JPS6369818A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- JPS6369818A JPS6369818A JP61213925A JP21392586A JPS6369818A JP S6369818 A JPS6369818 A JP S6369818A JP 61213925 A JP61213925 A JP 61213925A JP 21392586 A JP21392586 A JP 21392586A JP S6369818 A JPS6369818 A JP S6369818A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- diisocyanate
- polyfunctional
- component
- electron
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 18
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- 150000002118 epoxides Chemical class 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- -1 polycyclic aromatic compound Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 3
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000012492 regenerant Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- JUSWGNJYSBSOFM-UHFFFAOYSA-N 1,3,6,8-tetranitro-9h-carbazole Chemical compound C1=C([N+]([O-])=O)C=C2C3=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C3NC2=C1[N+]([O-])=O JUSWGNJYSBSOFM-UHFFFAOYSA-N 0.000 claims 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims 1
- FMXDVBRYDYFVGS-UHFFFAOYSA-N 2-methoxy-1,3,5-trinitrobenzene Chemical compound COC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O FMXDVBRYDYFVGS-UHFFFAOYSA-N 0.000 claims 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 claims 1
- 238000005266 casting Methods 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 7
- 239000000370 acceptor Substances 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RXUVWJWQFPJWOV-OWOJBTEDSA-N (e)-1,2-diisocyanatoethene Chemical compound O=C=N\C=C\N=C=O RXUVWJWQFPJWOV-OWOJBTEDSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SIZPGZFVROGOIR-UHFFFAOYSA-N 1,4-diisocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=C(N=C=O)C2=C1 SIZPGZFVROGOIR-UHFFFAOYSA-N 0.000 description 1
- DDHYZBVBQZYMTO-UHFFFAOYSA-N 1-(dimethylamino)pentan-1-ol Chemical compound CCCCC(O)N(C)C DDHYZBVBQZYMTO-UHFFFAOYSA-N 0.000 description 1
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 1
- HJRJRUMKQCMYDL-UHFFFAOYSA-N 1-chloro-2,4,6-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1 HJRJRUMKQCMYDL-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- BPHYZRNTQNPLFI-UHFFFAOYSA-N 2,4,6-trihydroxytoluene Chemical compound CC1=C(O)C=C(O)C=C1O BPHYZRNTQNPLFI-UHFFFAOYSA-N 0.000 description 1
- KPRZOPQOBJRYSW-UHFFFAOYSA-N 2-(aminomethyl)phenol Chemical compound NCC1=CC=CC=C1O KPRZOPQOBJRYSW-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- NZHNJOJQMPJLFA-UHFFFAOYSA-N 2-[3,5-bis(oxiran-2-yl)phenyl]oxirane Chemical compound C1OC1C1=CC(C2OC2)=CC(C2OC2)=C1 NZHNJOJQMPJLFA-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-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 compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- 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
- WLDMPODMCFGWAA-UHFFFAOYSA-N 3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione Chemical compound C1CCCC2C(=O)NC(=O)C21 WLDMPODMCFGWAA-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VUPOPVGVEARXGA-UHFFFAOYSA-N C[SiH2]C.N=C=O.N=C=O Chemical compound C[SiH2]C.N=C=O.N=C=O VUPOPVGVEARXGA-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- IUJJPSLPEWPXBV-UHFFFAOYSA-N N=C=O.N=C=O.C(C=C1)=CC=C1[SiH2]C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C(C=C1)=CC=C1[SiH2]C1=CC=CC=C1 IUJJPSLPEWPXBV-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- SGLGUTWNGVJXPP-UHFFFAOYSA-N benzene-1,3,5-tricarbonitrile Chemical compound N#CC1=CC(C#N)=CC(C#N)=C1 SGLGUTWNGVJXPP-UHFFFAOYSA-N 0.000 description 1
- WDWRGQPWWISEKM-UHFFFAOYSA-N benzyl(16-methylheptadecyl)azanium;chloride Chemical compound [Cl-].CC(C)CCCCCCCCCCCCCCC[NH2+]CC1=CC=CC=C1 WDWRGQPWWISEKM-UHFFFAOYSA-N 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GLROGUSVUGSGPO-UHFFFAOYSA-N bis(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1C2OC2CC(C)C1OC(=O)CCCCC(=O)OC1CC2OC2CC1C GLROGUSVUGSGPO-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- YIFWXQBNRQNUON-UHFFFAOYSA-M dodecyl(trimethyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCC[N+](C)(C)C YIFWXQBNRQNUON-UHFFFAOYSA-M 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 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
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000000015 trinitrotoluene Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、多官能イソシアネート再生体と水酸基含有多
官能エポキシドとを硬化性成分として含む、貯蔵安定性
の良好な樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition with good storage stability, which contains a regenerated polyfunctional isocyanate and a hydroxyl group-containing polyfunctional epoxide as curable components.
従来、ドイツ連邦共和国特許公告１，１１５゜９２２号
に記載のように、多官能イソシアネートと水酸基含有多
官能エポキシドとから成る樹脂組成物は、加熱すると高
温寸法安定性を示す硬仕物となるため、注型用樹脂、接
着剤、塗料などの形で工業的利用が拡がりつつある。多
官能イソシアネートは１周知のように、極めて反応性に
富み、アルコールや大気中の水分と容易に反応するため
、水酸基含有多官能エポキシドと混合すると、ウレタン
に変化したり、空気中の水分と反応し、極めて短時間の
うちに使用に耐えない迄に変質するといった欠点があっ
た。この欠点を改善するため、発明者らは、種々検討を
行った。特公昭５３−６９７９■公報に記載されている
ように、多官能イソシアネートと多官能エポキシドとか
ら成る樹脂組成物の貯蔵安定性の向上には、多官能イン
シアネート再生体、多官能エポキシドと酸性物質とから
成る樹脂組成物に構成を変えることが望ましい。アルコ
ールは多官能イソシアネート再生体と容易に反応するこ
とから、多官能エポキシドの代りに水酸基含有多官能エ
ポキシドを用いた場合、アルコールの影響で酸性物質が
必ずしも貯蔵安定性を向上させるとは限らない。そこで
、酸性物化を添加した場合の貯蔵安定性を種々検討し、
本発明に至った。Conventionally, as described in Patent Publication No. 1,115°922 of the Federal Republic of Germany, a resin composition composed of a polyfunctional isocyanate and a hydroxyl group-containing polyfunctional epoxide becomes a hard workpiece that exhibits high temperature dimensional stability when heated. , industrial use is expanding in the form of casting resins, adhesives, paints, etc. As is well known, polyfunctional isocyanates are extremely reactive and easily react with alcohol and moisture in the air, so when mixed with polyfunctional epoxides containing hydroxyl groups, they change into urethane and react with moisture in the air. However, it had the disadvantage that it deteriorated to the point that it could no longer be used in a very short period of time. In order to improve this drawback, the inventors conducted various studies. As described in Japanese Patent Publication No. 53-6979, in order to improve the storage stability of a resin composition consisting of a polyfunctional isocyanate and a polyfunctional epoxide, a regenerated polyfunctional incyanate, a polyfunctional epoxide, and an acidic substance are used. It is desirable to change the composition to a resin composition consisting of. Since alcohol easily reacts with the polyfunctional isocyanate regenerant, when a hydroxyl group-containing polyfunctional epoxide is used instead of a polyfunctional epoxide, the acidic substance does not necessarily improve storage stability due to the influence of the alcohol. Therefore, we conducted various studies on storage stability when adding acidification.
This led to the present invention.
本発明の目的は、多官能イソシアネートと水酸基含有多
官能エポキシドとから成る、樹脂組成物の貯蔵安定性を
高度に安定させることにある。An object of the present invention is to highly stabilize the storage stability of a resin composition comprising a polyfunctional isocyanate and a hydroxyl group-containing polyfunctional epoxide.
」１記目的は、（Ａ）多官能イソシアネート再生体と（
Ｂ）水酸基含有多官能エポキシドを含む樹脂組成物に、
（Ｃ）π型電子受容体を添加することにより達成される
。” 1. Purpose is to (A) regenerate polyfunctional isocyanate and (
B) A resin composition containing a hydroxyl group-containing polyfunctional epoxide,
(C) Achieved by adding a π-type electron acceptor.
π型電子受容体の作用機構は明らかではないが、恐らく
多官能イソシアネート再生体のウレタン結合が開裂して
、イソシアネートを再生する反応を抑制するため、貯蔵
安定性が大幅に向上したものと考えられる。The mechanism of action of the π-type electron acceptor is not clear, but it is thought that the urethane bonds in the polyfunctional isocyanate regenerant are cleaved and the reaction that regenerates the isocyanate is suppressed, resulting in a significant improvement in storage stability. .
多官能イソシアネート再生体とは、例えば、５ａｕｎｄ
ｅｒｓ ＆ Ｆｒ１ｓｃｈ著Ｐｏ１ｙｕｒｅｔｈａｎｅ
ｓ Ｐａｒｔ ＩＣｈｅｍｉｓｔｒｙ （インターサ
イエンス・パブリッシャ−ズ発行）１１８頁以降に記載
されているように、フェノール類、三級アルコール類、
芳香族第二級アミン類、ラクタムなどの活性水素化合物
で多官能イソシアネートのイソシアネー１−基をマスク
して得られ、加熱されると解離してイソシアネーｊ・を
再生する化合物である。この再生体の合成に使用される
多官能イソシアネートとして、例えば、メタンジイソシ
アネート、ブタン−１，１−ジイソシアネート、エタン
−１，２，ジイソイアネート、ブタン−１，２−ジイソ
シアネート、トランスビニレンジイソシアネート、プロ
パン−１，３−ジイソシアネート、ブタン−１，４−ジ
イソシアネート、２−ブテン−１，４−ジイソシアネー
ト、２−メチルブタン−１，４−ジイソシアネート、ペ
ンタン−１，５−ジイソシアネート、２゜２−ジメチル
ペンタン−１，５−ジイソシアネート、ヘキサン−１，
６−ジイソシアネート、ヘプタン−１，７−ジイソシア
ネート、オクタン−１゜８−ジイソシアネート、ノナン
−１，９−ジイソシアネ−１〜、デカン−１，１０−ジ
イソシアネート、ジメチルシランジイソシアネート、ジ
フェニルシランジイソシアネート、ω、ω’−１．３−
ジメチルベンゼンジイソシアネート、ω、ω′−１．４
−ジメチルベンゼンジイソシアネート、ω。The polyfunctional isocyanate regenerated product is, for example, 5 ound
Po1yurethane by ers & Fr1sch
s Part IChemistry (published by Interscience Publishers) As described from page 118 onwards, phenols, tertiary alcohols,
It is a compound obtained by masking the isocyanate 1-group of a polyfunctional isocyanate with an active hydrogen compound such as an aromatic secondary amine or a lactam, and when heated, it dissociates to regenerate isocyanate j. Examples of the polyfunctional isocyanate used in the synthesis of this regenerated product include methane diisocyanate, butane-1,1-diisocyanate, ethane-1,2, diisocyanate, butane-1,2-diisocyanate, transvinylene diisocyanate, propane-1 , 3-diisocyanate, butane-1,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, 2゜2-dimethylpentane-1, 5-diisocyanate, hexane-1,
6-diisocyanate, heptane-1,7-diisocyanate, octane-1°8-diisocyanate, nonane-1,9-diisocyanate-1-, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω, ω '-1.3-
Dimethylbenzene diisocyanate, ω, ω′-1.4
-dimethylbenzene diisocyanate, ω.
ω’−１，３−ジメチルシクロヘキサンジイソシアネー
ト、ω、ω’−１．４−ジメチルシクロヘキサンジイソ
シアネート、ω、ω’−１．４−ジメチルベンゼンジイ
ソシアネート、ω、ω′−１゜４−ジメチルナフタリン
ジイソシアネート、ω。ω'-1,3-dimethylcyclohexane diisocyanate, ω,ω'-1,4-dimethylcyclohexane diisocyanate, ω,ω'-1,4-dimethylbenzene diisocyanate, ω,ω'-1°4-dimethylnaphthalene diisocyanate, ω.
ω’−１，５−ジメチルナフタリンジイソシアネート、
シクロヘキサン−１，３−ジイソシアネート、シクロヘ
キサン−１，４−ジイソシアネ−１〜、ジシクムヘキサ
ンメタン−４，４′−ジイソシアネート、１，３−フェ
ニレンジイソシアネート、１．４−フェニレンジイソシ
アネート、１−メチルベンゼン、２，４−ジイソシアネ
ート、１−メチルベンゼン−２，５−ジイソシアネート
、１−メチルベンゼン−２，６−ジイソシアネート、１
−メチルベンゼン−３，５−ジイソシアネート、ジフェ
ニルエーテル−４，４′−ジイソシアネート、ジフェニ
ルエーテル−２，４′−ジイソシアネート、ナフタリン
−１，４−ジイソシアネート、ナフタリン−１，５−ジ
イソシアネ−１〜、ビフェニル−４，４′−ジイソシア
ネート、３．３’−ジメチルビフェニル−４，４′−ジ
イソシアネート、２，３′−ジメトキシビフェニル−４
，４′−ジイソシアネ−１〜、ジフェニルメタン、４゜
４′−ジイソシアネ−１〜、３，３′−ジメトキシジフ
ェニルメタン−４，４′−ジイソシアネート、４．４′
−ジメトキシジフェニルメタン−３゜３′−ジイソシア
ネート、ジフェニルサルファイド−４，４′−ジイソシ
アネート、ジフェニルスルホン−４，４′−ジイソシア
ネートなどの三官能のイソシアネー１〜、ポリメチレン
ポリフェニルイソシアネート、トリフェニルメタントル
イソシアネート、トリス（４−フェニルイソシアネート
チオホスフェート）、３．３’、４．４’−ジフェニル
メタンテトライソシアネ−１〜などの三官能以上のイソ
シアネートが用いられる。ω'-1,5-dimethylnaphthalene diisocyanate,
Cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate-1-, dicycumhexanemethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methylbenzene, 2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1
-Methylbenzene-3,5-diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate-1-, biphenyl-4 , 4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,3'-dimethoxybiphenyl-4
, 4'-diisocyane-1~, diphenylmethane, 4゜4'-diisocyane-1~, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4.4'
- Trifunctional isocyanes 1 to 1 such as dimethoxydiphenylmethane-3゜3'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane toluisocyanate , tris(4-phenylisocyanate thiophosphate), 3.3', 4.4'-diphenylmethanetetrisocyanate-1, etc. are used.
また、これらのイソシアネートの二量体、玉量体あるい
は４，４′−ジフェニルメタンジイソシアネ−１・の一
部をカルボジイミド化した液状イソシアネートなども用
いることができる。Also usable are dimers and gleamers of these isocyanates, or liquid isocyanates obtained by converting a portion of 4,4'-diphenylmethane diisocyanate-1 into carbodiimide.
又、水酸基含有多官能エポキシドとは、水酸基をもつ、
多官能エポキシドであれば、特に制限はない。例えば、
ビスフェノールＡのジグリシジルエーテル、ブタジエン
ジエポキサイド、３，４−エポキシシクロヘキシルメチ
ル−（３，４−エポキシ）シクロヘキサンカルボキシレ
ート、ビニルシクロヘキセンジオキサイド、４．４ ’
−（１゜２−エポキシエチル）ジフェニルエーテル、４
゜４’−（１，２−エポキシエチル）ビフェニル、２．
２−ビス（３，４−エポキシシクロヘキシル）プロパン
、レゾルシンのジグリシジルエーテル、フロログルシン
のジグリシジルエーテル、メチルフロログルシンのジグ
リシジルエーテル、ビス（２，３−エポキシシクロペン
チル）エーテル、２−（３，４−エポキシ）シクロヘキ
サン−５゜５−スピロ（３，４−エポキシ）−シクロヘ
キサン−ｍ−ジオキサン、ビス−（３，４−エポキシ−
６−メチルシクロヘキシル）アジペート、Ｎ。In addition, hydroxyl group-containing polyfunctional epoxide refers to hydroxyl group-containing polyfunctional epoxide,
There are no particular limitations as long as it is a polyfunctional epoxide. for example,
Diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate, vinylcyclohexene dioxide, 4.4'
-(1゜2-epoxyethyl)diphenyl ether, 4
゜4'-(1,2-epoxyethyl)biphenyl, 2.
2-bis(3,4-epoxycyclohexyl)propane, diglycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis(2,3-epoxycyclopentyl)ether, 2-(3, 4-epoxy)cyclohexane-5゜5-spiro(3,4-epoxy)-cyclohexane-m-dioxane, bis-(3,4-epoxy-
6-Methylcyclohexyl)adipate, N.
Ｎ’−ｍ−フェニレンビス（４，５−エポキシ−１，２
−シクロヘキサンジカルボキシイミドなどの三官能のエ
ポキサイド、パラアミノフェノールのトリグリシジルエ
ーテル、ポリアリルグリシジルエーテル、１，３．５−
トリ（１，２−エポキシエチル）ベンゼン、２．２’、
４．４’−テトラグリシドキシベンゾフェノン、テトラ
グリシドキシテトラフェニルエタン、フェノールホルム
アルデヒドノボラックポリグリシジルエーテル、グリセ
リンのトリグリシジルエーテル、トリメチロールプロパ
ンのトリグリシジエーテルなどの三官能以上のエポキサ
イドのオリゴマ、あるいは酸無水物、又は、アミン等の
付加物等がある。このうち、特に、ビスフェノールＡの
ジグリシジルエーテルのオリゴマやビスフェノールＦの
ジグリシジルエーテルのオリゴマが有用である。N'-m-phenylenebis(4,5-epoxy-1,2
-Trifunctional epoxides such as cyclohexanedicarboximide, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3.5-
tri(1,2-epoxyethyl)benzene, 2.2',
4. Oligomers of trifunctional or higher functional epoxides such as 4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, phenol formaldehyde novolac polyglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, or Examples include acid anhydrides and adducts such as amines. Among these, oligomers of diglycidyl ether of bisphenol A and oligomers of diglycidyl ether of bisphenol F are particularly useful.
なお、多官能イソシアネート再生体および水酸基含有多
官能エポキシドはそれぞれ単独もしくは二種以上混合し
て用いることができる。そして、多官能イソシアネート
再生体と水酸基含有多官能エポキシドの配合割合は、特
に、限定されないが、多官能インシアネート再生体の配
合量が多くなるほど、耐熱性が良好となるが固く脆くな
る傾向にある。逆に、多官能エポキシドの配合量が多く
なるほど、可どう性に富むが、耐熱性が低下する傾向に
ある。好ましくは、水酸基含有多官能エポキシド−当量
に対し、多官能イソシアネート再生体を０．５〜１５当
量配合するのが良い。Note that the polyfunctional isocyanate regenerated product and the hydroxyl group-containing polyfunctional epoxide can be used alone or in a mixture of two or more. The blending ratio of the recycled polyfunctional isocyanate and the hydroxyl group-containing polyfunctional epoxide is not particularly limited, but the larger the blended amount of the recycled polyfunctional isocyanate, the better the heat resistance becomes, but it tends to become harder and brittle. . Conversely, as the amount of polyfunctional epoxide increases, flexibility increases, but heat resistance tends to decrease. Preferably, 0.5 to 15 equivalents of the regenerated polyfunctional isocyanate are blended relative to the equivalent of the hydroxyl group-containing polyfunctional epoxide.
本発明において使用するπ型電子受容体とは、Ｒ、Ｓ
、 Ｍｕｌｌｉｋｅｎ ： Ｊｏｕｒｎａｌ ｄａ Ｃ
ｈｉｍｉｅ Ｐｈｙｓｉｑｕｅ。The π-type electron acceptors used in the present invention are R, S
, Mulliken: Journal da C
himie Physique.
６１巻、１９６４年、２１頁に定義されているような、
電荷移動力によって電子供与体と電荷移動錯体を作り得
り化合物であり、環に、例えば、−Ｎ Ｏ２、−ＣＮ
、 −ＣＯＯＲ、ＣＯＲなど電子求引性置換基をもつ単
環、多環もしくはヘテロ環芳香族化合物、キノン化合物
、および電子求引性基によって全ての水素原子が置換さ
れた脂肪族不飽和炭化水素から成る群から選ばれる。そ
のような化合物の具体例は、１，３．５−トリニ１〜口
ベンゼン、２，４．．６−トリニトロトルエン、２゜４
．６−トリニトロ安息香酸エステル、ピクリン酸、ピク
リルクロライド、２，４．６−１−リニトロアニソール
、１，３，６．８−テｌ〜ラニＩ〜ロ力ルバゾール、１
，３．５−トリシアノベンゼン、１．２，４．５−テト
ラシアノベンゼン、１，３゜５−トリメトキ力ルポニル
ベンゼンアントラキノン、クロラニル、２，３−ジクロ
ル−５，６−ジシアツーＰ−ベンゾキノン、２，３，５
．６−チトラシアノーＰ−ベンゾキノン、テトラシアノ
キノジメタン、テ１〜ラシアノエチレンなどが挙げられ
る。61, 1964, p. 21,
It is a compound that can form a charge transfer complex with an electron donor by charge transfer force, and the ring contains, for example, -N O2, -CN
, monocyclic, polycyclic or heterocyclic aromatic compounds having electron-withdrawing substituents such as -COOR and COR, quinone compounds, and aliphatic unsaturated hydrocarbons in which all hydrogen atoms are substituted with electron-withdrawing groups. selected from the group consisting of. Specific examples of such compounds include 1,3,5-trini-benzene, 2,4. ．． 6-trinitrotoluene, 2゜4
．． 6-trinitrobenzoic acid ester, picric acid, picryl chloride, 2,4.6-1-linitroanisole, 1,3,6.8-tel-rani-I-rotribazole, 1
, 3.5-tricyanobenzene, 1.2,4.5-tetracyanobenzene, 1,3゜5-trimethoxyluponylbenzene anthraquinone, chloranil, 2,3-dichloro-5,6-dicyatu-P-benzoquinone ,2,3,5
．． Examples include 6-titracyano-P-benzoquinone, tetracyanoquinodimethane, and 1-lacyanoethylene.
π型電子受容体の添加量は、特に、限定されないが、一
般にＩ Ｘ １０−５〜５重量％の添加が望ましい。The amount of the π-type electron acceptor added is not particularly limited, but it is generally desirable to add 10-5 to 5% by weight of IX.
本発明の樹脂組成物に粘度を低下させる目的で、溶剤を
添加したり、加熱硬化を促進する硬化触媒。A curing catalyst to which a solvent is added to the resin composition of the present invention for the purpose of lowering the viscosity or to accelerate heat curing.
ポリブタジェンやポリクロロプレン等の合成ゴムによる
変性、ポリエステル変性、シリカ、アルミナ、ガラス粉
、マイカ等の無機充填剤や有数充填剤を配合して使用す
ることができる。Modification with synthetic rubber such as polybutadiene or polychloroprene, modification with polyester, inorganic fillers or major fillers such as silica, alumina, glass powder, mica, etc. can be blended and used.
なお、本発明に配合し得る硬化促進剤には、例えば、ト
リメチルジアミン、トリエチルアミン、テ１〜ラメチル
ブタンジアミン、トリエチレンジアミンなどの二級アミ
ン類、ジメチルアミノエタノール、ジメチルアミノペン
タノール、トリス（ジメチルアミノメチル）フェノール
、Ｎ−メチルモルホリンなどの各種アミン類がある。In addition, examples of curing accelerators that can be incorporated in the present invention include secondary amines such as trimethyldiamine, triethylamine, te-1-ramethylbutanediamine, and triethylenediamine, dimethylaminoethanol, dimethylaminopentanol, and tris(dimethyl There are various amines such as (aminomethyl)phenol and N-methylmorpholine.
また、セチルトリメチルアンモニウムブロマイド、セチ
ルトリメチルアンモニウムクロライド。Also, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride.
ドデシルトリメチルアンモニウムアイオダイド、トルメ
チルドデシルアンモニウムクロライド、ベンジルジメチ
ルテトラデシルアンモニウムクロライド、ベンジルジメ
チルパルミチルアンモニウムクロライド、アリルドテシ
ル１〜リメチルアンモニウムブロマイド、ベンジルジメ
チルステアリルアンモニウムプロマイト、ステアリルト
リメチルアンモニウムクロライド、ベンジルジメチルテ
１〜ラデシルアンモニウムアセチレートなど第四級アン
モニウム塩がある。さらに、２−メチルイミダゾ−ル、
２−エチルイミダゾール、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−メチル−４−エ
チルイミダゾール、２−メチル−４−エチルイミダゾー
ル、１−ブタルイミダゾール、１−プロピル−２−メチ
ルイミダゾール、１′−ベンジル−２−メチルイミダゾ
ール、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−ウンデシルイミダゾール、１−シ
アノエチル−２−フェニルイミダゾール、１−アジン−
２−メチルイミダゾール、１−アジン−２−メチルイミ
ダゾール、１−アジン−２−ウンデシルイミダゾール、
１−アジン−２−ウンデシルイミダゾールなどのイミダ
ゾール類が有用である。あるいは、これらの金属塩も用
いることができる。Dodecyltrimethylammonium iodide, tolumethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethylpalmitylammonium chloride, allyldotecyl-1-limethylammonium bromide, benzyldimethylstearylammonium bromite, stearyltrimethylammonium chloride, benzyldimethylte1 ~ There are quaternary ammonium salts such as rhadecylammonium acetylate. Furthermore, 2-methylimidazole,
2-ethylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-methyl-4-ethylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1'-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1
-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-
2-methylimidazole, 1-azine-2-methylimidazole, 1-azine-2-undecylimidazole,
Imidazoles such as 1-azine-2-undecylimidazole are useful. Alternatively, these metal salts can also be used.
次に、実施例および従来技術による比較例によって本発
明を説明する。貯蔵安定性の評価は有枠ガラス容器に３
０℃で貯蔵した際の外観変化のほか、貯蔵後のワニスを
２００℃、３０分焼付けて得た塗膜の鉛筆硬度によった
。硬度が９Ｈ以上であれば変質していないと認められる
。Next, the present invention will be explained with reference to examples and comparative examples according to the prior art. The storage stability rating is 3 for framed glass containers.
In addition to the change in appearance when stored at 0°C, the pencil hardness of the paint film obtained by baking the varnish after storage at 200°C for 30 minutes was measured. If the hardness is 9H or higher, it is recognized that there is no deterioration.
〈実施例１〜１５〉
（ＣＨ３）２＜ン○−Ｃ−Ｎ＜ンＣＨｘ−＋１ １
Ｈ
Ｏ
で表わされる多官能イソシアネート再生体（日本ポリウ
レタン社製ＭＳ −５０）と水酸基含有ビスフェノール
Ａのジグリシジエーテル（油化シェル社、 Ｅｐｏｎ
１０１０ ）、硬化触媒２−エテル−４−メチル−イミ
ダゾール（四国化成製２Ｅ４ＭＺ）および酸性化合物を
使用した場合について説明する。<Examples 1 to 15> (CH3)2 Sydiether (Yuka Shell Co., Ltd., Epon)
1010), a curing catalyst 2-ethel-4-methyl-imidazole (2E4MZ manufactured by Shikoku Kasei), and an acidic compound will be described.
いずれの場合もトルエンで希釈し、濃度５０％の溶液と
して貯蔵した。得られた結果を第１表（次頁）に示す。In each case, it was diluted with toluene and stored as a 50% solution. The results obtained are shown in Table 1 (next page).
π型電子受容体を添加すると特に。Especially when adding π-type electron acceptors.
加温貯蔵安定性が優れることが分かる。It can be seen that the heating storage stability is excellent.
で示される多官能イソシアネート再生体（日本ポリウレ
タン社製、ＡＰ ステーブル）１００部、水酸基含有
ビスフェノールＡのジグリシジルエーテル（油化シェル
社、 Ｅｐｏｎ １０１０ ）と塩化ベンザルコニウム
一部とから成る系をメチルエチルケトンとトルエン（５
０１５０重量比）の混合溶剤に溶解し、濃度４０重量％
になるようにし、２，４゜６−ドリニトロアニソール
１ｗｔ％添加した。A system consisting of 100 parts of a polyfunctional isocyanate regenerated product (AP Stable, manufactured by Nippon Polyurethane Co., Ltd.) shown in Methyl ethyl ketone and toluene (5
0150 weight ratio) in a mixed solvent with a concentration of 40% by weight.
2,4゜6-dolinitroanisole
1 wt% was added.
この樹脂組成物を有枠ガラス容器に入れ、３０℃で保管
した。六ケ月後も何ら異常が詔められず、又、貯蔵後の
樹脂組成物を焼付けた塗膜の鉛筆硬度は９部以上であっ
た。This resin composition was placed in a framed glass container and stored at 30°C. No abnormality was observed even after six months, and the pencil hardness of the paint film baked from the resin composition after storage was 9 parts or higher.
〈実施例１６〉
ジフェニルメタンジイソシアネート（日本ポリウレタン
社製 ＭＤＩ）１００部、水酸基含有ビスフェノールＡ
のジグリシジルエーテル（油化シェル社製、 Ｅｐｏｎ
１０１０ ） ５６部および硬化触媒２Ｅ４Ｍ２ １
．５６ 部を酢酸セロソルブ１００部に溶解し、１００
℃で一時間反応させてイソシアタレート・オキサゾリド
ンプレポリマ（主としてイソシアタラード）を得た。こ
れに、メタクレゾール４３部を５０℃において加え、プ
レポリマ分子の末端イソシアネート基を反応させてウレ
タン化した。その後、酢酸セロソルブで希釈して固形分
濃度４０％のワニスにした。とのワニスおよび２，４．
６−ドリニパアニソールを１ ｗ ｔ％添加したワニス
の貯蔵安定性は三ケ月以上あった。<Example 16> 100 parts of diphenylmethane diisocyanate (MDI manufactured by Nippon Polyurethane Co., Ltd.), hydroxyl group-containing bisphenol A
diglycidyl ether (manufactured by Yuka Shell Co., Ltd., Epon)
1010) 56 parts and curing catalyst 2E4M2 1
．． Dissolve 56 parts in 100 parts of cellosolve acetate,
The reaction was carried out at ℃ for 1 hour to obtain an isocyatalate/oxazolidone prepolymer (mainly isocyatalade). To this, 43 parts of metacresol was added at 50°C, and the terminal isocyanate group of the prepolymer molecule was reacted to form a urethane. Thereafter, it was diluted with cellosolve acetate to obtain a varnish with a solid content concentration of 40%. varnish with and 2,4.
The storage stability of the varnish containing 1 wt% of 6-drinipaanisole was more than three months.
すなわち、三ケ月以」二経過しても何ら異常が認められ
ず、又、貯蔵後の樹脂組成物を焼付けた塗膜の鉛筆硬化
は９部以上であった。That is, no abnormality was observed even after 3 months or more, and the pencil hardening of the paint film obtained by baking the resin composition after storage was 9 parts or more.
本発明によれば、その貯蔵安定性を大幅に向上させるこ
とができる。According to the present invention, its storage stability can be significantly improved.
Claims (1)
び（Ｂ）水酸基含有多官能エポキシドを含む樹脂組成物
において、 （Ｃ）π型電子受容体を含むことを特徴とする樹脂組成
物。 ２、前記π型電子受容体が （ａ）環に電子吸引性置換基をもつ単環、多環芳香族化
合物もしくはヘテロ環芳香族化合物 （ｂ）キノン化合物および （ｃ）電子吸引性基によって全ての水素原子が置換され
た脂肪族不飽和炭化水素 から成る群から選ばれた、少なくとも一種の化合物であ
ることを特徴とする特許請求の範囲第１項記載の樹脂組
成物。 ３、前記π型電子受容体が、（Ａ）多官能イソシアネー
ト再生体と（Ｂ）水酸基含有エポキシドとの混合物の重
量を基準にして、１×１０＾−＾５〜５重量％含まれて
いることを特徴とする特許請求の範囲第１項または第２
項記載の樹脂組成物。 ４、前記π型電子受容体がピクリン酸、ピクリンクロラ
イド、２，４，６−トリニトロ安息香酸エステル、２，
４，６−トリニトロアニソール、２，３−ジクロロ−５
，６−ジシアノベンゾキノン、１，３，６，８−テトラ
ニトロカルバゾールまたはテトラシアノエチレンから選
ばれる、少なくとも一種であることを特徴とする特許請
求の範囲第１項または第３項記載の樹脂組成物。[Scope of Claims] 1. A resin composition comprising at least (A) a regenerated polyfunctional isocyanate and (B) a hydroxyl group-containing polyfunctional epoxide, the resin composition comprising (C) a π-type electron acceptor. thing. 2. The π-type electron acceptor is formed by (a) a monocyclic, polycyclic aromatic compound or a heterocyclic aromatic compound having an electron-withdrawing substituent on the ring, (b) a quinone compound, and (c) an electron-withdrawing group. 2. The resin composition according to claim 1, wherein the resin composition is at least one compound selected from the group consisting of aliphatic unsaturated hydrocarbons in which hydrogen atoms are substituted. 3. The π-type electron acceptor is contained in an amount of 1×10^-^5 to 5% by weight, based on the weight of the mixture of (A) polyfunctional isocyanate regenerant and (B) hydroxyl group-containing epoxide. Claim 1 or 2 characterized in that
The resin composition described in . 4. The π-type electron acceptor is picric acid, picrin chloride, 2,4,6-trinitrobenzoic acid ester, 2,
4,6-trinitroanisole, 2,3-dichloro-5
, 6-dicyanobenzoquinone, 1,3,6,8-tetranitrocarbazole, or tetracyanoethylene. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61213925A JPS6369818A (en) | 1986-09-12 | 1986-09-12 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61213925A JPS6369818A (en) | 1986-09-12 | 1986-09-12 | Resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6369818A true JPS6369818A (en) | 1988-03-29 |
Family
ID=16647316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61213925A Pending JPS6369818A (en) | 1986-09-12 | 1986-09-12 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6369818A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995005411A2 (en) * | 1993-08-17 | 1995-02-23 | Minnesota Mining And Manufacturing Company | Latent, thermal cure accelerators for epoxy-aromatic amine resins |
-
1986
- 1986-09-12 JP JP61213925A patent/JPS6369818A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995005411A2 (en) * | 1993-08-17 | 1995-02-23 | Minnesota Mining And Manufacturing Company | Latent, thermal cure accelerators for epoxy-aromatic amine resins |
| WO1995005411A3 (en) * | 1993-08-17 | 1995-04-27 | Minnesota Mining & Mfg | Latent, thermal cure accelerators for epoxy-aromatic amine resins |
| US5541000A (en) * | 1993-08-17 | 1996-07-30 | Minnesota Mining And Manufacturing Company | Latent, thermal cure accelerators for epoxy-aromatic amine resins having lowered peak exotherms |
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