TWI813549B - 聚碳二亞胺共聚物 - Google Patents
聚碳二亞胺共聚物 Download PDFInfo
- Publication number
- TWI813549B TWI813549B TW106139636A TW106139636A TWI813549B TW I813549 B TWI813549 B TW I813549B TW 106139636 A TW106139636 A TW 106139636A TW 106139636 A TW106139636 A TW 106139636A TW I813549 B TWI813549 B TW I813549B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- polycarbodiimide copolymer
- polycarbodiimide
- diisocyanate
- copolymer
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 103
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 73
- -1 aliphatic amines Chemical class 0.000 claims abstract description 48
- 239000011342 resin composition Substances 0.000 claims abstract description 47
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 25
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- 229920005862 polyol Polymers 0.000 claims description 34
- 150000003077 polyols Chemical class 0.000 claims description 34
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 20
- 229940043279 diisopropylamine Drugs 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 6
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 6
- NNWUEBIEOFQMSS-UHFFFAOYSA-N 2-Methylpiperidine Chemical compound CC1CCCCN1 NNWUEBIEOFQMSS-UHFFFAOYSA-N 0.000 claims description 5
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002981 blocking agent Substances 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical group CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 claims description 5
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 claims description 4
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 3
- LADVLFVCTCHOAI-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.CC1=CC=CC=C1 LADVLFVCTCHOAI-UHFFFAOYSA-N 0.000 claims description 2
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 claims description 2
- FLNMQGISZVYIIK-UHFFFAOYSA-N 1-ethylpyrazole Chemical compound CCN1C=CC=N1 FLNMQGISZVYIIK-UHFFFAOYSA-N 0.000 claims 1
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000003860 storage Methods 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 32
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 125000005442 diisocyanate group Chemical group 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical group CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 239000008159 sesame oil Substances 0.000 description 3
- 235000011803 sesame oil Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 2
- XHFGWHUWQXTGAT-UHFFFAOYSA-N n-methylpropan-2-amine Chemical compound CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- IGJDIGJIINCEDE-UHFFFAOYSA-N 1,3,5-trimethylpiperidine Chemical compound CC1CC(C)CN(C)C1 IGJDIGJIINCEDE-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-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
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- NOIXNOMHHWGUTG-UHFFFAOYSA-N 2-[[4-[4-pyridin-4-yl-1-(2,2,2-trifluoroethyl)pyrazol-3-yl]phenoxy]methyl]quinoline Chemical compound C=1C=C(OCC=2N=C3C=CC=CC3=CC=2)C=CC=1C1=NN(CC(F)(F)F)C=C1C1=CC=NC=C1 NOIXNOMHHWGUTG-UHFFFAOYSA-N 0.000 description 1
- FEUFNKALUGDEMQ-UHFFFAOYSA-N 2-isocyanato-1,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=O FEUFNKALUGDEMQ-UHFFFAOYSA-N 0.000 description 1
- DUUSMHZSZWMNCB-UHFFFAOYSA-N 2-isocyanatobutane Chemical compound CCC(C)N=C=O DUUSMHZSZWMNCB-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
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 1
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 1
- VWYHWAHYVKZKHI-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 Chemical compound N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 VWYHWAHYVKZKHI-UHFFFAOYSA-N 0.000 description 1
- INWVTRVMRQMCCM-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 INWVTRVMRQMCCM-UHFFFAOYSA-N 0.000 description 1
- WMTLVUCMBWBYSO-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 WMTLVUCMBWBYSO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- PVNFUHRSPUCTEN-UHFFFAOYSA-N isocyanic acid;1,2-xylene Chemical compound N=C=O.CC1=CC=CC=C1C PVNFUHRSPUCTEN-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AQHHHDLHHXJYJD-UHFFFAOYSA-N propranolol Chemical compound C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 AQHHHDLHHXJYJD-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/095—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to carbodiimide or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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Abstract
本發明針對含有羧基之樹脂組成物的硬化物,提供一種聚碳二亞胺共聚物及改質聚碳二亞胺共聚物,其適合作為不損及耐水性且可改良柔軟性的硬化劑,此外,並提供一種含有羧基之樹脂組成物的硬化劑及含有羧基之樹脂組成物。本發明,藉由在聚碳二亞胺的分子中導入既定的軟段,在作為硬化劑使用時,可提升硬化物的耐水性,進一步藉由以脂肪族胺或是具有芳香族性之雜環胺進行改質,可提升含有羧基之樹脂組成物的保存穩定性。
Description
本發明係關於分子中含有軟段的聚碳二亞胺共聚物,及將其改質所得之改質聚碳二亞胺共聚物。此外關於包含聚碳二亞胺共聚物的含有羧基之樹脂的硬化劑,以及含有羧基之樹脂組成物。
溶液中之儲存穩定性經改善的改質聚碳二亞胺組成物及改質聚碳二亞胺已為人所知(例如,參照專利文獻1)。分子內具有軟段的聚碳二亞胺共聚物雖柔軟性優異,但所使用的軟段其極性高,故包含該共聚物之組成物的硬化物,具有耐水性不佳這樣的課題。
此外,作為聚對苯二甲酸乙二酯的耐水解穩定劑,已知將聚酯多元醇及聚碳酸酯多元醇導入芳香族聚碳二亞胺之中的聚碳二亞胺共聚物(例如,參照專利文獻2)。然而,使用該聚碳二亞胺共聚物作為硬化劑的情況則具有下述的課題:因為摻合量變多而使得酯基及碳酸酯基變多,導致聚對苯二甲酸乙二酯的吸濕性變高,耐水性降低。
專利文獻1 日本特開2007-138080號公報
專利文獻2 日本特開2015-147838號公報
本發明之目的係針對含有羧基之樹脂組成物的硬化物,提供一種聚碳二亞胺共聚物及將其改質所得之改質聚碳二亞胺共聚物,其適合作為不損及耐水性且可改良柔軟性的硬化劑,此外並提供一種含有羧基之樹脂的硬化劑及含有羧基之樹脂組成物。
本發明中,為了達成上述目的而反覆詳盡檢討的結果,發現藉由將既定軟段導入聚碳二亞胺的分子中,在作為硬化劑使用時,可提升硬化物的耐水性。進一步發現,包含在分子中導入軟段之聚碳二亞胺共聚物的含有羧基之樹脂組成物,其保存穩定性亦優良,因而完成本發明。
亦即,本發明如下所述。
[1]一種聚碳二亞胺共聚物,其係具有:含有將選自篦蔴油、官能基數2~10之篦蔴油系多元醇以及以HO-R1-OH表示之長鏈脂肪族二醇(R1係表示含有30~150個碳原子之直鏈或分支之飽和或不飽和的伸烷基)之至少1種多元醇的羥基去除而得到之殘基的軟段;以及經由胺基甲酸酯鍵而與該軟段結合之包含源自芳香族二異氰酸酯化合物之聚碳二亞胺的硬段。
[2]如上述[1]之聚碳二亞胺共聚物,其中該芳香族二異氰酸酯係選自包含4,4’-二苯甲烷二異氰酸酯、2,4-二異氰酸甲苯酯、2,6-二異氰酸甲苯酯以及4,4’-二異氰酸-3,3’-二甲基聯苯的群組中之至少1種。
[3]如上述[1]或[2]之聚碳二亞胺共聚物,其中該多元醇係篦蔴油或官能基數2~10的篦蔴油系多元醇。
[4]如上述[3]之聚碳二亞胺共聚物,其中該多元醇係官能基數2~3的篦蔴油系多元醇。
[5]一種含有羧基之樹脂的硬化劑,其係包含如上述[1]至[4]中任一項之聚碳二亞胺共聚物。
[6]一種含有羧基之樹脂組成物,其係包含如上述[5]之硬化劑及含有羧基之樹脂。
[7]一種改質聚碳二亞胺共聚物,其係將如上述[1]至[4]中任一項之聚碳二亞胺共聚物,藉由脂肪族胺或具有芳香族性之雜環胺改質而成。
[8]如上述[7]之改質聚碳二亞胺共聚物,其中該脂肪族胺係選自包含二乙胺、二異丙胺、三級丁基乙胺、二正丁胺、二-二級丁胺、二-三級丁胺、二環己胺、2-甲哌啶及2,6-二甲哌啶之群組的至少1種。
[9]如上述[8]之改質聚碳二亞胺共聚物,其中該脂肪族胺為二異丙胺。
[10]如上述[7]之改質聚碳二亞胺共聚物,其中該具有芳香族性之雜環胺係選自包含3,5-二甲基吡唑、咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑之群組的至少1種。
[11]一種含有羧基之樹脂的硬化劑,其係包含如上述[7]至[10]中任一項之改質聚碳二亞胺共聚物。
[12]一種含有羧基之樹脂組成物,其係包含如上述[11]之硬化劑及含有羧基之樹脂。
藉由將本發明之聚碳二亞胺共聚物或是改質聚碳二亞胺共聚物使用於硬化劑,可提升含有羧基之樹脂組成物的硬化物之耐水性,同時可具有優異之柔軟性,進一步可將含有羧基之樹脂組成物作為保存穩定性優異之物。
[聚碳二亞胺共聚物]
本發明之聚碳二亞胺共聚物,具有由既定的聚碳二亞胺所構成之硬段與由既定的多元醇所構成之軟段。藉由將該聚碳二亞胺共聚物作成硬化劑使用,可提供柔軟性經改良且耐水性優異之含有羧基之樹脂組成物的硬化物。該硬化物,因為優異之柔軟性與耐水性,在用於屋外塗料及電子零件用途的情況下,可發揮提升耐久性這樣優異的效果。
此外,該聚碳二亞胺共聚物,可使包含硬化劑的含有羧基之樹脂組成物作為保存穩定性優異之物。
(聚碳二亞胺)
本發明之聚碳二亞胺共聚物具有硬段與軟段,而硬段係由聚碳二亞胺所構成。又,本發明中所指的聚碳二亞胺,係指聚碳二亞胺共聚物中所包含的結構單元。
本發明之聚碳二亞胺共聚物中的聚碳二亞胺,係源自芳香族二異氰酸酯化合物的聚碳二亞胺。此處,芳香族二異氰酸酯化合物,係指分子中具有2個異氰酸酯基的異氰酸酯化合物,且分子中存在的2個異氰酸酯基與芳香環直接鍵結的異氰酸酯化合物。
源自二異氰酸酯化合物的聚碳二亞胺中,具有例如源自芳香族二異氰酸酯化合物的聚碳二亞胺與源自脂肪族二異氰酸酯化合物的聚碳二亞胺。源自芳香族二異氰酸酯化合物的聚碳二亞胺,其耐熱性優於源自脂肪族二異氰酸酯化合物的聚碳二亞胺,故較佳係源自芳香族二異氰酸酯化合物的聚碳二亞胺。
源自二異氰酸酯化合物的聚碳二亞胺,具有例如下述通式(1)所示之基。
(式中,R表示從二異氰酸酯化合物去除異氰酸酯基而得到的殘基)。
[二異氰酸酯;(a)成分]
作為本發明之聚碳二亞胺共聚物中的聚碳二亞胺之來源的芳香族二異氰酸酯化合物(以下亦稱為 「二異氰酸酯(a)」或是「(a)成分」),可列舉例如:二異氰酸伸苯酯、二異氰酸甲苯酯、聯甲苯胺二異氰酸酯、1,5-二異氰酸萘酯、二苯甲烷二異氰酸酯、二苯二甲基甲烷二異氰酸酯、二苯醚二異氰酸酯等。該等可單獨使用1種,亦可組合2種以上。從耐熱性的觀點來看,較佳的芳香族二異氰酸酯化合物係選自二異氰酸甲苯酯、聯甲苯胺二異氰酸酯、及二苯甲烷二異氰酸酯的至少1種,更佳為二異氰酸甲苯酯。
(多元醇)
本發明之聚碳二亞胺共聚物,係使該聚碳二亞胺與多元醇(以下亦稱為「多元醇(b)」或是「(b)成分」)反應所得。本發明之聚碳二亞胺共聚物中,軟段係由多元醇所構成。又,本說明書中,多元醇係指分子中具有2個以上之羥基的化合物。
本發明之聚碳二亞胺共聚物,在碳二亞胺基之間具有去除該多元醇之羥基而得到的2價以上的殘基,其與含有羧基之樹脂的匹配性質良好,與羧基的反應率提高,因此含有羧基之樹脂的耐熱性提高,此外,因為多元醇(b)的極性低,故含有羧基之樹脂的耐水性提高。此外,可將柔軟性賦予含有羧基之樹脂。
[多元醇;(b)成分]
作為該(b)成分,可列舉:篦蔴油、官能基數2~10之篦蔴油系多元醇、及HO-R1-OH所表示之長鏈脂肪族二醇(R1係表示含有30~150個碳原子之直鏈或分支之飽和或不飽和的伸烷基)。又,此處所指的官能基係指羥基。
作為該篦蔴油系多元醇,可列舉以篦蔴油作為原料而衍伸者。具體而言,可列舉:伊藤製油股份有限公司製的URIC H-30、URIC H-62、URIC Y-403;豐國製油股份有限公司製的HS 2G-120、HS SG-160R、HS 2G-270B、HS 2B-5500、HS KA-001等,但不限於此等。
作為該長鏈脂肪族二醇,可列舉聚伸烷基二醇等。具體而言,可列舉:日本曹達股份有限公司製的兩末端羥基聚丁二烯G系列、兩末端羥基氫化聚丁二烯GI系列;出光興產股份有限公司製的羥基末端液狀聚丁二烯Poly bd(註冊商標)、羥基末端液狀聚烯烴EPOL(註冊商標)、三菱化學股份有限公司製聚羥基聚烯烴寡聚物POLYTAIL(註冊商標)等,但不限於此等。
長鏈脂肪族二醇的數量平均分子量,從有效成分的觀點來看,較佳為500以上5000以下,更佳為500以上3000以下,再佳為500以上2000以下。
該等之中,從相溶性之觀點來看,較佳為篦蔴油系多元醇,再佳為官能基數2的篦蔴油系多元醇。
(封端)
本發明之聚碳二亞胺共聚物中,殘留作為硬段末端的末端異氰酸酯,較佳係以封端劑(以下亦稱為「封端封材(c)」或是「(c)成分」)進行封端。藉此,可提高聚碳二亞胺共聚物的耐熱性、生產穩定性及保存穩定性,而可提高品質。
[封端劑;(c)成分]
作為該(c)成分,可列舉:單醇、單酚、單異氰酸酯、單胺等。
作為該單醇,可列舉:甲醇、乙醇、環己醇、聚乙二醇單甲醚、聚丙二醇單甲醚等。
作為該單酚,可列舉:酚、甲酚、二甲酚、萘酚等。
作為該單異氰酸酯,可列舉:異氰酸甲酯、異氰酸乙酯、異氰酸丙酯、異氰酸正丁酯、異氰酸二級丁酯、異氰酸三級丁酯等的低級烷單異氰酸酯;異氰酸環己酯等的脂環式脂肪族單異氰酸酯;異氰酸苯酯、異氰酸甲苯酯、二甲基苯異氰酸酯、2,6-二異丙基苯異氰酸酯等的芳香族單異氰酸酯等。
作為該單胺,可列舉:丁胺、環己胺等的1級胺;二乙胺、二丁胺、二環己胺等的2級胺。
該等之中,從反應性之觀點來看,較佳為單醇或是單異氰酸酯,更佳為單異氰酸酯,再佳為芳香族單異氰酸酯,再更佳為異氰酸苯酯。
封端劑(c)可單獨使用1種,亦可組合2種以上使用。
(碳二亞胺當量)
聚碳二亞胺共聚物之碳二亞胺當量(碳二亞胺基每1莫耳的化學式量),從含有羧基之樹脂組成物的耐水解穩定性、熔融黏度以及溶液黏度的觀點來看,較佳為200~1,500、更佳為250~1,250、再佳為300~1,000。
(聚碳二亞胺共聚物的數量平均分子量)
該聚碳二亞胺共聚物的數量平均分子量,從含有羧基之樹脂組成物之耐水解性、熔融黏度及溶液黏度的觀點來看,較佳為250~50,000,更佳為300~10,000,再佳為400~5,000,再更佳為500~3,000。又,係藉由凝膠滲透層析法(GPC法)並使用聚苯乙烯作為標準物質來測定數量平均分子量。
(聚碳二亞胺共聚物之製造方法)
本發明之聚碳二亞胺共聚物可以習知的方法製造。例如,可列舉:(i)於溶劑存在下使二異氰酸酯(a)及多元醇(b)反應而產生包含胺基甲酸酯鍵的兩末端異氰酸酯之化合物(以下亦稱為「(d)成分」),之後,在觸媒的存在下,使(a)成分、(d)成分及封端劑(c)反應,以進行碳二亞胺化及封端的方法;(ii)在溶劑及觸媒的存在下,使二異氰酸酯(a)進行碳二亞胺化而產生聚碳二亞胺(以下亦稱為「(e)成分」),接著在(e)成分中添加多元醇(b)及封端劑(c)以使其反應,而進行共聚合及封端的方法;(iii)在溶劑及觸媒的存在下使二異氰酸酯(a)、多元醇(b)及封端劑(c)反應,以進行胺基甲酸酯化、碳二亞胺化及封端的方法等。
該等之中,從生產性的觀點來看,較佳係以該(i)之方法進行製造。具體而言,較佳係以使二異氰酸酯(a)之異氰酸酯基相對於多元醇(b)之羥基成為過量 的方式將二異氰酸酯(a)及多元醇(b)混合以進行胺基甲酸酯化反應,接著添加封端劑(c)以及作為碳二亞胺化觸媒的有機磷系化合物或有機金屬化合物等,而在無溶劑或是非活性溶劑中進行碳二亞胺化反應。
作為該碳二亞胺化觸媒的具體例,可列舉:3-甲基-1-苯基-2-磷烯-1-氧化物、3-甲基-1-乙基-2-磷烯-1-氧化物、1,3-二甲基-2-磷烯-1-氧化物、1-苯基-2-磷烯-1-氧化物、1-乙基-2-磷烯-1-氧化物、1-甲基-2-磷烯-1-氧化物等。該等之中,較佳為在工業上容易取得的3-甲基-1-苯基-2-磷烯-1-氧化物。碳二亞胺化觸媒可單獨使用1種,亦可組合2種以上使用。
該(a)成分與(b)成分之胺基甲酸酯化反應的反應溫度,雖可因應所使用之原料適當設定,但從生產性之觀點來看,較佳為30~200℃,更佳為40~150℃,再佳為50~120℃。
該碳二亞胺化反應的反應溫度,從生產性的觀點來看,較佳為40~250℃,更佳為60~200℃,再佳為80~150℃。
該碳二亞胺化反應的反應時間,從相同的觀點來看,較佳為2~20小時,更佳為3~15小時,再佳為4~10小時。
碳二亞胺化觸媒的使用量,雖可因應所使用之觸媒種類適當設定,但相對於二異氰酸酯(a)100質量份,較佳為0.01~10質量份,更佳為0.05~5質量份,再佳為0.1~3質量份。
<含有羧基之樹脂的硬化劑>
本發明之一態樣的硬化劑,包含本發明之聚碳二亞胺共聚物。若使用該硬化劑,可有效地使含有羧基之樹脂組成物硬化。較佳的熱硬化溫度為90~180℃。熱硬化溫度若為90~180℃,則可使含有羧基之樹脂組成物充分硬化,同時可抑制因主劑(樹脂)及基材之加熱所導致的劣化以及經硬化之樹脂的黃變等。
<含有羧基之樹脂組成物>
本發明之一態樣的含有羧基之樹脂組成物,包含該一態樣的硬化劑、及含有羧基之樹脂。該含有羧基之樹脂組成物中所含之樹脂,只要是與碳二亞胺基進行交聯反應的樹脂則無特別限定。從與碳二亞胺基之交聯反應的容易程度來看,含有羧基之樹脂較佳係選自包含聚胺基甲酸酯樹脂、聚醯胺樹脂、丙烯酸樹脂、乙酸乙烯酯樹脂、聚烯烴樹脂及聚醯亞胺樹脂之群組的至少1種。
(聚碳二亞胺共聚物的添加量)
該一態樣的含有羧基之樹脂組成物,例如,係以下述方式添加:相對於主劑(樹脂)之官能基1莫耳當量,該一態樣之硬化劑所含之聚碳二亞胺共聚物較佳為0.5~1.5莫耳當量,更佳為0.8~1.2莫耳當量。
該一態樣的含有羧基之樹脂組成物,可因應用途等,只要有需求,則可適當摻合溶劑及各種添加成分,例如,顏料、填充劑、均染劑、界面活性劑、分散劑、塑化劑、紫外線吸收劑、抗氧化劑等。
[改質聚碳二亞胺共聚物]
本發明之改質聚碳二亞胺共聚物,係以脂肪族胺或是具有芳香族性之雜環胺將該聚碳二亞胺共聚物改質而得。
(脂肪族胺)
作為該脂肪族胺,較佳係可將該聚碳二亞胺共聚物的碳二亞胺基封端,在較高溫下從改質聚碳二亞胺共聚物開始解離且解離性高者。
本發明之改質聚碳二亞胺共聚物中所使用的脂肪族胺,較佳係選自包含二乙胺、二異丙胺、甲基異丙胺、三級丁基乙胺、二-二級丁胺、二環己胺、2-甲哌啶及2,6-二甲哌啶之群組的至少1種,更佳係選自包含二乙胺、二異丙胺、三級丁基乙胺、二-二級丁胺、二環己胺、2-甲哌啶及2,6-二甲哌啶之群組的至少1種,再佳係選自包含二乙胺、二異丙胺、三級丁基乙胺、二-二級丁胺、二環己胺及2-甲哌啶之群組的至少1種,特佳為二異丙胺。
(具有芳香族性之雜環胺)
本發明之改質聚碳二亞胺共聚物中所使用之具有芳香族性之雜環胺,只要係環內具有2級胺之氮的具有芳香族性之雜環胺,則無特別限定。此處,環內 具有2級胺之氮的具有芳香族性之雜環胺,係指雜環內具有胺的化合物。
作為該具有芳香族性之雜環胺,從改質聚碳二亞胺共聚物開始解離之溫度較低的觀點來看,較佳為環內氮的數量為2以上的雜環胺,更佳為選自包含未取代或亦可取代的吡唑及未取代或亦可取代之咪唑的群組的至少1種芳香族雜環化合物,再佳為選自包含3,5-二甲基吡唑、咪唑、2-甲基咪唑、2-乙基-4-甲基-咪唑、2-苯基咪唑及2-苯基-4-甲基咪唑之群組的至少1種。
又,以脂肪族胺或是具有芳香族性之雜環胺封端的碳二亞胺基,因為與羧基的反應性低,故幾乎不會使含有羧基之樹脂組成物硬化。然而,若脂肪族胺或是具有芳香族性之雜環胺從改質聚碳二亞胺共聚物解離,則經封端之碳二亞胺基回到以脂肪族胺或是具有芳香族性之雜環胺改質前之狀態的碳二亞胺基。由於碳二亞胺基與羧基的反應性高,故因為脂肪族胺或是具有芳香族性之雜環胺從改質聚碳二亞胺共聚物解離所生成之碳二亞胺基,而導致含有羧基之樹脂組成物熱硬化。若來自脂肪族胺或是具有芳香族性之雜環胺中的改質聚碳二亞胺共聚物的解離性高,則從已封端之碳二亞胺基所產生之碳二亞胺基的數量增加,因而促進了含有羧基之樹脂組成物的硬化。
例如,若以脂肪族胺對聚碳二亞胺共聚物進行改質,則脂肪族胺為二異丙胺的情況,下述式(2)所示之碳二亞胺基,成為下述式(3)所示之經封端的碳二亞 胺基。式(3)的經封端之碳二亞胺基,因為在式(3)之中的下述式(4)所示之部分的立體障礙,而與羧基的反應性低。若二異丙胺解離,則產生反應性高的式(2)的碳二亞胺基,該聚碳二亞胺共聚物使含有羧基之樹脂組成物硬化。
-N=C=N- (2)
此外,例如,若以具有芳香族性之雜環胺對聚碳二亞胺共聚物進行改質,則具有芳香族性之雜環胺為3,5-二甲基吡唑的情況,式(2)所示之碳二亞胺基成為下述式(5)所示之經封端的碳二亞胺基。式(3)的經封端的碳二亞胺基,若3,5-二甲基吡唑解離,則回到反應性高的式(2)的碳二亞胺基的狀態,該聚碳二亞胺共聚物使含有羧基之樹脂組成物硬化。
(改質聚碳二亞胺共聚物之製造方法)
如上所述,本發明之改質聚碳二亞胺共聚物,係以脂肪族胺或是具有芳香族性之雜環胺將碳二亞胺基封端,以將聚碳二亞胺共聚物進行改質所得。以脂肪族胺或是具有芳香族性之雜環胺對聚碳二亞胺共聚物所進行之改質,例如,可在無溶劑下進行,此外,亦可以下述方式進行:將聚碳二亞胺共聚物與有機溶劑混合,於其中,以相對於碳二亞胺基成為既定當量的方式添加脂肪族胺或是具有芳香族性之雜環胺,並攪拌以使其反應。
使用有機溶劑的情況,脂肪族胺或是具有芳香族性之雜環胺的添加量,相對於碳二亞胺基1莫耳當量,較佳為1~2莫耳當量,從抑制過剩之胺量及加熱處理時胺容易揮發的觀點來看,更佳為1~1.2莫耳當量。此外,以脂肪族胺或是具有芳香族性之雜環胺對聚碳二亞胺共聚物進行改質時的反應溫度,從反應速度及抑制碳二亞胺基被封端時之副反應的觀點來看,較佳為常溫(25℃左右)或是40~80℃。進行該改質時的反應,較佳係一邊攪拌一邊進行,反應時間雖因溫度而不同,但較佳為0.1~10小時左右。
<含有羧基之樹脂的硬化劑>
本發明之另一態樣的硬化劑,包含本發明之改質聚碳二亞胺共聚物。若使用該硬化劑,則可將含有羧基之樹脂組成物的乾燥溫度,設定為低於脂肪族胺或是具有芳香族性之雜環胺開始從改質之聚碳二亞胺共 聚物解離的溫度,而可在乾燥步驟中,抑制含有羧基之樹脂組成物的硬化。
此外,藉由將含有羧基之樹脂組成物的熱硬化溫度設定為高於脂肪族胺或是具有芳香族性之雜環胺開始從改質聚碳二亞胺共聚物解離的溫度,可在熱硬化步驟中確實地使含有羧基之樹脂組成物硬化。此外,可使含有羧基之樹脂組成物的熱硬化溫度為較低的溫度。較佳的熱硬化溫度為90~180℃。熱硬化溫度若為90~180℃,則可充分使熱硬化樹脂組成物硬化,並且可抑制因主劑(樹脂)及基材之加熱所導致的劣化,及經硬化之樹脂的黃變等。
又,該另一態樣的硬化劑,亦可包含未改質的該聚碳二亞胺共聚物。
<含有羧基之樹脂組成物>
本發明之另一態樣的含有羧基之樹脂組成物,包含該另一態樣的硬化劑及含有羧基之樹脂。該含有羧基之樹脂組成物所包含之樹脂,只要係與碳二亞胺基交聯反應的樹脂,則無特別限定。從與碳二亞胺基之交聯反應的容易程度來看,含有羧基之樹脂較佳係選自包含聚胺基甲酸酯樹脂、聚醯胺樹脂、丙烯酸樹脂、乙酸乙烯酯樹脂、聚烯烴樹脂及聚醯亞胺樹脂之群組的至少1種。
(改質聚碳二亞胺共聚物的添加量)
該另一態樣的含有羧基之樹脂組成物,例如,可以下述方式添加:相對於主劑(樹脂)的官能基1 莫耳當量,該另一態樣的硬化劑所含之改質聚碳二亞胺共聚物較佳為0.5~1.5莫耳當量,更佳為0.8~1.2莫耳當量。
此外,該另一態樣的含有羧基之樹脂組成物,可因應用途等,若有需要亦可適當摻合溶劑及各種添加成分,例如,顏料、填充劑、均染劑、界面活性劑、分散劑、塑化劑、紫外線吸收劑、抗氧化劑等。
以下列舉實施例及比較例,更具體地說明本發明,但本發明不限於此等例子。
[聚碳二亞胺共聚物的製作]
實施例1(聚碳二亞胺共聚物P1的合成)
將100質量份的二異氰酸甲苯酯、144質量份的篦蔴油系多元醇(伊藤製油股份有限公司製「URIC H-30」,官能基數2.7)、49.9質量份的異氰酸苯酯及402質量份的甲苯放入附有回流管及攪拌機的反應容器,在氮氣流下,於100℃攪拌1小時。接著,添加1.5質量份的3-甲基-1-苯基-2-磷烯-1-氧化物作為碳二亞胺化觸媒,於100℃攪拌6小時,在紅外吸收(IR)光譜測定中,確認波長2270cm-1前後的異氰酸酯基所造成的吸收峰值幾乎消失,而得到聚碳二亞胺共聚物P1的甲苯溶液。
比較例1(聚碳二亞胺化合物P9的合成)
將100質量份的二異氰酸甲苯酯、34.2質量份的異氰酸苯酯、163質量份的甲苯及作為碳二亞胺化觸媒的1.3質量份的3-甲基-1-苯基-2-磷烯-1-氧化物 放入附有回流管及攪拌機的反應容器,於氮氣流下,於100℃攪拌3小時,在IR光譜測定中,確認波長2270cm-1前後的異氰酸酯基所造成的吸收峰值幾乎消失,得到聚碳二亞胺化合物P9的甲苯溶液。
實施例2~8及比較例2~3(聚碳二亞胺共聚物P2~P8、P10及P11的合成)
實施例1中,除了將原料組成變更為下表1所記載之條件以外,以與實施例1相同的方式,得到聚碳二亞胺共聚物P2~P8、P10及P11。
又,表1的原料組成的詳細內容如下。
<二異氰酸酯(a)>
.TDI:二異氰酸甲苯酯(混合物:2,4-二異氰酸甲苯酯(80質量%)、2,6-二異氰酸甲苯酯(20質量%))
.MDI:4,4’-二苯甲烷二異氰酸酯
.TODI:4,4’-二異氰酸-3,3’-二甲基聯苯
<多元醇(b)>
.A:篦蔴油系多元醇,伊藤製油股份有限公司製「URIC H-30」,官能基數2.7
.B:篦蔴油系多元醇,伊藤製油股份有限公司製「URIC Y-403」,官能基數2
.C:篦蔴油系多元醇,豐國製油股份有限公司製「HS 2G-160R」,官能基數2
.D:羥基末端液狀聚丁二烯,出光興產股份有限公司製「Poly bd(註冊商標)R-15HT」,數量平均分子量1000
.E:兩末端羥基氫化聚丁二烯,日本曹達股份有限公司製「GI-1000」,數量平均分子量1500
.F:聚四亞甲基二醇,日油股份有限公司製「PB-700」,數量平均分子量700
.G:聚碳酸酯二醇,Asahi Kasei Chemicals股份有限公司製「DURANOL(註冊商標)T-5650J」,數量平均分子量700
<封端劑(c)>
.PhNCO:異氰酸苯酯
<碳二亞胺化觸媒>
.3-甲基-1-苯基-2-磷烯-1-氧化物
[改質聚碳二亞胺共聚物的製作]
實施例9(改質聚碳二亞胺共聚物PP1的製作)
在實施例1中所得之聚碳二亞胺共聚物P1的甲苯溶液中,添加59.3質量份的二異丙胺,於室溫(約25℃)下攪拌5小時,於IR光譜測定中,產生波長1740cm-1前後的胍基所造成的吸收峰值,並確認波長2150cm-1前後的碳二亞胺基所造成的吸收峰值幾乎消失,得到改質聚碳二亞胺共聚物PP1的甲苯溶液。
比較例4(改質聚碳二亞胺化合物PP9的製作)
在比較例1所得之聚碳二亞胺化合物P9的甲苯溶液中,添加59.3質量份的二異丙胺,於室溫下攪拌5小時,於IR光譜測定中,產生波長1740cm-1前後的胍基所造成的吸收峰值,確認波長2150cm-1前後的碳二亞胺基所造成的吸收峰值幾乎消失,得到改質聚碳二亞胺化合物PP9。
實施例10~16、比較例5及6(改質聚碳二亞胺共聚物PP2~PP8、PP10及PP11的製作)
實施例9中,除了將原料組成變更為下表2所記載的條件以外,以與實施例6相同的方式,得到改質聚碳二亞胺共聚物PP2~PP8、PP10及PP11。
又,表2的胺化合物的詳細內容如下。
.DIPA:二異丙胺
.DsBA:二-二級丁胺
[含有羧基之樹脂組成物的製作]
實施例17
將10質量份的實施例1所得之聚碳二亞胺共聚物P1與100質量份的非晶性聚酯樹脂(東洋紡股份有限公司製「VYLON(註冊商標)296」)的甲苯溶液(濃度30質量%)混合,得到含有羧基之樹脂組成物。
將該含有羧基之樹脂組成物澆注在脫模聚對苯二甲酸乙二酯(PET)膜上,以80℃乾燥5分鐘,製作厚度100μm的未硬化膜。在帶有脫模PET膜的狀態下,將該未硬化膜於170℃乾燥1小時使樹脂硬化,以製作硬化膜。
使用該硬化膜進行柔軟性試驗及耐水性試驗。各試驗結果顯示於下表3。
實施例18~34及比較例7~12
除了將聚碳二亞胺共聚物及含有羧基之樹脂變更為下表3所記載之條件以外,以與實施例17相同的方式,製作含有羧基之樹脂組成物,進一步製作硬化膜。使用該等的硬化膜進行柔軟性試驗及耐水性試驗。
又,作為含有羧基之樹脂使用的丙烯酸樹脂B,不以甲苯稀釋,而是直接作為產品使用。
使用改質聚碳二亞胺共聚物的實施例26~34、比較例10~12,亦進行含有羧基之樹脂組成物的保存穩定性試驗。各試驗結果顯示於下表3。
各試驗的評價方法如下。
(柔軟性試驗)
在將所製作之硬化膜摺疊時,缺乏柔軟性而破裂者為×,未裂開而回復原來之形狀者為○。
(耐水性試驗)
從所製作之硬化膜製作10mm×70mm的短片,以拉伸試驗機測定拉伸強度及伸度強度。之後,將所製作之短片放入高度加速壽命試驗裝置(ESPEC股份有限公司「HAST CHAMBER EHS-210M」),於121℃、100%RH的條件下經過24小時後、與經過40小時後,將樣本取出,於拉伸試驗機中,測定短片的拉伸強度及拉伸伸度。試驗前及試驗後,分別算出5片之拉伸強度及拉伸伸度的平均值,以下式算出之拉伸強度保持率及拉伸伸度保持率皆超過80%者為○,至少一個在80%以下者為×。評價為「○」者,可說是即使在濕熱環境下亦可保持硬化膜的強度,其耐水性優異。
拉伸強度保持率[%]=(試驗後的拉伸強度的平均值)/(試驗前的拉伸強度的平均值)×100
拉伸伸度保持率[%]=(試驗後的拉伸伸度的平均值)/(試驗前的拉伸伸度的平均值)×100
(保存穩定性試驗)
將所製作之含有羧基之樹脂組成物放置於40℃的環境下,觀察既定時間後是否膠化。96小時以內膠化者為×,超過96小時的時間點未觀察到膠化者為○。
又,表3的含有羧基之樹脂的詳細內容如下。
.A:聚酯樹脂,東洋紡股份有限公司製「VYLON(註冊商標)296」,數量平均分子量14000,酸價6
.B:丙烯酸樹脂,DIC股份有限公司製「ACRYDIC A-814」,不揮發份44.0~46.0質量%(溶劑:甲苯,乙酸乙酯),酸價(溶液)2.0~4.0
從表3所示之評價結果可知,實施例中,因為用以賦予柔軟性的軟段其極性低,故可在濕熱環境下抑制吸濕性,而可保持強度(拉伸強度及伸度強度)。另一方面,比較例中,因為軟段中大量包含高極性的化學鍵,故可觀察到其在濕熱環境下的強度降低。
本發明之聚碳二亞胺共聚物組成物的硬化物,其柔軟性及耐水性優良,而可合適地用於塗料等。
Claims (11)
- 一種聚碳二亞胺共聚物,其係具有:含有將選自篦蔴油及官能基數2~10之篦蔴油系多元醇之至少1種多元醇的羥基去除而得到之殘基的軟段;以及經由胺基甲酸酯鍵而與該軟段結合之包含源自芳香族二異氰酸酯化合物之聚碳二亞胺的硬段,作為該硬段之末端而殘留的末端異氰酸酯係以封端劑進行封端。
- 如請求項1之聚碳二亞胺共聚物,其中該芳香族二異氰酸酯係選自包含4,4’-二苯甲烷二異氰酸酯、2,4-二異氰酸甲苯酯、2,6-二異氰酸甲苯酯以及4,4’-二異氰酸-3,3’-二甲基聯苯的群組中之至少1種。
- 如請求項1或2之聚碳二亞胺共聚物,其中該多元醇係官能基數2~3的篦蔴油系多元醇。
- 一種含有羧基之樹脂的硬化劑,其係包含如請求項1至3中任一項之聚碳二亞胺共聚物。
- 一種含有羧基之樹脂組成物,其係包含如請求項4之硬化劑及含有羧基之樹脂。
- 一種改質聚碳二亞胺共聚物,其係將如請求項1至3中任一項之聚碳二亞胺共聚物,藉由脂肪族胺或具有芳香族性之雜環胺改質而成。
- 如請求項6之改質聚碳二亞胺共聚物,其中該脂肪族胺係選自包含二乙胺、二異丙胺、三級丁基乙胺、二 正丁胺、二-二級丁胺、二-三級丁胺、二環己胺、2-甲哌啶及2,6-二甲哌啶之群組的至少1種。
- 如請求項7之改質聚碳二亞胺共聚物,其中該脂肪族胺為二異丙胺。
- 如請求項6之改質聚碳二亞胺共聚物,其中該具有芳香族性之雜環胺係選自包含3,5-二甲基吡唑、咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑之群組的至少1種。
- 一種含有羧基之樹脂的硬化劑,其係包含如請求項6至9中任一項之改質聚碳二亞胺共聚物。
- 一種含有羧基之樹脂組成物,其係包含如請求項10之硬化劑及含有羧基之樹脂。
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WO2024004976A1 (ja) * | 2022-06-27 | 2024-01-04 | 日清紡ケミカル株式会社 | ポリカルボジイミド化合物、樹脂組成物、及び樹脂硬化物 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4169866A (en) * | 1976-04-08 | 1979-10-02 | Bayer Aktiengesellschaft | Polymer systems containing polycarbodiimides and thermoplastic polymer |
JP2002025342A (ja) * | 2000-07-13 | 2002-01-25 | Sanyu Rec Co Ltd | 電気絶縁用ウレタン樹脂組成物 |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2941966A (en) * | 1956-08-27 | 1960-06-21 | Du Pont | Carbodiimide polymers |
US3960950A (en) * | 1973-06-08 | 1976-06-01 | Minnesota Mining And Manufacturing Company | Process for carbodiiomide synthesis |
JPS5933605B2 (ja) * | 1977-02-10 | 1984-08-16 | 日本ポリウレタン工業株式会社 | 電気絶縁用注型ポリウレタン樹脂 |
US5574083A (en) * | 1993-06-11 | 1996-11-12 | Rohm And Haas Company | Aromatic polycarbodiimide crosslinkers |
JPH1041175A (ja) * | 1996-07-22 | 1998-02-13 | Hitachi Chem Co Ltd | イグニッションコイルの製造方法 |
JP3971491B2 (ja) * | 1996-11-13 | 2007-09-05 | 三洋化成工業株式会社 | 注型用ポリウレタン樹脂形成性組成物 |
JP3654619B2 (ja) * | 1998-03-20 | 2005-06-02 | 日清紡績株式会社 | ポリカルボジイミド共重合体及びその製造方法 |
EP0943642A1 (en) * | 1998-03-20 | 1999-09-22 | Nisshinbo Industries, Inc. | Polycarbodiimide copolymer and process for production thereof |
JP2004269691A (ja) * | 2003-03-07 | 2004-09-30 | Nitto Denko Corp | ポリカルボジイミド共重合体およびその製造方法 |
EP1598383A1 (en) | 2004-05-21 | 2005-11-23 | Nisshinbo Industries, Inc. | Thermosetting polycarbodiimide copolymer |
JP2007138080A (ja) | 2005-11-21 | 2007-06-07 | Nisshinbo Ind Inc | 変性ポリカルボジイミド組成物及び変性ポリカルボジイミド |
NL1031053C2 (nl) | 2006-02-02 | 2007-08-03 | Stahl Int Bv | Werkwijze voor de bereiding van dispersies van vernettingsmiddelen in water. |
JP2008214366A (ja) * | 2007-02-28 | 2008-09-18 | Sanyo Chem Ind Ltd | 膜モジュールのシール材用注型ポリウレタン樹脂形成性組成物 |
WO2009037826A1 (ja) * | 2007-09-21 | 2009-03-26 | Nippon Polyurethane Industry Co., Ltd. | ポリウレタン樹脂形成性組成物、シール材及び中空糸膜モジュール |
JP5288324B2 (ja) * | 2008-05-09 | 2013-09-11 | 日本ポリウレタン工業株式会社 | ポリウレタン樹脂形成性組成物、シール材及び中空糸膜モジュール |
JP2010275425A (ja) * | 2009-05-28 | 2010-12-09 | Dai Ichi Kogyo Seiyaku Co Ltd | 2液反応型ポリウレタン樹脂組成物及びこれを硬化させてなるポリウレタン樹脂 |
JP4993038B2 (ja) * | 2010-04-22 | 2012-08-08 | Dic株式会社 | 2液硬化型発泡ポリウレタン樹脂組成物、それを用いてなる成形体、及び靴底 |
NL2005163C2 (nl) * | 2010-07-28 | 2012-01-31 | Stahl Int Bv | Werkwijze voor de bereiding van multifunctionele polycarbodiimides, welke gebruikt worden als vernettingsmiddel. |
CN102070863B (zh) | 2010-12-15 | 2013-05-29 | 中国科学技术大学 | 一种防污材料及其应用 |
JP5833900B2 (ja) | 2011-11-29 | 2015-12-16 | 日清紡ホールディングス株式会社 | 樹脂架橋剤及び水性樹脂組成物 |
US9181460B2 (en) * | 2013-03-06 | 2015-11-10 | H.B. Fuller Company | Gas transmitting polyurethane adhesive |
JP5793585B2 (ja) * | 2014-02-05 | 2015-10-14 | 日清紡ケミカル株式会社 | ポリエステル系樹脂組成物、及び該ポリエステル系樹脂組成物を用いた成形品 |
JP5793586B2 (ja) * | 2014-02-05 | 2015-10-14 | 日清紡ケミカル株式会社 | ポリエステル系樹脂組成物、該ポリエステル系樹脂組成物の製造方法、及び該ポリエステル系樹脂組成物を用いた成形品 |
US20150353771A1 (en) * | 2014-06-10 | 2015-12-10 | Bayer Materialscience Llc | Coating compositions with an aqueous dispersion containing a polyurethane and an acid reactive crosslinking agent |
JP6849268B2 (ja) * | 2015-04-06 | 2021-03-24 | 日清紡ケミカル株式会社 | 変性ポリカルボジイミド化合物、硬化剤及び熱硬化性樹脂組成物 |
JP6849269B2 (ja) * | 2015-04-06 | 2021-03-24 | 日清紡ケミカル株式会社 | 変性ポリカルボジイミド化合物、硬化剤及び熱硬化性樹脂組成物 |
EP3582005B1 (en) * | 2017-02-07 | 2022-02-09 | Arisawa Mfg. Co., Ltd. | Photosensitive resin composition, solder resist film using said photosensitive resin composition, flexible printed circuit, and image display device |
US11609493B2 (en) * | 2017-02-07 | 2023-03-21 | Arisawa Mfg. Co., Ltd. | Photosensitive resin composition, solder resist film using said photosensitive resin composition, flexible printed circuit and image display device |
-
2017
- 2017-11-14 US US16/344,749 patent/US11028216B2/en active Active
- 2017-11-14 WO PCT/JP2017/040863 patent/WO2018092752A1/ja unknown
- 2017-11-14 EP EP17871311.1A patent/EP3543274A4/en not_active Withdrawn
- 2017-11-14 JP JP2018551632A patent/JP7031824B2/ja active Active
- 2017-11-14 KR KR1020197011548A patent/KR102441738B1/ko active IP Right Grant
- 2017-11-14 CN CN201780070323.XA patent/CN109952333B/zh active Active
- 2017-11-16 TW TW106139636A patent/TWI813549B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4169866A (en) * | 1976-04-08 | 1979-10-02 | Bayer Aktiengesellschaft | Polymer systems containing polycarbodiimides and thermoplastic polymer |
JP2002025342A (ja) * | 2000-07-13 | 2002-01-25 | Sanyu Rec Co Ltd | 電気絶縁用ウレタン樹脂組成物 |
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