JP2019011402A - Modified organic polyisocyanate composition, and two-liquid-type coating composition using the same - Google Patents
Modified organic polyisocyanate composition, and two-liquid-type coating composition using the same Download PDFInfo
- Publication number
- JP2019011402A JP2019011402A JP2017127614A JP2017127614A JP2019011402A JP 2019011402 A JP2019011402 A JP 2019011402A JP 2017127614 A JP2017127614 A JP 2017127614A JP 2017127614 A JP2017127614 A JP 2017127614A JP 2019011402 A JP2019011402 A JP 2019011402A
- Authority
- JP
- Japan
- Prior art keywords
- organic polyisocyanate
- modified organic
- group
- polyisocyanate composition
- phosphite
- 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.)
- Granted
Links
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 60
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000008199 coating composition Substances 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims description 42
- -1 2,6-di-tert-butyl-4-methylphenoxy Chemical group 0.000 claims description 41
- 150000003077 polyols Chemical class 0.000 claims description 39
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 9
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- SLHYOPBSTLVPFZ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) 2-ethylhexyl hydrogen phosphite Chemical compound CCCCC(CC)COP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C SLHYOPBSTLVPFZ-UHFFFAOYSA-N 0.000 claims description 2
- XKZGIJICHCVXFV-UHFFFAOYSA-N 2-ethylhexyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCC(CC)CCCC)OC1=CC=CC=C1 XKZGIJICHCVXFV-UHFFFAOYSA-N 0.000 claims description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 2
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 claims description 2
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC(C)C)OC1=CC=CC=C1 RYUJRXVZSJCHDZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 13
- 238000010790 dilution Methods 0.000 abstract description 3
- 239000012895 dilution Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 31
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- 125000005442 diisocyanate group Chemical group 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000004359 castor oil Substances 0.000 description 7
- 235000019438 castor oil Nutrition 0.000 description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 5
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical class O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IHAYMIVQKCTBBS-UHFFFAOYSA-N 2-[2-(2-hydroxyethyl)phenyl]ethanol Chemical compound OCCC1=CC=CC=C1CCO IHAYMIVQKCTBBS-UHFFFAOYSA-N 0.000 description 3
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 3
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 239000004677 Nylon Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
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- 230000002378 acidificating effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 3
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 229920001778 nylon Polymers 0.000 description 3
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- 150000001412 amines Chemical class 0.000 description 2
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- 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 2
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- 238000002156 mixing Methods 0.000 description 2
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- 150000002989 phenols Chemical class 0.000 description 2
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000000806 elastomer Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- VHBJYSCOEUIVQO-UHFFFAOYSA-N nonane-1,9-diol;octane-1,8-diol Chemical compound OCCCCCCCCO.OCCCCCCCCCO VHBJYSCOEUIVQO-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000006076 specific stabilizer Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、有機溶剤で希釈した際の外観安定性を向上させることができる変性有機ポリイソシアネート組成物に関するものである。 The present invention relates to a modified organic polyisocyanate composition capable of improving the appearance stability when diluted with an organic solvent.
有機ポリイソシアネートを変性した変性有機ポリイソシアネートは、ポリウレタンプラスチックの分野において有用であり、各方面で使用されている。例えば、発泡体、繊維、フィルム、エラストマー及びペイントを製造するにあたり、ポリオールとともに用いられる。その使用の際には、変性有機ポリイソシアネートは度々有機溶剤にて希釈され使用される。しかしながら、変性有機ポリイソシアネートを有機溶剤で希釈すると、貯蔵中に変色する傾向がある。この性質は、変性有機ポリイソシアネートが比較的高温において貯蔵されなければならない場合、特に顕著である。 Modified organic polyisocyanates obtained by modifying organic polyisocyanates are useful in the field of polyurethane plastics and are used in various fields. For example, it is used with polyols in the production of foams, fibers, films, elastomers and paints. In its use, the modified organic polyisocyanate is often diluted with an organic solvent. However, when the modified organic polyisocyanate is diluted with an organic solvent, it tends to discolor during storage. This property is particularly noticeable when the modified organic polyisocyanate must be stored at relatively high temperatures.
変性有機ポリイソシアネートの変色傾向を低減させるために種々の安定剤を該変性有機ポリイソシアネートに添加する、ということが既に提案されている。公知の安定剤には、立体障害フェノール、ジアルキルジフェニルアミン、フェノチアジン、ホスファイト並びにこれらの化合物の代表的なものの混合物がある(特許文献1、2)。 It has already been proposed to add various stabilizers to the modified organic polyisocyanate in order to reduce the tendency to discolor the modified organic polyisocyanate. Known stabilizers include sterically hindered phenols, dialkyldiphenylamines, phenothiazines, phosphites, and mixtures of representatives of these compounds (Patent Documents 1 and 2).
その中でトリフェニルホスファイト(TPP)は、高温での変色防止のために効果的である(特許文献3)。しかしTPPは、有機溶剤に希釈し貯蔵した際に外観不良を生じるという欠点がある。そこで、この問題点を克服した安定剤や製法が求められていた。 Among them, triphenyl phosphite (TPP) is effective for preventing discoloration at high temperatures (Patent Document 3). However, TPP has a drawback that it causes poor appearance when diluted and stored in an organic solvent. Therefore, there has been a demand for a stabilizer and a production method that overcome this problem.
本発明は、上記した背景技術に鑑みてなされたものであり、有機溶剤にて希釈後の経時外観安定性を改善した変性有機ポリイソシアネート組成物を提供することを目的とする。 The present invention has been made in view of the background art described above, and an object thereof is to provide a modified organic polyisocyanate composition having improved appearance stability over time after dilution with an organic solvent.
本発明者らは、検討を重ねた結果、特定の安定剤を含有させた変性有機ポリイソシアネートにより、前記課題が解決できることを見出し、本発明に到達した。 As a result of repeated studies, the present inventors have found that the above problems can be solved by a modified organic polyisocyanate containing a specific stabilizer, and have reached the present invention.
すなわち本発明は、以下の[1]〜[5]の実施形態を含むものである。 That is, the present invention includes the following embodiments [1] to [5].
[1]アロファネート基を含有する変性有機ポリイソシアネート組成物(A1)、及びウレタン基を含有する変性有機ポリイソシアネート組成物(A2)からなる群より選ばれる少なくとも一種と、式1で示されるホスファイト構造を持つ化合物(B)とを含む変性有機ポリイソシアネート組成物。 [1] At least one selected from the group consisting of a modified organic polyisocyanate composition (A1) containing an allophanate group and a modified organic polyisocyanate composition (A2) containing a urethane group, and a phosphite represented by Formula 1 A modified organic polyisocyanate composition comprising a compound (B) having a structure.
*R1〜R3は、それぞれ独立してアルキル基又はベンゼン環上にアルキル基を有するフェニル基を表し、R1〜R3のうち少なくとも一つの分子量が78以上である。 * R 1 to R 3 each independently represents an alkyl group or a phenyl group having an alkyl group on a benzene ring, and at least one of R 1 to R 3 has a molecular weight of 78 or more.
[2]ホスファイト構造を持つ化合物(B)が、トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト、3,9−ビス(2,6−ジ−tert−ブチル−4−メチルフェノキシ)−2,4,8,10−テトラオキサ−3,9−ジホスファスピロ[5.5]ウンデカン、3,9−ビス(オクタデシルオキシ)−2,4,8,10−テトラオキサ−3,9−ジホスファスピロ[5.5]ウンデカン、2,2−メチレンビス(4,6−ジ−tert−ブチルフェニル)2−エチルヘキシルホスファイト、トリス(ノニルフェニル)ホスファイト、テトラ−C12−15−アルキル(プロパン−2,2−ジイルビス(4,1−フェニレン))ビス(ホスファイト)、2−エチルヘキシルジフェニルホスファイト、イソデシルジフェニルホスファイト、トリイソデシルホスファイトから選ばれる、少なくとも一種であることを特徴とする、上記[1]に記載の変性有機ポリイソシアネート組成物。 [2] Compound (B) having a phosphite structure is tris (2,4-di-tert-butylphenyl) phosphite, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy). ) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5.5] undecane, 2,2-methylenebis (4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, tris (nonylphenyl) phosphite, tetra-C 12-15 -alkyl (propane-2, 2-diylbis (4,1-phenylene)) bis (phosphite), 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite Fight, selected from tri isodecyl phosphite, characterized in that at least one, modified organic polyisocyanate composition according to the above [1].
[3]アロファネート基を含有する変性有機ポリイソシアネート組成物(A1)、及びウレタン基を含有する変性有機ポリイソシアネート組成物(A2)からなる群より選ばれる少なくとも一種が、ヘキサメチレンジイソシアネートの変性体であることを特徴とする上記[1]又は[2]に記載の変性有機ポリイソシアネート組成物。 [3] At least one selected from the group consisting of a modified organic polyisocyanate composition (A1) containing an allophanate group and a modified organic polyisocyanate composition (A2) containing a urethane group is a modified product of hexamethylene diisocyanate. The modified organic polyisocyanate composition according to [1] or [2], which is characterized in that it is present.
[4]上記[1]乃至[3]のいずれかに記載の変性有機ポリイソシアネート組成物と、ポリオールとを含む二液型塗料組成物。 [4] A two-component coating composition comprising the modified organic polyisocyanate composition according to any one of [1] to [3] above and a polyol.
[5]上記[4]に記載の二液型塗料組成物から得られる塗膜。 [5] A coating film obtained from the two-component coating composition according to [4].
本発明の変性有機ポリイソシアネート組成物によれば、有機溶剤希釈後、高温における貯蔵後の外観が大いに改善され、その後のポリウレタンの製造のために有利に用いることができる。 According to the modified organic polyisocyanate composition of the present invention, after diluting the organic solvent, the appearance after storage at a high temperature is greatly improved, and can be advantageously used for the subsequent production of polyurethane.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明における変性有機ポリイソシアネート組成物は、アロファネート基を含有する変性有機ポリイソシアネート組成物(A1)、及びウレタン基を含有する変性有機ポリイソシアネート組成物(A2)からなる群より選ばれる少なくとも一種と、下記式1のホスファイト構造を持つ化合物(B)とを含む変性有機ポリイソシアネート組成物である。 The modified organic polyisocyanate composition in the present invention is at least one selected from the group consisting of a modified organic polyisocyanate composition (A1) containing an allophanate group and a modified organic polyisocyanate composition (A2) containing a urethane group. And a modified organic polyisocyanate composition comprising a compound (B) having a phosphite structure of the following formula 1.
*R1〜R3は、それぞれ独立してアルキル基又はベンゼン環上にアルキル基を有するフェニル基を表し、R1〜R3のうち少なくとも一つの分子量が78以上である。 * R 1 to R 3 each independently represents an alkyl group or a phenyl group having an alkyl group on a benzene ring, and at least one of R 1 to R 3 has a molecular weight of 78 or more.
本発明における変性有機ポリイソシアネート組成物は、有機ジイソシアネートモノマーと水酸基含有化合物とを、アロファネート化触媒、又はウレタン化触媒の存在下、アロファネート化、又はウレタン化することにより好適に得ることができる。 The modified organic polyisocyanate composition in the present invention can be suitably obtained by allophanatization or urethanization of an organic diisocyanate monomer and a hydroxyl group-containing compound in the presence of an allophanatization catalyst or a urethanization catalyst.
有機ジイソシアネートモノマーとしては、特に限定するものではないが、例えば、脂肪族ジイソシアネート、脂環族ジイソシアネート、芳香族ジイソシアネート、芳香脂肪族ジイソシアネート等が挙げられる。 Although it does not specifically limit as an organic diisocyanate monomer, For example, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, araliphatic diisocyanate, etc. are mentioned.
<脂肪族ジイソシアネート>
脂肪族ジイソシアネートの具体例としては、例えばヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、2−メチル−ペンタン−1,5−ジイソシアネート、3−メチル−ペンタン−1,5−ジイソシアネート、リジンジイソシアネート、トリオキシエチレンジイソシアネート等を挙げることができ、これらの混合物も使用することができる。
<Aliphatic diisocyanate>
Specific examples of the aliphatic diisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate and the like. And mixtures thereof can also be used.
<脂環族ジイソシアネート>
脂環族ジイソシアネートの具体例としては、例えばイソホロンジイソシアネート、シクロヘキサンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、ノルボルナンジイソシアネート、水素添加トリレンジイソシアネート、水素添加キシレンジイソシアネート、水素添加テトラメチルキシレンジイソシアネート等を挙げることができ、これらの混合物も使用することができる。
<Alicyclic diisocyanate>
Specific examples of the alicyclic diisocyanate include isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, and the like. A mixture of these can also be used.
<芳香族ジイソシアネート>
芳香族ジイソシアネートの具体例としては、例えば2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、4,4’−ジフェニルメタンジイソシアネート、2,4’−ジフェニルメタンジイソシアネート、2,2’−ジフェニルメタンジイソシアネート、4,4’−ジフェニルエーテルジイソシアネート、2−ニトロジフェニル−4,4’−ジイソシアネート、2,2’−ジフェニルプロパン−4,4’−ジイソシアネート、3,3’−ジメチルジフェニルメタン−4,4’−ジイソシアネート、4,4’−ジフェニルプロパンジイソシアネート、m−フェニレンジイソシアネート、p−フェニレンジイソシアネート、ナフチレン−1,4−ジイソシアネート、ナフチレン−1,5−ジイソシアネート、3,3’−ジメトキシジフェニル−4,4’−ジイソシアネート等を挙げることができ、これらの混合物も使用することができる。
<Aromatic diisocyanate>
Specific examples of the aromatic diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4′-diisocyanate, 2,2′-diphenylpropane-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3′-dimethoxydiphenyl 4,4'-diisocyanate and the like can be mentioned, may also be used a mixture thereof.
<芳香脂肪族ジイソシアネート>
芳香脂肪族ジイソシアネートの具体例としては、例えば1,3−又は1,4−キシリレンジイソシアネート、1,3−又は1,4−ビス(1−イソシアナト−1−メチルエチル)ベンゼン、ω,ω’−ジイソシアナト−1,4−ジエチルベンゼン等を挙げることができ、これらの混合物も使用することができる。
<Aromatic aliphatic diisocyanate>
Specific examples of the aromatic aliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene, ω, ω ′. -Diisocyanato-1, 4-diethylbenzene etc. can be mentioned, These mixtures can also be used.
水酸基含有化合物としては、特に限定するものではないが、一分子中に水酸基を1つ以上含有する化合物を挙げることができる。このような水酸基含有化合物としては、例えば、メタノール、エタノール、プロパノール、n−ブタノール、イソブタノール、n−ペンタノール、2−ペンタノール、n−ヘキサノール、2−ヘキサノール、n−ヘプタノール、n−オクタノール、2−エチル−1−ヘキサノール、3,3,5−トリメチル−1−ヘキサノール、n−トリデカノール、2−トリデカノール、2−オクチルドデカノール、ペンタデカノール、パルミチルアルコール、ステアリルアルコール、シクロペンタノール、シクロヘキサノール、メチルシクロヘキサノール、トリメチルシクロヘキサノール等のモノアルコール、C2〜C18のアルカンジオール等が挙げられる。 Although it does not specifically limit as a hydroxyl-containing compound, The compound which contains one or more hydroxyl groups in 1 molecule can be mentioned. Examples of such a hydroxyl group-containing compound include methanol, ethanol, propanol, n-butanol, isobutanol, n-pentanol, 2-pentanol, n-hexanol, 2-hexanol, n-heptanol, n-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, n-tridecanol, 2-tridecanol, 2-octyldodecanol, pentadecanol, palmityl alcohol, stearyl alcohol, cyclopentanol, cyclo Examples thereof include monoalcohols such as hexanol, methylcyclohexanol and trimethylcyclohexanol, and C2 to C18 alkanediols.
触媒としては、実施する反応に応じて、公知の触媒から適宜選択して用いることができ、本発明においては、アロファネート化触媒、又はウレタン化触媒を用いることが好ましい。 As a catalyst, it can select from a well-known catalyst suitably according to reaction to implement, and it is preferable to use an allophanatization catalyst or a urethanization catalyst in this invention.
アロファネート化触媒としては、カルボン酸金属塩等の塩基性触媒等を用いることができ、例えば酢酸、プロピオン酸、ウンデシル酸、カプリン酸、オクチル酸、ミリスチン酸等のカルボン酸の亜鉛塩、スズ塩、ジルコニウム塩等を挙げることができる。 As the allophanatization catalyst, a basic catalyst such as a carboxylic acid metal salt can be used, for example, a zinc salt of a carboxylic acid such as acetic acid, propionic acid, undecyl acid, capric acid, octylic acid, myristic acid, tin salt, A zirconium salt etc. can be mentioned.
ウレタン化触媒としては、カルボン酸金属塩等の塩基性触媒等を用いることができ、例えば酢酸、プロピオン酸、ウンデシル酸、カプリン酸、オクチル酸、ミリスチン酸等のカルボン酸のスズ塩、ビスマス塩等を挙げることができる。 As the urethanization catalyst, basic catalysts such as carboxylic acid metal salts can be used. For example, tin salts of carboxylic acids such as acetic acid, propionic acid, undecyl acid, capric acid, octylic acid, myristic acid, bismuth salts, etc. Can be mentioned.
本発明における変性有機ポリイソシアネート組成物は、ホスファイト化合物(B)を含むものである。 The modified organic polyisocyanate composition in the present invention contains a phosphite compound (B).
本発明におけるホスファイト化合物(B)としては、上記した式1に示される化合物であり、酸化防止剤として市場で入手できるホスファイト系酸化防止剤のうち、例えばトリス(2,4−ジ−tert−ブチルフェニル)ホスファイト、3,9−ビス(2,6−ジ−tert−ブチル−4−メチルフェノキシ)−2,4,8,10−テトラオキサ−3,9−ジホスファスピロ[5.5]ウンデカン等、BASF社からイルガフォス(IRGAFOS)の商品名で得られるものや、あるいはADEKA社からアデカスタブの商品名で入手できるホスファイト構造を持つ化合物等を挙げることができる。 The phosphite compound (B) in the present invention is a compound represented by the above formula 1, and among phosphite antioxidants available on the market as antioxidants, for example, tris (2,4-di-tert. -Butylphenyl) phosphite, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane Examples thereof include compounds obtained from BASF under the trade name IRGAFOS, and compounds having a phosphite structure available from ADEKA under the trade name ADK STAB.
式1のR1〜R3は、それぞれ独立してアルキル基もしくはベンゼン環上にアルキル基を有するフェニル基を表し、R1〜R3のうちの少なくとも一つの分子量が78以上である。外観不良抑制効果を高めるために、R1〜R3のうち少なくとも一つの分子量は、113以上であることが好ましく、190以上であることが更に好ましい。 R 1 to R 3 in Formula 1 each independently represents an alkyl group or a phenyl group having an alkyl group on the benzene ring, and the molecular weight of at least one of R 1 to R 3 is 78 or more. In order to enhance the appearance defect suppressing effect, at least one molecular weight of R 1 to R 3 is preferably 113 or more, and more preferably 190 or more.
ホスファイト構造を持つ化合物(B)の含有量は、アロファネート基を含有する変性有機ポリイソシアネート組成物(A1)、又はウレタン基を含有する変性有機ポリイソシアネート組成物(A2)に対して0.01〜1質量%含有することが好ましく、0.05〜0.5質量%含有することが更に好ましい。 The content of the compound (B) having a phosphite structure is 0.01 with respect to the modified organic polyisocyanate composition (A1) containing an allophanate group or the modified organic polyisocyanate composition (A2) containing a urethane group. It is preferable to contain-1 mass%, and it is still more preferable to contain 0.05-0.5 mass%.
次に、本発明の変性有機ポリイソシアネート組成物の具体的な製造方法について説明する。 Next, a specific method for producing the modified organic polyisocyanate composition of the present invention will be described.
第1工程では、有機ジイソシアネートモノマーと水酸基含有化合物とを、水酸基に対してイソシアネート基が過剰になる量を仕込んで、有機溶剤の存在下または非存在下、50〜150℃で、ウレタン化及びアロファネート化反応のうち少なくとも一種の反応をさせてイソシアネート基末端プレポリマーIを製造する。ここでの反応の目安としては、中和滴定法によるイソシアネート基含有量と屈折率上昇値により完結を判断する。 In the first step, an organic diisocyanate monomer and a hydroxyl group-containing compound are charged in an amount in which an isocyanate group becomes excessive with respect to a hydroxyl group, and urethanized and allophanate at 50 to 150 ° C. in the presence or absence of an organic solvent. An isocyanate group-terminated prepolymer I is produced by performing at least one reaction among the conversion reactions. As a measure of the reaction here, the completion is judged by the isocyanate group content and the refractive index increase value by the neutralization titration method.
第2工程では、イソシアネート基末端プレポリマーIに反応停止剤を添加することによって、反応の停止を行う。 In the second step, the reaction is stopped by adding a reaction terminator to the isocyanate group-terminated prepolymer I.
これら第1工程〜第2工程においては、窒素ガス、若しくは、乾燥空気気流下で反応を進行させる。 In these 1st process-2nd process, reaction is advanced under nitrogen gas or a dry air stream.
第3工程では、第2工程で得られたイソシアネート基末端プレポリマーを薄膜蒸留又は溶剤抽出によって、遊離の有機ジイソシアネートモノマーの含有量を1質量%未満になるまで除去し、変性有機ポリイソシアネートを得る。 In the third step, the isocyanate group-terminated prepolymer obtained in the second step is removed by thin film distillation or solvent extraction until the content of free organic diisocyanate monomer is less than 1% by mass to obtain a modified organic polyisocyanate. .
ここで、第1工程における「イソシアネート基が過剰になる量」とは、イソシアネート基と水酸基とのモル比が、R=イソシアネート基/水酸基で5〜75になるように仕込むことが好ましく、R=5〜50になるように仕込むことがさらに好ましい。下限未満の場合には、目的物よりも分子量の高いポリイソシアネート組成物の生成量が多くなり、粘度の上昇を招く恐れがある。上限を超える場合には、粘度の上昇及び製品収率が下がり、生産性の低下を招く恐れがある。 Here, the “amount of isocyanate group excess” in the first step is preferably such that the molar ratio of isocyanate group to hydroxyl group is 5 to 75 (R = isocyanate group / hydroxyl group). It is more preferable to prepare so that it may become 5-50. When the amount is less than the lower limit, the amount of a polyisocyanate composition having a molecular weight higher than that of the target product is increased, which may increase the viscosity. If the upper limit is exceeded, the viscosity increases and the product yield decreases, which may lead to a decrease in productivity.
第1工程で用いる有機ジイソシアネートモノマーとしては、前記した各種ジイソシアネートを挙げることができる。 Examples of the organic diisocyanate monomer used in the first step include various diisocyanates described above.
第1工程で用いる水酸基含有化合物としては、前記した各種水酸基含有化合物を挙げることができる。 Examples of the hydroxyl group-containing compound used in the first step include the various hydroxyl group-containing compounds described above.
また、第1工程では触媒を用いることができ、反応に用いる触媒としては、前記した触媒を挙げることができる。 In the first step, a catalyst can be used, and examples of the catalyst used for the reaction include the above-described catalysts.
第1工程の反応は、反応に影響を与えない各種有機溶媒中で行うこともでき、有機溶媒の例としては、例えば脂肪族炭化水素類、脂環族炭化水素類、ケトン類、エステル類、グリコールエーテルエステル類、エーテル類、ハロゲン化炭化水素類、極性非プロトン溶媒等が挙げられる。 The reaction in the first step can also be performed in various organic solvents that do not affect the reaction. Examples of the organic solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, esters, Examples include glycol ether esters, ethers, halogenated hydrocarbons, and polar aprotic solvents.
脂肪族炭化水素類としては、例えばn−ヘキサン、オクタン等が挙げられる。 Examples of the aliphatic hydrocarbons include n-hexane and octane.
脂環族炭化水素類としては、例えばシクロヘキサン、メチルシクロヘキサン等が挙げられる。 Examples of the alicyclic hydrocarbons include cyclohexane and methylcyclohexane.
ケトン類としては、例えばアセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等が挙げられる。 Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
エステル類としては、例えば酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル等が挙げられる。 Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate.
グリコールエーテルエステル類としては、例えばエチレングリコールエチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、3−メチル−3−メトキシブチルアセテート、エチル−3−エトキシプロピオネート等が挙げられる。 Examples of glycol ether esters include ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, and the like.
エーテル類としては、例えばジエチルエーテル、テトラヒドロフラン、ジオキサン等が挙げられる。 Examples of ethers include diethyl ether, tetrahydrofuran, dioxane and the like.
ハロゲン化炭化水素類としては例えば、塩化メチル、塩化メチレン、クロロホルム、四塩化炭素、臭化メチル、ヨウ化メチレン、ジクロロエタン等が挙げられる。 Examples of halogenated hydrocarbons include methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloroethane, and the like.
極性非プロトン溶媒としては、例えばN−メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホニルアミド等が挙げられる。 Examples of the polar aprotic solvent include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphonilamide and the like.
これらの溶媒は単独で、または2種以上組み合わせて用いることができる。 These solvents can be used alone or in combination of two or more.
反応で使用した有機溶媒は、第3工程における遊離の有機ジイソシアネートの除去時に同時に除去される。 The organic solvent used in the reaction is removed simultaneously with the removal of free organic diisocyanate in the third step.
第2工程における反応停止剤としては、触媒の活性を失活させる作用があるものであり、具体的には、リン酸、塩酸等の無機酸、スルホン酸基、スルファミン酸基等を有する有機酸およびこれらのエステル類、アシルハライド等公知の化合物が使用される。これらの反応停止剤は、単独または2種以上を併用することができる。尚、添加時期は、反応終了後、速やかな添加が好ましい。 The reaction terminator in the second step has a function of deactivating the activity of the catalyst. Specifically, the organic acid has an inorganic acid such as phosphoric acid or hydrochloric acid, a sulfonic acid group, a sulfamic acid group, or the like. In addition, known compounds such as esters and acyl halides are used. These reaction terminators can be used alone or in combination of two or more. In addition, the addition time is preferably a rapid addition after completion of the reaction.
また、反応停止剤の添加量は、反応停止剤や使用した触媒の種類によって異なるが、触媒の0.5〜10当量となるのが好ましく、0.8〜5.0当量が特に好ましい。反応停止剤が少ない場合には、得られるポリイソシアネート組成物の貯蔵安定性が低下しやすく、多すぎる場合は変性ポリイソシアネートが着色する場合がある。 Moreover, although the addition amount of reaction terminator changes with kinds of reaction terminator and the catalyst used, it is preferable that it becomes 0.5-10 equivalent of a catalyst, and 0.8-5.0 equivalent is especially preferable. When there are few reaction terminators, the storage stability of the obtained polyisocyanate composition tends to be lowered, and when it is too much, the modified polyisocyanate may be colored.
ホスファイト構造を持つ化合物(B)の添加については、いずれのタイミングで添加しても良いが、第2工程の始めから第3工程の終わりまでに添加することが好ましく、第2工程終了後から第3工程開始前がより好ましい。 The compound (B) having a phosphite structure may be added at any timing, but is preferably added from the beginning of the second step to the end of the third step. More preferably, before the start of the third step.
第3工程の精製工程では、反応混合物中に存在している遊離の未反応の有機ジイソシアネートモノマーを、例えば、10〜100Paの高真空下、120〜150℃で薄膜蒸留による除去法や有機溶剤による抽出法により、残留含有率を1.0質量%以下にする。尚、有機ジイソシアネートモノマーの残留含有率が上限値を超える場合は、臭気の発生や貯蔵安定性の低下を招く恐れがある。 In the purification step of the third step, the free unreacted organic diisocyanate monomer present in the reaction mixture is removed, for example, by thin film distillation at 120 to 150 ° C. under a high vacuum of 10 to 100 Pa or with an organic solvent. The residual content is adjusted to 1.0% by mass or less by an extraction method. In addition, when the residual content rate of an organic diisocyanate monomer exceeds an upper limit, there exists a possibility of causing the generation | occurrence | production of an odor and the fall of storage stability.
精製して得られた変性有機ポリイソシアネートは、ポットライフの延長や塗料組成物の一液化を目的として、公知のブロック剤を用いてブロックイソシアネートとすることも可能である。これにより、ブロック化されたポリイソシアネートは、常温時は不活性であるが、加熱することでブロック剤が解離し、再びイソシアネート基が活性化することで、活性水素基と反応する潜在的な機能を付加することができる。 The modified organic polyisocyanate obtained by purification can be converted to a blocked isocyanate using a known blocking agent for the purpose of extending the pot life or making the coating composition one component. As a result, the blocked polyisocyanate is inactive at room temperature, but when heated, the blocking agent dissociates, and the isocyanate group is activated again, thereby causing a potential function to react with the active hydrogen group. Can be added.
本発明に用いることができる、ブロック剤としては、活性水素基を分子内に1個有する化合物であり、例えば、アルコール系、アルキルフェノール系、フェノール系、活性メチレン、メルカプタン系、酸アミド系、酸イミド系、イミダゾール系、尿素系、オキシム系、アミン系、イミド系、ピラゾール系化合物等がある。 The blocking agent that can be used in the present invention is a compound having one active hydrogen group in the molecule, and examples thereof include alcohols, alkylphenols, phenols, active methylenes, mercaptans, acid amides, and acid imides. , Imidazole, urea, oxime, amine, imide, and pyrazole compounds.
また、一連の反応で得られた変性有機ポリイソシアネートは、ポリオールを配合することによって、本発明の二液型塗料組成物を得ることができる。 Moreover, the modified organic polyisocyanate obtained by a series of reactions can obtain the two-component coating composition of the present invention by blending a polyol.
ここで、本発明の二液型塗料組成物に使用されるポリオールとしては、特に限定されるものではないが、イソシアネート基との反応基として活性水素基を含有する化合物であり、例えばポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリオレフィンポリオール、アクリルポリオール、シリコーンポリオール、ヒマシ油系ポリオール、フッ素系ポリオール、2種類以上のポリオールのエステル交換物、及びポリイソシアネートとウレタン化反応した水酸基末端プレポリマー等が好適に用いられ、これらは1種類又は2種類以上の混合物として使用することもできる。 Here, the polyol used in the two-component coating composition of the present invention is not particularly limited, but is a compound containing an active hydrogen group as a reactive group with an isocyanate group, such as a polyester polyol, Suitable examples include polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, silicone polyols, castor oil-based polyols, fluorine-based polyols, transesterification products of two or more polyols, and hydroxyl-terminated prepolymers that have undergone a urethanization reaction with polyisocyanates. These can be used as one kind or a mixture of two or more kinds.
<ポリエステルポリオール>
ポリエステルポリオールの具体例としては、例えばフタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸、コハク酸、酒石酸、シュウ酸、マロン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、グルタコン酸、アゼライン酸、セバシン酸、1,4−シクロヘキシルジカルボン酸、α−ハイドロムコン酸、β−ハイドロムコン酸、α−ブチル−α−エチルグルタル酸、α,β−ジエチルサクシン酸、マレイン酸、フマル酸等のジカルボン酸またはこれらの無水物等の1種類以上と、エチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、1,8−オクタンジオール、1,9−ノナンジオール、3−メチル−1,5−ペンタンジオール、3,3−ジメチロールヘプタン、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール、シクロヘキサン−1,4−ジオール、シクロヘキサン−1,4−ジメタノール、ダイマー酸ジオール、ビスフェノールAのエチレンオキサイドやプロピレンオキサイド付加物、ビス(β−ヒドロキシエチル)ベンゼン、キシリレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の分子量500以下の低分子ポリオール類の1種類以上との縮重合反応から得られるもの等を挙げることができる。また、ε−カプロラクトン、アルキル置換ε−カプロラクトン、δ−バレロラクトン、アルキル置換δ−バレロラクトン等の環状エステルモノマーの開環重合から得られるラクトン系ポリエステルポリオール等を挙げることができる。更に、低分子ポリオールの一部をヘキサメチレンジアミン、イソホロンジアミン、モノエタノールアミン等の低分子ポリアミンや低分子アミノアルコールに代えて得られるポリエステル−アミドポリオールを使用することもできる。
<Polyester polyol>
Specific examples of the polyester polyol include, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid. , Sebacic acid, 1,4-cyclohexyl dicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid, maleic acid, fumaric acid, etc. One or more of acids or anhydrides thereof, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4- Low molecular weight polyols having a molecular weight of 500 or less such as dimethanol, dimer acid diol, bisphenol A ethylene oxide and propylene oxide adducts, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. Examples thereof include those obtained from a condensation polymerization reaction with one or more kinds. Also, lactone polyester polyols obtained from ring-opening polymerization of cyclic ester monomers such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone. Furthermore, a polyester-amide polyol obtained by replacing a part of the low molecular polyol with a low molecular polyamine such as hexamethylene diamine, isophorone diamine, monoethanolamine, or a low molecular amino alcohol can also be used.
<ポリエーテルポリオール>
ポリエーテルポリオールの具体例としては、例えばエチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、1,8−オクタンジオール、1,9−ノナンジオール、3−メチル−1,5−ペンタンジオール、3,3−ジメチロールヘプタン、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール、シクロヘキサン−1,4−ジオール、シクロヘキサン−1,4−ジメタノール、ダイマー酸ジオール、ビスフェノールA、ビス(β−ヒドロキシエチル)ベンゼン、キシリレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の低分子ポリオール類、またはエチレンジアミン、プロピレンジアミン、トルエンジアミン、メタフェニレンジアミン、ジフェニルメタンジアミン、キシリレンジアミン等の低分子ポリアミン類等のような活性水素基を2個以上、好ましくは2〜3個有する化合物を開始剤として、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等のようなアルキレンオキサイド類を付加重合させることによって得られるポリエーテルポリオール、或いはメチルグリシジルエーテル等のアルキルグリシジルエーテル類、フェニルグリシジルエーテル等のアリールグリシジルエーテル類、テトラヒドロフラン等の環状エーテルモノマーを開環重合することで得られるポリエーテルポリオール等を挙げることができる。
<Polyether polyol>
Specific examples of the polyether polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol , Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol Small molecules such as Initiates compounds having 2 or more, preferably 2-3 active hydrogen groups such as diols or low molecular weight polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, etc. As an agent, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., or alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether And polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as tetrahydrofuran.
<ポリカーボネートポリオール>
ポリカーボネートポリオールの具体例としては、例えばエチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、1,8−オクタンジオール、1,9−ノナンジオール、3−メチル−1,5−ペンタンジオール、3,3−ジメチロールヘプタン、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール、シクロヘキサン−1,4−ジオール、シクロヘキサン−1,4−ジメタノール、ダイマー酸ジオール、ビスフェノールAのエチレンオキサイドやプロピレンオキサイド付加物、ビス(β−ヒドロキシエチル)ベンゼン、キシリレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の低分子ポリオールの1種類以上と、ジメチルカーボネート、ジエチルカーボネート等のジアルキルカーボネート類、エチレンカーボネート、プロピレンカーボネート等のアルキレンカーボネート類、ジフェニルカーボネート、ジナフチルカーボネート、ジアントリルカーボネート、ジフェナントリルカーボネート、ジインダニルカーボネート、テトラヒドロナフチルカーボネート等のジアリールカーボネート類との脱アルコール反応や脱フェノール反応から得られるもの等を挙げることができる。
<Polycarbonate polyol>
Specific examples of the polycarbonate polyol include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A ethylene oxide or propylene oxide adduct, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin The One or more kinds of low molecular polyols such as methylolpropane and pentaerythritol, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, di Examples thereof include those obtained from dealcoholization reaction and dephenol reaction with diaryl carbonates such as phenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate.
また、ポリカーボネートポリオールとポリエステルポリオールと低分子ポリオールのエステル交換反応により得られたポリオールも好適に用いることができる。 Moreover, the polyol obtained by transesterification of polycarbonate polyol, polyester polyol, and low molecular polyol can also be used suitably.
<ポリオレフィンポリオール>
ポリオレフィンポリオールの具体例としては、例えば水酸基を2個以上有するポリブタジエン、水素添加ポリブタジエン、ポリイソプレン、水素添加ポリイソプレン等を挙げることができる。
<Polyolefin polyol>
Specific examples of the polyolefin polyol include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and the like.
<アクリルポリオール>
アクリルポリオールとしては、例えばアクリル酸エステル及び/又はメタクリル酸エステル〔以下(メタ)アクリル酸エステルという〕と、反応点となりうる少なくとも分子内に1個以上の水酸基を有するアクリル酸ヒドロキシ化合物及び/又はメタクリル酸ヒドロキシ化合物〔以下(メタ)アクリル酸ヒドロキシ化合物という〕と、重合開始剤とを熱エネルギーや紫外線または電子線などの光エネルギー等を使用し、アクリルモノマーを共重合したもの等を挙げることができる。
<Acrylic polyol>
Examples of the acrylic polyol include acrylic acid ester and / or methacrylic acid ester (hereinafter referred to as (meth) acrylic acid ester), acrylic acid hydroxy compound having at least one hydroxyl group in the molecule and / or methacrylic acid which can be a reaction point. An acid hydroxy compound (hereinafter referred to as a (meth) acrylic acid hydroxy compound) and a polymerization initiator may be used in which an acrylic monomer is copolymerized using thermal energy, light energy such as ultraviolet rays or electron beams, and the like. .
<(メタ)アクリル酸エステル>
(メタ)アクリル酸エステルの具体例としては、例えば炭素数1〜20のアルキルエステル等を挙げることができる。このような(メタ)アクリル酸エステルの具体例としては、例えば(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸−2−エチルヘキシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル等の(メタ)アクリル酸アルキルエステル、シクロヘキシル(メタ)アクリレート等の(メタ)アクリル酸の脂環属アルコールとのエステル、(メタ)アクリル酸フェニル、(メタ)アクリル酸ベンジル等の(メタ)アクリル酸アリールエステル等を挙げることができる。このような(メタ)アクリル酸エステルは単独または2種類以上組み合わせたものを挙げることができる。
<(Meth) acrylic acid ester>
Specific examples of (meth) acrylic acid esters include alkyl esters having 1 to 20 carbon atoms. Specific examples of such (meth) acrylate esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. (Meth) such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate Acrylic acid alkyl ester, cyclohexyl (meth) acrylate and other (meth) acrylic acid esters with alicyclic alcohols, (meth) acrylic acid phenyl and (meth) acrylic acid aryl esters such as benzyl (meth) acrylate Can be mentioned. Such (meth) acrylic acid esters can be used singly or in combination of two or more.
<(メタ)アクリル酸ヒドロキシ化合物>
(メタ)アクリル酸ヒドロキシ化合物の具体例としては、ポリイソシアネートとの反応点となりうる少なくとも分子内に1個以上の水酸基を有しており、具体的には、例えば2−ヒドロキシエチルアクリレート、2−ヒドロキシプロピルアクリレート、4−ヒドロキシブチルアクリレート、3−ヒドロキシ−2,2−ジメチルプロピルアクリレート、ペンタエリスリトールトリアクリレート等のアクリル酸ヒドロキシ化合物等が挙げられる。また、2−ヒドロキシエチルメタクリレート、2−ヒドロキシプロピルメタクリレート、4−ヒドロキシブチルメタクリレート、3−ヒドロキシ−2,2−ジメチルプロピルメタクリレート、ペンタエリスリトールトリメタクリレート等のメタクリル酸ヒドロキシ化合物等が挙げられる。これら(メタ)アクリル酸ヒドロキシ化合物は、単独または2種以上を組み合わせたものを挙げることができる。
<(Meth) acrylic acid hydroxy compound>
Specific examples of the (meth) acrylic acid hydroxy compound have at least one hydroxyl group in the molecule that can be a reaction point with polyisocyanate. Specifically, for example, 2-hydroxyethyl acrylate, 2-hydroxy Acrylic hydroxy compounds such as hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, pentaerythritol triacrylate and the like can be mentioned. Moreover, methacrylic acid hydroxy compounds, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, pentaerythritol trimethacrylate, etc. are mentioned. As these (meth) acrylic acid hydroxy compounds, one or a combination of two or more may be mentioned.
<シリコーンポリオール>
シリコーンポリオールの具体例としては、例えばγ−メタクリロキシプロピルトリメトキシシラン等を重合したビニル基含有シリコーン化合物、及び分子中に少なくとも1個の末端水酸基を有する、α,ω−ジヒドロキシポリジメチルシロキサン、α,ω−ジヒドロキシポリジフェニルシロキサン等のポリシロキサン等を挙げることができる。
<Silicone polyol>
Specific examples of the silicone polyol include, for example, a vinyl group-containing silicone compound obtained by polymerizing γ-methacryloxypropyltrimethoxysilane and the like, α, ω-dihydroxypolydimethylsiloxane having at least one terminal hydroxyl group in the molecule, α , Ω-dihydroxypolydiphenylsiloxane, and the like.
<ヒマシ油系ポリオール>
ヒマシ油系ポリオールの具体例としては、例えばヒマシ油脂肪酸とポリオールとの反応により得られる線状または分岐状ポリエステルポリオール等が挙げられる。また、脱水ヒマシ油、一部分を脱水した部分脱水ヒマシ油、水素を付加させた水添ヒマシ油も使用することができる。
<Castor oil-based polyol>
Specific examples of the castor oil-based polyol include linear or branched polyester polyols obtained by the reaction of castor oil fatty acid and polyol. Dehydrated castor oil, partially dehydrated castor oil partially dehydrated, and hydrogenated castor oil added with hydrogen can also be used.
<フッ素系ポリオール>
フッ素系ポリオールの具体例としては、例えば含フッ素モノマーとヒドロキシ基を有するモノマーとを必須成分として共重合反応により得られる線状または分岐状のポリオールである。ここで、含フッ素モノマーとしては、フルオロオレフィンであることが好ましく、例えば、テトラフルオロエチレン、クロロトリフルオロエチレン、トリクロロフルオロエチレン、ヘキサフルオロプロピレン、フッ化ビニリデン、フッ化ビニル、トリフルオロメチルトリフルオロエチレン等が挙げられる。また、ヒドロキシル基を有するモノマーとしては、例えばヒドロキシエチルビニルエーテル、4−ヒドロキシブチルビニルエーテル、シクロヘキサンジオールモノビニルエーテル等のヒドロキシアルキルビニルエーテル、2−ヒドロキシエチルアリルエーテル等のヒドロキシアルキルアリルエーテル、ヒドロキシアルキルクロトン酸ビニル等のヒドロキシル基含有カルボン酸ビニル又はアリルエステル等のヒドロキシル基を有するモノマー等が挙げられる。
<Fluorine-based polyol>
Specific examples of the fluorine-based polyol include linear or branched polyols obtained by a copolymerization reaction using, for example, a fluorine-containing monomer and a monomer having a hydroxy group as essential components. Here, the fluorine-containing monomer is preferably a fluoroolefin, for example, tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyl trifluoroethylene. Etc. Examples of the monomer having a hydroxyl group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and cyclohexanediol monovinyl ether, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, and hydroxyalkyl vinyl crotonates. And monomers having a hydroxyl group, such as a hydroxyl group-containing vinyl carboxylate or allyl ester.
また、ポリオールは、1分子中の活性水素基数(平均官能基数)が1.9〜6.0であることが好ましい。活性水素基数が下限値未満の場合には、塗膜物性が低下する恐れがある。また、上限値を超える場合には、密着性が低下する恐れがある。 The polyol preferably has an active hydrogen group number (average functional group number) in one molecule of 1.9 to 6.0. When the number of active hydrogen groups is less than the lower limit, the physical properties of the coating film may be reduced. Moreover, when exceeding an upper limit, there exists a possibility that adhesiveness may fall.
また、ポリオールの数平均分子量は、500〜50000の範囲にあることが好ましい。下限値未満の場合には、密着性低下の恐れがあり、上限値を超えると低極性有機溶剤に対する溶解性の低下や密着性低下を招く恐れがある。 Moreover, it is preferable that the number average molecular weight of a polyol exists in the range of 500-50000. If it is less than the lower limit, the adhesion may be reduced, and if it exceeds the upper limit, the solubility in a low-polar organic solvent may be lowered or the adhesion may be lowered.
また、本発明の二液型塗料組成物のポリイソシアネート組成物と、ポリオールとの配合割合は、特に限定するものではないが、イソシアネート組成物中のイソシアネート基とポリオール中の水酸基のモル比が、R=イソシアネート基/水酸基で0.5〜2.5となるように配合することが好ましい。下限値未満の場合には水酸基が過剰になり、密着性の低下を招く恐れがある。また、架橋密度が低下し耐久性の低下や塗膜の機械的強度が低下する恐れがある。上限値を超える場合にはイソシアネート基が過剰になり、空気中の水分と反応し、塗膜の膨れやこれに伴う密着性の低下を生じる恐れがある。 Further, the blending ratio of the polyisocyanate composition of the two-component coating composition of the present invention and the polyol is not particularly limited, but the molar ratio of the isocyanate group in the isocyanate composition to the hydroxyl group in the polyol is It is preferable that R = isocyanate group / hydroxyl group to be 0.5 to 2.5. If it is less than the lower limit, the hydroxyl group becomes excessive, which may cause a decrease in adhesion. Moreover, there exists a possibility that a crosslinking density may fall and durability and the mechanical strength of a coating film may fall. When the upper limit is exceeded, the isocyanate group becomes excessive and reacts with moisture in the air, which may cause swelling of the coating film and a decrease in adhesion.
また、希釈溶剤として使用する有機溶剤としては、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、酢酸エチル、酢酸ブチル、酢酸セロソルブ等のエステル類、ブタノール、イソプロピルアルコール等のアルコール類、トルエン、キシレン、シクロヘキサン、ミネラルスピリット、ナフサ等の炭化水素類等からなる群から、目的及び用途に応じて適宜選択して使用することができる。これらの溶剤は単独で用いてもよく、2種以上を併用してもよい。 Moreover, as an organic solvent used as a diluting solvent, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate and cellosolve, alcohols such as butanol and isopropyl alcohol, toluene, xylene, From the group consisting of hydrocarbons such as cyclohexane, mineral spirits, naphtha and the like, it can be appropriately selected and used according to the purpose and application. These solvents may be used alone or in combination of two or more.
また、本発明の二液型塗料組成物は、ポットライフ、硬化条件、及び作業条件等を考慮し、適宜に公知のウレタン化触媒を用いることができる。具体的には、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジオクチル錫ジラウレート等の有機金属化合物や、トリエチレンジアミンやトリエチルアミン等の有機アミンやその塩を選択して用いる。これらの触媒は、単独または2種以上併用することができる。 Moreover, the two-component coating composition of the present invention can use a known urethanization catalyst as appropriate in consideration of pot life, curing conditions, working conditions, and the like. Specifically, organic metal compounds such as dibutyltin diacetate, dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof are selected and used. These catalysts can be used alone or in combination of two or more.
また、本発明の二液型塗料組成物の硬化条件としては、特に限定されるものではないが、硬化温度が−5〜120℃、湿度が10〜95%RH、養生時間が0.5〜168時間であることが好ましい。 Further, the curing conditions of the two-component coating composition of the present invention are not particularly limited, but the curing temperature is -5 to 120 ° C, the humidity is 10 to 95% RH, and the curing time is 0.5 to 0.5. Preferably it is 168 hours.
本発明によって得られた二液型塗料組成物は、スプレー、刷毛、浸漬、コーター等の公知の方法により被着体の表面上に塗布され、塗膜を形成する。 The two-component coating composition obtained by the present invention is applied onto the surface of an adherend by a known method such as spraying, brushing, dipping, or coater to form a coating film.
ここで、被着体は特に限定されるものではなく、ステンレス、リン酸処理鋼、亜鉛鋼、鉄、銅、アルミニウム、真鍮、ガラス、スレート、アクリル樹脂、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリブチレンフタレート樹脂、ポリスチレン樹脂、AS樹脂、ABS樹脂、ポリカーボネート−ABS樹脂、6−ナイロン樹脂、6,6−ナイロン樹脂、MXD6ナイロン樹脂、ポリ塩化ビニル樹脂、ポリビニルアルコール樹脂、ポリウレタン樹脂、フェノール樹脂、メラミン樹脂、ポリアセタール樹脂、塩素化ポリオレフィン樹脂、ポリオレフィン樹脂、ポリアミド樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンスルフィド樹脂、NBR樹脂、クロロプレン樹脂、SBR樹脂、SEBS樹脂などの素材で成形された被着体、コロナ放電処理やその他表面処理を施されたポリエチレン、ポリプロピレン等のオレフィン樹脂、または前記被着体表面にプライマ―層などの中間層が形成された被着体を用いることができる。 Here, the adherend is not particularly limited, and is stainless steel, phosphate-treated steel, zinc steel, iron, copper, aluminum, brass, glass, slate, acrylic resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate. Resin, polybutylene phthalate resin, polystyrene resin, AS resin, ABS resin, polycarbonate-ABS resin, 6-nylon resin, 6,6-nylon resin, MXD6 nylon resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyurethane resin, phenol Resin, melamine resin, polyacetal resin, chlorinated polyolefin resin, polyolefin resin, polyamide resin, polyether ether ketone resin, polyphenylene sulfide resin, NBR resin, chloroprene resin, SBR resin, SE An adherend formed of a material such as S resin, an olefin resin such as polyethylene or polypropylene subjected to corona discharge treatment or other surface treatment, or an intermediate layer such as a primer layer was formed on the adherend surface. An adherend can be used.
被着体表層に形成される塗膜の膜厚は、リコート性や耐久性に優れるため、被着体に少なくとも10μmの膜厚を形成すれば良い。膜厚が10μm未満である場合には耐久性が低下し、衝撃により塗膜の破れ等を生じる恐れがある。 Since the film thickness of the coating film formed on the adherend surface layer is excellent in recoatability and durability, a film thickness of at least 10 μm may be formed on the adherend. When the film thickness is less than 10 μm, the durability is lowered, and there is a possibility that the coating film is torn by impact.
以下、実施例に基づいて本発明を更に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。なお、実施例における%表記は、特に断りのない限り質量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a following example. In addition, the% description in an Example is a mass reference | standard unless there is particular notice.
<ポリイソシアネート組成物の合成>
<実施例1>
攪拌機、温度計、冷却管、および窒素ガス導入管を備えた容量1リットルの四つ口フラスコに、ヘキサメチレンジイソシアネート(東ソー社製、NCO含量:49.9質量%、以下HDIという)910g、及びn−オクタノール(三洋化成工業社製)90gを仕込み、これらを撹拌しながら60℃に昇温し、この反応液中にアロファネート化触媒であるオクチル酸ジルコニール(第一稀元素化学工業社製)0.1gを添加し、110℃にて所定の屈折率に達するまで反応させた後、反応停止剤である酸性リン酸エステル(JP−508、城北化学工業社製)0.11gを添加し、60℃で1時間停止反応を行った。ここで、トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト(BASF社製、IRGAFOS 168)を0.3g添加し、60℃で1時間撹拌混合した。その後、反応生成物から、薄膜蒸留(条件:140℃,0.04kPa)により過剰のHDIを除去し、変性有機ポリイソシアネートP−1を430g得た。
<Synthesis of polyisocyanate composition>
<Example 1>
Into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introduction pipe, 910 g of hexamethylene diisocyanate (manufactured by Tosoh Corporation, NCO content: 49.9% by mass, hereinafter referred to as HDI), and 90 g of n-octanol (manufactured by Sanyo Kasei Kogyo Co., Ltd.) was charged and the temperature was raised to 60 ° C. while stirring. Zirconyl octylate (manufactured by Daiichi Rare Element Chemical Co., Ltd.) as an allophanate catalyst was added to this reaction solution. 0.1 g is added and reacted at 110 ° C. until a predetermined refractive index is reached. Then, 0.11 g of acidic phosphate ester (JP-508, manufactured by Johoku Chemical Industry Co., Ltd.) as a reaction terminator is added. A stop reaction was carried out at 1 ° C. for 1 hour. Here, 0.3 g of tris (2,4-di-tert-butylphenyl) phosphite (manufactured by BASF, IRGAFOS 168) was added, and the mixture was stirred and mixed at 60 ° C. for 1 hour. Thereafter, excess HDI was removed from the reaction product by thin film distillation (conditions: 140 ° C., 0.04 kPa) to obtain 430 g of modified organic polyisocyanate P-1.
<実施例2>
表1に示す条件で合成を行い,実施例1と同様な手順にて各変性ポリイソシアネートP−2を得た。
<Example 2>
Synthesis was performed under the conditions shown in Table 1, and each modified polyisocyanate P-2 was obtained in the same procedure as in Example 1.
<実施例3>
攪拌機、温度計、冷却管、および窒素ガス導入管を備えた容量1リットルの四つ口フラスコに、HDI592g、及びトリメチロールプロパン(三菱ガス化学社製)158g、酢酸エチル(昭和電工社製)250gを仕込み、これらを撹拌しながら60℃に昇温し,所定のNCO含量に達するまで反応させた。その後、トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト(BASF社製、IRGAFOS 168)を0.3g添加し、60℃で1時間撹拌混合し、変性有機ポリイソシアネートP−3を1000g得た。
<Example 3>
In a 1 liter four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 592 g of HDI, 158 g of trimethylolpropane (Mitsubishi Gas Chemical Co., Ltd.), and 250 g of ethyl acetate (manufactured by Showa Denko KK) The mixture was heated to 60 ° C. with stirring, and reacted until a predetermined NCO content was reached. Thereafter, 0.3 g of tris (2,4-di-tert-butylphenyl) phosphite (manufactured by BASF, IRGAFOS 168) was added and mixed with stirring at 60 ° C. for 1 hour, and 1000 g of modified organic polyisocyanate P-3 was added. Obtained.
<比較例1>
表1に示す条件で合成を行い,実施例1と同様な手順にて各変性ポリイソシアネートP−4を得た。
<Comparative Example 1>
Synthesis was performed under the conditions shown in Table 1, and each modified polyisocyanate P-4 was obtained in the same procedure as in Example 1.
<比較例2>
攪拌機、温度計、冷却管、および窒素ガス導入管を備えた容量1リットルの四つ口フラスコに、HDI910g、及びn−オクタノール(三洋化成工業社製)90gを仕込み、これらを撹拌しながら60℃に昇温し,この反応液中にアロファネート化触媒であるオクチル酸ジルコニール(第一稀元素化学工業社製)0.1gを添加し、110℃にて所定の屈折率に達するまで反応させた後、反応停止剤である酸性リン酸エステル(JP−508、城北化学工業社製)0.11gを添加し、60℃で1時間停止反応を行った。その後、反応生成物から、薄膜蒸留(条件:140℃,0.04kPa)により過剰のHDIを除去し、変性有機ポリイソシアネートP−5を430g得た。
<Comparative Example 2>
910 g of HDI and 90 g of n-octanol (manufactured by Sanyo Kasei Kogyo Co., Ltd.) were charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introduction pipe, and these were stirred at 60 ° C. After adding 0.1 g of zirconyl octylate (Daiichi Rare Element Chemical Co., Ltd.), which is an allophanatization catalyst, to this reaction solution, the reaction was carried out at 110 ° C. until a predetermined refractive index was reached. Then, 0.11 g of acidic phosphate ester (JP-508, manufactured by Johoku Chemical Industry Co., Ltd.) as a reaction terminator was added, and a termination reaction was performed at 60 ° C. for 1 hour. Thereafter, excess HDI was removed from the reaction product by thin-film distillation (conditions: 140 ° C., 0.04 kPa) to obtain 430 g of modified organic polyisocyanate P-5.
表1で使用した原料は以下の通り。
・酸性リン酸エステル:リン酸ジ−2−エチルヘキシル (JP−508、城北化学工業社製)
・触媒−1:オクチル酸ジルコニール (第一稀元素化学工業社製)
・酸化防止剤−1:トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト (IRGAFOS 168、BASF社製)
・酸化防止剤−2:3,9−ビス(2,6−ジ−tert−ブチル−4−メチルフェノキシ)−2,4,8,10−テトラオキサ−3,9−ジホスファスピロ[5.5]ウンデカン (アデカスタブ PEP−36、ADEKA社製)
・酸化防止剤−3:トリフェニルホスファイト (アデカスタブ TPP、ADEKA社製)。
The raw materials used in Table 1 are as follows.
Acidic phosphate ester: di-2-ethylhexyl phosphate (JP-508, manufactured by Johoku Chemical Industry Co., Ltd.)
・ Catalyst-1: Zirconyl octylate (Daiichi Rare Element Chemical Co., Ltd.)
Antioxidant-1: Tris (2,4-di-tert-butylphenyl) phosphite (IRGAFOS 168, manufactured by BASF)
Antioxidant-2: 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (ADK STAB PEP-36, manufactured by ADEKA)
Antioxidant-3: Triphenyl phosphite (Adeka Stub TPP, manufactured by ADEKA).
<色数評価>
色数の評価は、JIS K 0071−1に示されるハーゼン単位色数(白金−コバルト スケール)の方法を使用した。
<Evaluation of the number of colors>
For the evaluation of the number of colors, the Hazen unit color number (platinum-cobalt scale) method described in JIS K0071-1 was used.
<濁度評価>
濁度の評価は、JIS K 0101に示されるカオリン濁度(視覚法)の方法を使用した。
<Turbidity evaluation>
For the evaluation of turbidity, the method of kaolin turbidity (visual method) shown in JIS K 0101 was used.
<溶剤希釈安定性>
<初期値>
それぞれ得られた変性有機ポリイソシアネートP−1〜P−5をメチルエチルケトン(MEK)にて固形分20%になるよう希釈し、その色数・濁度を測定した。
<50℃×3ヶ月後>
変性有機ポリイソシアネートP−1〜P−5を、MEKにて固形分20%に希釈したものを50℃で3ヶ月保管した後、その色数・濁度を測定した。
<Solvent dilution stability>
<Initial value>
The obtained modified organic polyisocyanates P-1 to P-5 were diluted with methyl ethyl ketone (MEK) to a solid content of 20%, and the number of colors and turbidity were measured.
<50 ° C x 3 months later>
A modified organic polyisocyanate P-1 to P-5 diluted with MEK to a solid content of 20% was stored at 50 ° C. for 3 months, and its color number and turbidity were measured.
各実施例においては、良好な結果が得られた。一方、比較例であるP−4をMEKに希釈したものは、50℃で3ヶ月保管した後の色数に大きな変化はみられなかったが、濁度の上昇がみられた。P−5はサンプルの色数が高い傾向にあり、またMEKに希釈したものについても、50℃で3ヶ月保管した後に色数が高くなる傾向がみられた。 In each example, good results were obtained. On the other hand, when P-4 as a comparative example was diluted with MEK, the number of colors after 3 months storage at 50 ° C. did not change greatly, but an increase in turbidity was observed. P-5 had a tendency for the number of colors of the sample to be high, and those diluted with MEK also showed a tendency for the number of colors to increase after storage at 50 ° C. for 3 months.
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JP2007177171A (en) * | 2005-12-28 | 2007-07-12 | Mitsui Chemicals Polyurethanes Inc | Method for producing polyisocyanate containing allophanate group, urethane prepolymer and polyurethane resin composition |
JP2009007409A (en) * | 2007-06-26 | 2009-01-15 | Mitsui Chemicals Polyurethanes Inc | Water-dispersible isocyanate composition and aqueous polyurethane resin composition |
JP2017048270A (en) * | 2015-08-31 | 2017-03-09 | 旭化成株式会社 | Polyisocyanate composition and method for producing the same |
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JPH08188566A (en) * | 1995-01-06 | 1996-07-23 | Takeda Chem Ind Ltd | Allophanation and two-part type resin composition |
JP2007177171A (en) * | 2005-12-28 | 2007-07-12 | Mitsui Chemicals Polyurethanes Inc | Method for producing polyisocyanate containing allophanate group, urethane prepolymer and polyurethane resin composition |
JP2009007409A (en) * | 2007-06-26 | 2009-01-15 | Mitsui Chemicals Polyurethanes Inc | Water-dispersible isocyanate composition and aqueous polyurethane resin composition |
JP2017048270A (en) * | 2015-08-31 | 2017-03-09 | 旭化成株式会社 | Polyisocyanate composition and method for producing the same |
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