polyfunctional maleimides were formed by casting or the like, there was a drawback of low impact strength. Furthermore, products made of cyclopentadiene resin also had the disadvantage of being brittle. The present inventors have discovered that polyfunctional cyanate esters,
The resin composition obtained by mixing or pre-reacting polyfunctional maleimides and dicyclopentadienes has been shown to have good adhesion to the base material and can yield a cured product with improved impact strength. Heading, the present invention has been completed. The polyfunctional cyanate ester, which is a component of the composition of the present invention, is an organic compound having two or more cyanate ester groups, and a suitable cyanate ester has the following general formula R(-O-C≡ N)m...(1) [In the formula, m is an integer of 2 or more and usually 5 or less, R is an aromatic organic group, and the cyanate ester group is attached to the aromatic ring of the organic group R. It is a compound represented by Specific examples include 1,3- or 1,4-dicyanatobenzene,
1,3,5-tricyanatobenzene, 1,3
-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonafretane, 1,3,
6-tricyanatonaphrethane, 4,4'-dicyanatobiphenyl, bis(4-dyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis( 3,5-dichloro-4-cyanatophenyl)propane, 2,2
-Bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)
Thioether, bis(4-cyanatophenyl)
Sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl)
These include phosphates, and cyanate esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, etc.
Cyanic acid esters described in Japanese Patent Publication No. 44-4791, Japanese Patent Publication No. 45-11712, Japanese Patent Publication No. 46-41112, and Japanese Patent Publication No. 51-63149 can also be used. Further, a prepolymer obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence of a catalyst such as a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylphosphine. It can be used as These prepolymers are symylamines formed by trimerization of the cyanide groups in the cyanate ester.
- Generally has a triazine ring in the molecule.
In the present invention, it is preferable to use the prepolymer having an average molecular weight of 400 to 6,000. Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines. Examples of amines that can be suitably used include meta or paraphenylene diamine, meta or para xylylene diamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylene diamine,
4,4'-diaminobiphenyl, bis(4-aminophenyl)methane, bis(4-aminophenyl)
Ether, bis(4-aminophenyl) sulfone, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-aminophenyl)cyclohexane, 2,2- Bis(4-aminophenyl)propane, 2,2-bis(4-amino-3-
methylphenyl)propane, 2,2-bis(3,
5-dibromo-4-aminophenyl)propane,
bis(4-aminophenyl)phenylmethane,
3,4-diaminophenyl-4'-aminophenylmethane, 1,1-bis(4-aminophenyl)-
1-phenylethane and the like. Of course, the above-mentioned polyfunctional cyanate ester,
The prepolymers, and the prepolymers with amines, can be used in the form of mixtures. The polyfunctional maleimide as component b of the composition of the present invention is a compound having two or more N-maleimide groups in the molecule. The polyfunctional maleimide suitably used in the present invention has the following general formula: [Wherein, R is a divalent or trivalent aromatic or alicyclic organic group, X 1 and X 2 are hydrogen, halogen, or an alkyl group, and n is 2 or 3. ] It is a compound represented by Maleimides represented by the above formula are prepared by reacting maleic anhydride with divalent or trivalent amines to prepare maleamic acid,
It can then be produced by a method known per se in which maleamic acid is cyclodehydrated. The polyvalent amines used are preferably aromatic amines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. You can. Furthermore, it is particularly desirable that the polyvalent amines be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include those exemplified in the production of the prepolymer of polyfunctional cyanate ester and amine, and melamine having an s-triazine ring;
Examples include polyamines in which benzene rings are linked with methylene bonds by reacting aniline and formalin. In the present invention, the above-mentioned polyfunctional maleimide can be used in the form of a prepolymer instead of in the form of a so-called monomer, and furthermore, it can be used in the form of a prepolymer with the amine used in the synthesis of the polyfunctional maleimide. It can also be suitably used in the form of Next, dicyclopentadiene, component (c) of the present invention, is a dimer that is easily produced simply by storing cyclopentadiene (a liquid with a boiling point of 41.5°C) at room temperature without a catalyst, and a substance with a melting point of 33.6°C. It is. this is,
It produces cyclopentadiene when heated at room temperature or under reduced pressure, and produces a polymer when heated under pressure or heat. In the present invention, dicyclopentadiene may be used as it is in the form of a monomer, or it may be made into a multimer by using small amounts of other monomers as necessary under pressure and heat. It may also be used as a resin. The curable resin composition of the present invention consisting of the above components a, b, and c can be produced by a simple mixing method or a pre-reaction method. The resin composition of the present invention itself has the property of becoming a heat-resistant resin by being bonded and reticulated by heating, but in order to promote crosslinking and reticulation, it is usually used in the form of a catalyst. Such a catalyst is
2-Methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-ethyl 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1
-cyanoethyl-2-methylimidazole, 1-
Imidazoles exemplified by cyanoethyl-2ethyl-4methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole, and further, these imidazoles such as trimellitic acid adducts; N,N-dimethylbenzylamine, N,N-
Dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl-p-anisidine, p-halogeno-N,N-dimethylaniline, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, Tertiary amines such as N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutanediamine, N-methylpiperidine; phenol, cresol, xylenol, resorcin, phloroglucin, etc. Phenols; lead naphthenate, lead stearate, zinc naphthenate,
Organometallic compounds such as zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; inorganic metal compounds such as SnCl 4 , ZnCl 2 , AlCl 3 ; benzoyl peroxide, lauroyl peroxide, Examples include peroxides such as caprylyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and tertiary butyl perphthalate. In addition, what is generally known as a curing agent or catalyst for epoxy resins can also be used in combination. The amount of the catalyst to be added is sufficient within the general range of the catalyst amount, for example, it may be used in an amount of 5% by weight or less based on the total composition. The composition of the present invention may contain various additives as desired, as long as the original properties of the composition are not impaired. These additives include:
Natural or synthetic resins for imparting new properties to the composition of the present invention; fibrous reinforcement; filler;
Various known additives such as facial cleansers, thickeners, lubricants, and flame retardants are included, and can be used in appropriate combinations as desired. The temperature for curing the curable resin composition of the present invention varies depending on the presence or absence of a curing agent and catalyst, the types of composition components, etc., but may be generally selected within the range of 100 to 250°C. When used in the production of molded products, laminated products, adhesive structures, etc., it is preferable to apply pressure during heat curing;
Appropriately selected within the range of 10 to 500Kg/ cm2 . The curable resin composition of the present invention described in detail above has the advantage that it has a relatively fast curing speed and can be cured under relatively mild conditions.
Excellent workability and productivity are obtained when used for various purposes, and the cured resin obtained by curing this composition has various properties such as adhesiveness, adhesion, heat resistance, and electrical properties. It has a desirable combination of properties, and has excellent mechanical properties, particularly impact resistance, as well as chemical resistance and moisture resistance. Thus, the composition of the present invention can be used for various purposes such as rust prevention, fire prevention, disaster prevention, and other various paints; electrical insulating varnishes, adhesives; laminated materials suitable for use in furniture, building materials, exterior materials, electrical insulation materials, etc.; Useful as a molding resin. The present invention will be explained in more detail below using Examples and Comparative Examples. Examples 1 to 3 and Comparative Examples 1 and 2 Compositions of the present invention and comparative compositions were prepared according to the composition ratios shown in Table 1, placed in a mold and cured to form a mold with a thickness of 4 mm and a diameter of 10 cm. A casting board was obtained. The test results for these casting plates are shown in Table 2. The composition components listed in the table were prepared and the impact resistance was tested as follows. A-1: 2,2-bis(4-cyanatophenyl)
Propane and bis(4-maleimidophenyl)
and ether at a weight ratio of 7:3 at 150°C.
Cyanate ester-maleimide pre-reacted product A-2 obtained by pre-reacting for 180 minutes: 2,2-bis(4-cyanatophenyl)
and propane and bis(4-maleimidophenyl)methane at a weight ratio of 5:5, 160
Cyanate ester-maleimide pre-reacted product obtained by pre-reacting at ℃ for 90 minutes B: Dicyclopentadiene resin with a softening point of 100℃ C: Novolac type epoxy resin (product name: ECN
-1280, manufactured by Ciba Geigy) Impact resistance: A 55g iron ball is thrown from a height of 70cm to a diameter of 9cm.
drop it onto a casting board fixed to a frame. O: Does not break. X: Breaks.
【表】【table】
【表】【table】
【表】
実施例 ４
２，２―ビス（４―シアナトフエニル）プロパ
ン610ｇとビス（４―マレイミドフエニル）メタ
ン260ｇとを160℃で130分間予備反応させ、これ
に軟化点100℃のジシクロペンタジエン樹脂130
ｇ、さらに、触媒としてオクチル酸亜鉛0.4ｇ及
びジクミルパーオキサイド0.6ｇ、充墳剤として
ウオラストナイト1500ｇ及びカーボンブラツク４
ｇ加え、加熱ロールで80℃にて５分間均一に混練
して成形材料を得た。
この成形材料を用い、圧力60Kg／cm2、170℃で
90分間で成形し、200℃で４時間後硬化させた。
この成形品の試験結果を第３表に示した。
比較例 ３
実施例４において、ジシクロペンタジエン樹脂
を用いず、樹脂成分に対する充墳剤量比は同一と
して成形材料を得、同様に成形品を作成し、試験
した。結果を第３表に示した。[Table] Example 4 610 g of 2,2-bis(4-cyanatophenyl)propane and 260 g of bis(4-maleimidophenyl)methane were pre-reacted at 160°C for 130 minutes, and dicyclopentadiene with a softening point of 100°C was added to the reaction. resin 130
g, furthermore, 0.4 g of zinc octylate and 0.6 g of dicumyl peroxide as a catalyst, 1500 g of wollastonite and carbon black 4 as a filler.
g was added and kneaded uniformly for 5 minutes at 80°C with a heating roll to obtain a molding material. Using this molding material, at a pressure of 60Kg/cm 2 and at 170℃.
It was molded for 90 minutes and post-cured at 200°C for 4 hours.
The test results for this molded article are shown in Table 3. Comparative Example 3 In Example 4, a molding material was obtained without using the dicyclopentadiene resin and the ratio of the amount of filler to the resin component was the same, and a molded article was prepared and tested in the same manner. The results are shown in Table 3.
【表】
実施例５及び比較例４
２，２―ビス（４―シアナートフエニル）プロ
パン950ｇを160℃で１時間予備反応を行つてプレ
ポリマーを得た。これにビス（４―マレイミドフ
エニル）メタン40ｇおよび４―マレイミドフエニ
ル―3′，4′―ジマレイミドフエニルメタンと４―
マレイミドフエニル―2′，4′―ジマレイミドフエ
ニルメタンとの混合物60ｇを入れ、更にジシクロ
ペンタジエン樹脂（軟化点125℃）を200ｇ入れて
150℃で１時間反応させた。これをジメチルホル
ムアミドとメチルエチルケトンとの混合溶剤に溶
解し、触媒としてオクチル酸亜鉛0.5ｇ、トリエ
チレンジアミン0.4ｇ、過酸化ベンゾイル0.1ｇを
混合しワニスとした。このワニスをガラス織布に
含浸させ加熱乾燥してＢ―stageのプリプレグと
した。
上記プリプレグを数枚重ね、両側に厚さ35μの
銅箔を入れて、温度180℃、圧力50Kg／cm2で２時
間プレス成形した。得られた積層板の試験結果を
第４表に示した。
比較例 ４
実施例５でジシクロペンタジエン樹脂を用い
ず、他は同様にして銅張積層板を得た。その板の
試験結果を第４表に示した。[Table] Example 5 and Comparative Example 4 950 g of 2,2-bis(4-cyanatophenyl)propane was subjected to a preliminary reaction at 160° C. for 1 hour to obtain a prepolymer. To this was added 40 g of bis(4-maleimidophenyl)methane, 4-maleimidophenyl-3',4'-dimaleimidophenylmethane and 4-
Add 60 g of a mixture with maleimidophenyl-2',4'-dimaleimidophenylmethane, and then add 200 g of dicyclopentadiene resin (softening point 125°C).
The reaction was carried out at 150°C for 1 hour. This was dissolved in a mixed solvent of dimethylformamide and methyl ethyl ketone, and 0.5 g of zinc octylate, 0.4 g of triethylenediamine, and 0.1 g of benzoyl peroxide were mixed as catalysts to prepare a varnish. A glass woven fabric was impregnated with this varnish and dried by heating to obtain a B-stage prepreg. Several sheets of the above prepreg were stacked, copper foil with a thickness of 35 μm was placed on both sides, and press molding was performed at a temperature of 180° C. and a pressure of 50 kg/cm 2 for 2 hours. The test results of the obtained laminates are shown in Table 4. Comparative Example 4 A copper-clad laminate was obtained in the same manner as in Example 5 except that the dicyclopentadiene resin was not used. The test results for the board are shown in Table 4.
【表】【table】
Claims (1)
エステルプレポリマー或いは該シアン酸エステ
ルとアミンとのプレポリマー、 (b) 多官能性マレイミド、該マレイミドプレポリ
マー或いは該マレイミドとアミンとのプレポリ
マー、及び (c) ジシクロペンタジエンあるいはジシクロペン
タジエン樹脂 を必須成分としてなる硬化性樹脂組成物。[Claims] 1 (a) a polyfunctional cyanate ester, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine; (b) a polyfunctional maleimide, the maleimide prepolymer, or the maleimide and (c) dicyclopentadiene or dicyclopentadiene resin as essential components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13008982A JPS5874750A (en) | 1982-07-26 | 1982-07-26 | Curable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13008982A JPS5874750A (en) | 1982-07-26 | 1982-07-26 | Curable resin composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8862079A Division JPS5611924A (en) | 1979-07-12 | 1979-07-12 | Curable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5874750A JPS5874750A (en) | 1983-05-06 |
| JPS648648B2 true JPS648648B2 (en) | 1989-02-14 |
Family
ID=15025702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13008982A Granted JPS5874750A (en) | 1982-07-26 | 1982-07-26 | Curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5874750A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4528366A (en) * | 1982-09-28 | 1985-07-09 | The Dow Chemical Company | Production of polytriazines from aromatic polycyanates with cobalt salt of a carboxylic acid as catalyst |
-
1982
- 1982-07-26 JP JP13008982A patent/JPS5874750A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5874750A (en) | 1983-05-06 |
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