JP2014159508A - Polyurethane resin aqueous dispersion and cured product using composition thereof - Google Patents
Polyurethane resin aqueous dispersion and cured product using composition thereof Download PDFInfo
- Publication number
- JP2014159508A JP2014159508A JP2013030153A JP2013030153A JP2014159508A JP 2014159508 A JP2014159508 A JP 2014159508A JP 2013030153 A JP2013030153 A JP 2013030153A JP 2013030153 A JP2013030153 A JP 2013030153A JP 2014159508 A JP2014159508 A JP 2014159508A
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- JP
- Japan
- Prior art keywords
- weight
- parts
- polyurethane resin
- aqueous dispersion
- resin aqueous
- Prior art date
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- Granted
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- 239000006185 dispersion Substances 0.000 title claims abstract description 45
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229920000728 polyester Polymers 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 30
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 126
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 229920005862 polyol Polymers 0.000 description 30
- 239000000243 solution Substances 0.000 description 28
- -1 aliphatic diols Chemical class 0.000 description 27
- 150000003077 polyols Chemical class 0.000 description 25
- 238000007664 blowing Methods 0.000 description 16
- 239000012948 isocyanate Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000010992 reflux Methods 0.000 description 16
- 239000005056 polyisocyanate Substances 0.000 description 14
- 229920001228 polyisocyanate Polymers 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 229920005906 polyester polyol Polymers 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 11
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 10
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 10
- 239000004359 castor oil Substances 0.000 description 10
- 235000019438 castor oil Nutrition 0.000 description 10
- 239000007810 chemical reaction solvent Substances 0.000 description 10
- 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 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- BPEWUONYVDABNZ-DZBHQSCQSA-N testolactone Chemical compound O=C1C=C[C@]2(C)[C@H]3CC[C@](C)(OC(=O)CC4)[C@@H]4[C@@H]3CCC2=C1 BPEWUONYVDABNZ-DZBHQSCQSA-N 0.000 description 10
- 229960005353 testolactone Drugs 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DVFGEIYOLIFSRX-UHFFFAOYSA-N 3-(2-ethylhexoxy)propan-1-amine Chemical compound CCCCC(CC)COCCCN DVFGEIYOLIFSRX-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- 150000004992 toluidines Chemical class 0.000 description 1
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- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明はポリウレタン樹脂水分散体に関し、特に基材に対する密着性を与えることのできるポリウレタン樹脂水分散体、及び該ポリウレタン樹脂水分散体を板状材料表面に塗布してなる硬化物に関する。 The present invention relates to an aqueous polyurethane resin dispersion, and more particularly to an aqueous polyurethane resin dispersion capable of providing adhesion to a substrate, and a cured product obtained by applying the aqueous polyurethane resin dispersion to a plate-like material surface.
ポリウレタン樹脂は、耐摩耗性、接着性、非粘着性、及びゴム弾性を有する塗膜や成形品を与えることから、塗料、接着剤、バインダー、及びコーティング剤等として広く用いられている。その中でも近年、対環境汚染や労働衛生等の安全性の面から、ポリウレタン樹脂水分散体の需要が高まっている。 Polyurethane resins are widely used as paints, adhesives, binders, coating agents, and the like because they provide coatings and molded articles having wear resistance, adhesion, non-tackiness, and rubber elasticity. Among them, in recent years, demand for polyurethane resin water dispersions is increasing from the viewpoint of safety against environmental pollution and occupational health.
しかし、ポリウレタン樹脂水分散体は、溶剤系或いは無溶剤系のものに比べて、基材に対する密着性が劣るという問題点を有する。
本発明者らは、これらの課題を解決すべくポリオレフィン基材に対する密着性、耐摩耗性、ブロッキング性に優れた水性樹脂組成物を開示した（特許文献１）。
一方で近年、より耐水性、耐薬品性(耐酸性、耐アルカリ性)、引張特性にも優れた水系ウレタンが強く要望されるようになってきた。
However, the polyurethane resin aqueous dispersion has a problem that the adhesiveness to the substrate is inferior to that of the solvent-based or solvent-free type.
In order to solve these problems, the present inventors have disclosed an aqueous resin composition excellent in adhesion to a polyolefin substrate, wear resistance, and blocking properties (Patent Document 1).
On the other hand, in recent years, there has been a strong demand for water-based urethanes that are more excellent in water resistance, chemical resistance (acid resistance, alkali resistance), and tensile properties.
上記課題に鑑み、本発明が解決しようとする課題は、接着性の低い基材を含めた各種基材に対しての密着性に優れ、かつ硬化物の耐水および耐溶剤性、引張特性にも優れたポリウレタン樹脂水分散体を提供することである。 In view of the above problems, the problem to be solved by the present invention is excellent in adhesion to various substrates including substrates having low adhesiveness, and also in water resistance, solvent resistance, and tensile properties of the cured product. It is to provide an excellent polyurethane resin aqueous dispersion.
本発明者らは、上記の従来技術の課題点を克服すべく、検討し本発明に至った。 The inventors of the present invention have studied and led to the present invention in order to overcome the above-mentioned problems of the prior art.
本発明は具体的には下記の通りである。
少なくとも、下記（Ａ）および（Ｂ）を反応して得られるポリエーテルポリエステル化合物を用いて得られるポリウレタン樹脂水分散体。
（Ａ）ポリオキシアルキレン誘導体
（Ｂ）４価のカルボン酸、その塩および４価のカルボン酸無水物から選ばれる１以上の化合物及び該ポリウレタン樹脂水分散体を硬化させてなる硬化物である。
The present invention is specifically as follows.
A polyurethane resin aqueous dispersion obtained by using a polyether polyester compound obtained by reacting at least the following (A) and (B).
(A) Polyoxyalkylene derivative (B) A cured product obtained by curing one or more compounds selected from a tetravalent carboxylic acid, a salt thereof, and a tetravalent carboxylic anhydride, and the polyurethane resin aqueous dispersion.
上記課題に鑑み、フリーのカルボン酸を残しつつ、且つ、分子内により多くの酸価を持たせることにより、水系ウレタンでありながら、当該ポリウレタン樹脂水分散体は、接着性の低い基材を含めた各種基材に対しての密着性に優れ、かつ硬化物の耐水および耐溶剤性、引張特性にも優れる。 In view of the above problems, the polyurethane resin aqueous dispersion includes a base material with low adhesiveness, while being a water-based urethane by leaving free carboxylic acid and giving more acid value in the molecule. In addition, it has excellent adhesion to various substrates and is excellent in water resistance, solvent resistance, and tensile properties of the cured product.
本発明のポリウレタン樹脂水分散体は、少なくとも、下記（Ａ）および（Ｂ）を反応して得られるポリエーテルポリエステル化合物を用いて得られる。
（Ａ）ポリオキシアルキレン誘導体
（Ｂ）４価のカルボン酸、その塩および４価のカルボン酸無水物から選ばれる１以上の化合物
前記（Ａ）ポリオキシアルキレン誘導体としては、例えばポリオキシアルキレン誘導体としては脂肪族ジオールのアルキレンオキサイド付加物及び芳香族含有ジオールのアルキレンオキサイド付加物が挙げられる。中でも耐溶剤性の観点から、芳香族含有ジオールのアルキレンオキサイド付加物が好ましい。
The aqueous polyurethane resin dispersion of the present invention is obtained using at least a polyether polyester compound obtained by reacting the following (A) and (B).
(A) Polyoxyalkylene derivative (B) One or more compounds selected from tetravalent carboxylic acids, salts thereof and tetravalent carboxylic anhydrides As the (A) polyoxyalkylene derivatives, for example, polyoxyalkylene derivatives Include alkylene oxide adducts of aliphatic diols and alkylene oxide adducts of aromatic-containing diols. Among these, from the viewpoint of solvent resistance, an alkylene oxide adduct of an aromatic-containing diol is preferable.
前記ポリオキシアルキレン誘導体を構成する脂肪族ジオールとしては、エチレングリコール、プロピレングリコール、１, ２−、１, ３−、２, ３−及び１, ４−ブタンジオール、ネオペンチルグリコール、１ ， ６ − ヘキサンジ オール、１ ， ９ − ノナンジオール等が挙げられる。また前記芳香族含有ジオールとしてはフェノール類が挙げられ、ヒドロキノン、カテコール、レゾルシン、ビスフェノールＡ、ビスフェノールＳ，ビスフェノールＦなどが挙げられる。 Examples of the aliphatic diol constituting the polyoxyalkylene derivative include ethylene glycol, propylene glycol, 1, 2-, 1, 3-, 2, 3- and 1,4-butane diol, neopentyl glycol, 1, 6- Hexanediol, 1,9-nonanediol and the like can be mentioned. Examples of the aromatic-containing diol include phenols such as hydroquinone, catechol, resorcin, bisphenol A, bisphenol S, and bisphenol F.
ポリオキシアルキレン誘導体を構成するアルキレンオキサイドとしては、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、テトラヒドロフラン、α − オレフィンオキサイド、スチレンオキサイド、エピハロヒドリン（ エピクロルヒドリン等） 、およびこれらの２ 種以上の併用（ ランダムおよび／ またはブロック） が挙げられる。特に好ましいのは、親疎水性のバランスが良好な点から、プロピレンオキサイドである。 Examples of the alkylene oxide constituting the polyoxyalkylene derivative include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, α-olefin oxide, styrene oxide, epihalohydrin (such as epichlorohydrin), and combinations of two or more thereof (random and / or) Block). Particularly preferred is propylene oxide because it has a good balance between hydrophilicity and hydrophobicity.
前記ポリオキシアルキレン誘導体は、重量平均分子量は２００〜４０００であることが好ましく、４００〜２０００であることがより好ましい。重量平均分子量が２００未満であると基材に対する密着性・引張特性が低下し、２０００を超えると、耐溶剤性が低下するからである。 The polyoxyalkylene derivative preferably has a weight average molecular weight of 200 to 4000, and more preferably 400 to 2000. This is because if the weight average molecular weight is less than 200, the adhesion and tensile properties to the substrate are lowered, and if it exceeds 2000, the solvent resistance is lowered.
前記４価のカルボン酸としては、例えば、１，２，３，４−シクロペンタンテトラカルボン酸、ビフェニルテトラカルボン酸、ピロメリット酸、ナフタレン−１，４，５，８−テトラカルボン酸などが挙げられる。これら４価のカルボン酸は、１種を単独で用いてもよく、２種以上を混合してもよい。入手性、耐溶剤性の観点から、ピロメリット酸が好ましい。 Examples of the tetravalent carboxylic acid include 1,2,3,4-cyclopentanetetracarboxylic acid, biphenyltetracarboxylic acid, pyromellitic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and the like. It is done. These tetravalent carboxylic acids may be used individually by 1 type, and may mix 2 or more types. From the viewpoints of availability and solvent resistance, pyromellitic acid is preferred.
４価のカルボン酸塩としては、例えば前記４価カルボン酸の金属塩またはアンモニウム塩等が挙げられるが、前記４価カルボン酸および該カルボン酸と塩を形成する物質を反応させて得られるものであれば特に限定はない。前記４価カルボン酸と塩を形成する物質としては、金属、アミン類等が挙げられる。金属類は乳化力が高いことから好ましい。アミン類はポリウレタン樹脂水分散体の揮発性が高いことから好ましい。該金属の具体例としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、フランシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、ラジウム、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、クロム、モリブデン、タングステン、マンガン、鉄、ルテニウム、オスミウム、コバルト、ロジウム、イリジウム、ニッケル、銅、銀、亜鉛、カドミウム、水銀、アルミニウム、ガリウム、インジウム、タリウム、ケイ素、ゲルマニウム、スズ、鉛、アンチモン、ビスマス、スカンジウム等があげられ、該アミン類の具体例としては、トリメチルアミン、トリエチルアミン、トリプロピルアミン、アンモニア、ピリジン、ピロリジン、ピロール、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ヘキサメチレンジアミン、１，４−ジアザビシクロ［２．２．２］オクタン、ヒドラジン、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、エタンアミン、アニリン、トルイジン、アリルアミン、ジアリルアミン、トリアリルアミン、イソプロピルアミン、ジイソプロピルアミン、３，３’−イミノビス（プロピルアミン）、２−エチルヘキシルアミン、３−（２−エチルヘキシルオキシ）プロピルアミン、３−エトキシプロピルアミン、ジイソブチルアミン、３−（ジエチルアミノ）プロピルアミン、ジ−２−エチルヘキシルアミン、３−（ジブチルアミノ）プロピルアミン、テトラメチルエチレンジアミン、トリ−ｎ−オクチルアミン、ｔ−ブチルアミン、２−ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ピコリン、ビニルピリジン、ピペコリン、ピペラジン、ピペリジン、ピラジン等があげられる。 Examples of the tetravalent carboxylate include metal salts or ammonium salts of the tetravalent carboxylic acid, which are obtained by reacting the tetravalent carboxylic acid and a substance that forms a salt with the carboxylic acid. If there is no particular limitation. Examples of the substance that forms a salt with the tetravalent carboxylic acid include metals and amines. Metals are preferred because of their high emulsifying power. Amines are preferred because of the high volatility of the polyurethane resin aqueous dispersion. Specific examples of the metal include lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, titanium, zirconium, hafnium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, Iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, copper, silver, zinc, cadmium, mercury, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony, bismuth, scandium, etc. Specific examples of the amines include trimethylamine, triethylamine, tripropylamine, ammonia, pyridine, pyrrolidine, pyrrole, dimethylamine, diethylamine, dipropylamine. , Hexamethylenediamine, 1,4-diazabicyclo [2.2.2] octane, hydrazine, N, N-dimethylcyclohexylamine, ethanamine, aniline, toluidine, allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, 3, 3′-iminobis (propylamine), 2-ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3 -(Dibutylamino) propylamine, tetramethylethylenediamine, tri-n-octylamine, t-butylamine, 2-butylamine, monoethanolamine, diethanolamine, triethanol Min, picoline, vinyl pyridine, pipecolic, piperazine, piperidine, pyrazine and the like.
４価のカルボン酸無水物としては、１，２，３，４−シクロペンタンテトラカルボン二酸無水物、ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、ナフタレン−１，４，５，８−テトラカルボン酸二無水物などが挙げられ、これら４価のカルボン酸は、１種を単独で用いてもよく、２種以上を混合してもよい。なかでも、ビフェニルテトラカルボン酸二無水物またはピロメリット酸二無水物が、取扱い上特に好ましい。
特に限定されるものではないが、４価のカルボン酸、その塩および４価のカルボン酸無水物のうち、取り扱いのし易さから４価のカルボン酸無水物が好ましい。
Examples of the tetravalent carboxylic acid anhydride include 1,2,3,4-cyclopentanetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, naphthalene-1,4,5, 8-tetracarboxylic dianhydride etc. are mentioned, These tetravalent carboxylic acid may be used individually by 1 type, and may mix 2 or more types. Among these, biphenyltetracarboxylic dianhydride or pyromellitic dianhydride is particularly preferable in handling.
Although not particularly limited, among tetravalent carboxylic acids, salts thereof and tetravalent carboxylic acid anhydrides, tetravalent carboxylic acid anhydrides are preferable because of easy handling.
本発明で用いられるポリエーテルエステル化合物は、前記ポリオキシアルキレン誘導体と前記４価のカルボン酸もしくはその塩または４価のカルボン酸無水物とのエステル化反応によって得られ、エステル化反応は特に制限されるものではなく、従来公知のエステル化反応を用いることができる。すなわち、窒素雰囲気下において前記ポリオキシアルキレン誘導体と４価のカルボン酸もしくはその塩または４価のカルボン酸無水物とを２．５：１〜２：１のモル比で仕込み、加熱攪拌することによって反応性生物が得られる。好ましい反応温度は８０℃〜２５０℃で、特に好ましくは１００℃〜２２０℃である。好ましい反応時間は２〜１２時間である。 The polyether ester compound used in the present invention is obtained by an esterification reaction between the polyoxyalkylene derivative and the tetravalent carboxylic acid or a salt thereof or a tetravalent carboxylic anhydride, and the esterification reaction is particularly limited. Instead, a conventionally known esterification reaction can be used. That is, by charging the polyoxyalkylene derivative and a tetravalent carboxylic acid or a salt thereof or a tetravalent carboxylic acid anhydride in a molar ratio of 2.5: 1 to 2: 1 in a nitrogen atmosphere, and stirring with heating. Reactive organisms are obtained. The preferred reaction temperature is 80 ° C to 250 ° C, particularly preferably 100 ° C to 220 ° C. The preferred reaction time is 2 to 12 hours.
本発明のポリウレタン樹脂は、前記ポリエステルポリオール化合物等からなるポリオール化合物とイソシアネート化合物とを反応させることにより得られる。また、必要に応じて、分子内に親水性基を有する親水性基含有化合物、又はポリアミン等の鎖伸長剤などの化合物をさらに反応させることにより得られる。 The polyurethane resin of the present invention can be obtained by reacting a polyol compound composed of the polyester polyol compound or the like with an isocyanate compound. Moreover, it can be obtained by further reacting a compound such as a hydrophilic group-containing compound having a hydrophilic group in the molecule or a chain extender such as polyamine as necessary.
前記ポリオール化合物としては、例えば低分子量ポリオール、ポリエステルポリオール、ポリエーテルポリオール、ひまし油系ポリオール、ポリカーボネートポリオール、又は炭化水素系ポリオールなどが挙げられる。これらのポリオール化合物は、１種が単独で、又は２種以上が組み合わされて用いられ得る。耐溶剤性の観点から芳香族を有するポリオール化合物が好ましい。 Examples of the polyol compound include low molecular weight polyols, polyester polyols, polyether polyols, castor oil-based polyols, polycarbonate polyols, and hydrocarbon-based polyols. These polyol compounds may be used alone or in combination of two or more. A polyol compound having an aromatic group is preferred from the viewpoint of solvent resistance.
前記低分子量ポリオールは分子量４００以下のものであり、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、ネオペンチルグリコール、１，３−ブタンジオール、１，４−ブタンジオール、３−メチルペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、２−メチル−１，３−プロパンジオール、ビスフェノールＡ、水添ビスフェノールＡ、シクロヘキサンジメタノール、グリセリン、又はトリメチロールプロパンなどが挙げられる。 The low molecular weight polyol has a molecular weight of 400 or less. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,3-butanediol, , 4-butanediol, 3-methylpentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, cyclohexanedimethanol, glycerin Or trimethylolpropane.
前記ポリエステルポリオールとしては例えば、前記低分子量ポリオールと多価カルボン酸とを反応させてなる水酸基末端エステル化縮合物が挙げられる。前記多価カルボン酸としては、例えば、コハク酸、グルタル酸、アジピン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、テトラヒドロフラン酸、エンドメチンテトラヒドロフラン酸、又はヘキサヒドロフタル酸などが挙げられる。 Examples of the polyester polyol include a hydroxyl-terminated esterified condensate obtained by reacting the low molecular weight polyol with a polyvalent carboxylic acid. Examples of the polyvalent carboxylic acid include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrofuran acid, endomethine tetrahydrofuran acid, and hexahydrophthalic acid. Can be mentioned.
前記ポリエーテルポリオールとしては例えば、ビスフェノールＡなどの前記低分子量ポリオール、ペンタエリスリトール、ソルビトール、又はショ糖などにアルキレンオキサイドを付加重合したものが挙げられる。前記アルキレンオキサイドとしては、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などが挙げられる。 Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide to the low molecular weight polyol such as bisphenol A, pentaerythritol, sorbitol, or sucrose. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like.
前記ひまし油系ポリオールとしては例えば、ひまし油、ひまし油に水素付加した水添ひまし油、ひまし油脂肪酸又はこれに水素付加した水添ひまし油脂肪酸を用いて製造されたポリオールなどが挙げられる。また、ひまし油と他の天然油脂とのエステル交換物、ひまし油と多価アルコールとの反応物、ひまし油脂肪酸と多価アルコールとのエステル化反応物、又はこれらに前記アルキレンオキサイドを付加重合したポリオールなどが挙げられる。 Examples of the castor oil-based polyol include castor oil, hydrogenated castor oil hydrogenated to castor oil, castor oil fatty acid, or polyol produced using hydrogenated castor oil fatty acid hydrogenated thereto. Further, a transesterification product of castor oil and other natural fats and oils, a reaction product of castor oil and polyhydric alcohol, an esterification reaction product of castor oil fatty acid and polyhydric alcohol, or a polyol obtained by addition polymerization of the alkylene oxide to these Can be mentioned.
前記ポリカーボネートポリオールとしては例えば、従来公知のものが挙げられ、該ポリカーボネートポリオールは、例えば、前記低分子量ポリオールとジフェニルカーボネートとの反応により、又は、前記低分子量ポリオールとホスゲンとの反応により得られる。
前記炭化水素系ポリオールとしては例えば、ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリブタジエンポリオール、又は水添ポリイソプレンポリオールなどが挙げられる。
Examples of the polycarbonate polyol include conventionally known ones. The polycarbonate polyol can be obtained, for example, by a reaction between the low molecular weight polyol and diphenyl carbonate or a reaction between the low molecular weight polyol and phosgene.
Examples of the hydrocarbon polyol include polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.
前記イソシアネート化合物としては例えば、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート、および芳香脂肪族ポリイソシアネート等のポリイソシアネートが挙げられる。前記イソシアネート化合物は、単独で、又は２種以上を組み合わされて用いることができる。前記脂肪族ポリイソシアネートとしては、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート、リジ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−ジイソシアネート等が挙げられる。前記脂環族ポリイソシアネートとしては、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、１，４−シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３−ビス（イソシアネートメチル）シクロヘキサン等が挙げられる。前記芳香族ポリイソシアネートとしては、トリレ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、２，４’−ジフェニルメタ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（ＭＤＩ）、４，４’−ジベンジルジイソシアネート、１，５−ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート等が挙げられる。前記芳香脂肪族ポリイソシアネートとしては、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α，α，α，α−テトラメチルキシリレンジイソシアネート等が挙げられる。また、前記イソシアネート化合物は、前記ポリイソシアネートの２量体もしくは３量体、ビューレット化イソシアネート等の変性体、ポリメチレンポリフェニルポリイソシアネート（ポリメリックＭＤＩ）などを用いることができる。尚、これらは、単独で又は２種以上を併用して用いることもできる。 Examples of the isocyanate compound include polyisocyanates such as aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. The said isocyanate compound can be used individually or in combination of 2 or more types. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane- Examples include 1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Is mentioned. Examples of the aromatic polyisocyanate include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1, Examples include 5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate. Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α, α, α, α-tetramethylxylylene diisocyanate. In addition, as the isocyanate compound, a dimer or trimer of the polyisocyanate, a modified product such as a buret isocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), or the like can be used. In addition, these can also be used individually or in combination of 2 or more types.
前記ポリアミン成分は、１級または２級のポリアミンである。かかるポリアミン成分は、上記ポリオール成分と上記ポリイソシアネート成分との反応生成物たるポリウレタンプレポリマー同士を、これを介して反応させるものであり、ポリウレタンプレポリマー同士がポリアミン成分を介して反応することにより、ウレア結合が形成されつつ上記ポリウレタンプレポリマー同士が重合され、これにより、ポリウレタン樹脂が生成される。すなわち、ポリアミン成分は、イソシアネート基と反応し得る第１級アミンまたは第２級アミンの少なくともいずれか１つである。 The polyamine component is a primary or secondary polyamine. Such a polyamine component is a product of reacting polyurethane prepolymers, which are reaction products of the polyol component and the polyisocyanate component, with each other, and the polyurethane prepolymers react with each other via the polyamine component. While the urea bond is formed, the polyurethane prepolymers are polymerized to produce a polyurethane resin. That is, the polyamine component is at least one of a primary amine or a secondary amine that can react with an isocyanate group.
かかるポリアミン成分のうち、ポリアミンとしては、例えば、エチレンジアミン、トリメチレンジアミン、4,4’-ジアミノジフェニルメタン、ピペラジンやイソホロンジアミン等のジアミン、ジエチレントリアミンやジプロピレントリアミン等のトリアミン、トリエチレンテトラミン等のテトラミン等が挙げられる。また、ポリアミン成分は、これらを組み合わせて用いることもできる。 Among such polyamine components, examples of the polyamine include ethylenediamine, trimethylenediamine, 4,4′-diaminodiphenylmethane, diamines such as piperazine and isophoronediamine, triamines such as diethylenetriamine and dipropylenetriamine, and tetramines such as triethylenetetramine. Is mentioned. Moreover, these polyamine components can also be used in combination.
上記ポリウレタン樹脂水分散体は、少なくともポリオール成分とポリイソシアネート成分とを用い、これらからポリウレタン樹脂が生成されればよく、ポリオール成分及びポリイソシアネート成分の他に、その他の成分を用いてポリウレタン樹脂を生成させることもできる。例えば、シランカップリング剤をさらに用いることができる。かかるシランカップリング剤としては、例えば、Ｎ−β（アミノエチル）γ-アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ-アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ-アミノプロピルメチルジメトキシシラン等が挙げられる。
さらに、本発明の水性樹脂組成物には、必要に応じて一般的に使用される各種添加剤を使用することができる。このような添加剤としては、例えば、耐候剤、抗菌剤、抗カビ剤、顔料、充填材、防錆剤、顔料、染料、造膜助剤、無機架橋剤、有機架橋剤（ 例えばブロックドイソシアネート系架橋剤、エポキシ系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、メラミン系架橋剤） 、シランカップリング剤、ブロッキング防止剤、粘度調整剤、レベリング剤、消泡剤、分散安定剤、光安定剤、酸化防止剤、紫外線吸収剤、無機、有機充填剤、可塑剤、滑剤、帯電防止剤等が挙げられる。
The polyurethane resin aqueous dispersion only needs to use at least a polyol component and a polyisocyanate component, and a polyurethane resin may be generated from them. In addition to the polyol component and the polyisocyanate component, other components are used to generate the polyurethane resin. It can also be made. For example, a silane coupling agent can be further used. Examples of such silane coupling agents include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-amino. Examples include propylmethyldimethoxysilane.
Furthermore, in the aqueous resin composition of the present invention, various commonly used additives can be used as necessary. Examples of such additives include weathering agents, antibacterial agents, antifungal agents, pigments, fillers, rust inhibitors, pigments, dyes, film-forming aids, inorganic crosslinking agents, organic crosslinking agents (for example, blocked isocyanates). -Based crosslinking agents, epoxy-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, melamine-based crosslinking agents), silane coupling agents, antiblocking agents, viscosity modifiers, leveling agents, antifoaming agents, dispersion stabilizers, light Stabilizers, antioxidants, ultraviolet absorbers, inorganic and organic fillers, plasticizers, lubricants, antistatic agents and the like can be mentioned.
以下に実施例および比較例について本発明を具体的に説明するが、本発明はこれによって限定するものではない。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.
＜合成例１＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに、ニューポールＢＰ−５Ｐ（三洋化成社製 水酸基価＝２０９ ｍｇＫＯＨ／ｇ）５４１重量部、ピロメリット酸二無水物１０９重量部を仕込み、テトラブチルチタネート３．４重量部を添加し、１１０℃にて２時間反応させ、ポリエーテルエステル化合物 (酸価＝８５．８ｍｇＫＯＨ／ｇ、水酸基価=９４．０ ｍｇＫＯＨ／ｇ)を得た。得られたポリエステルエーテル化合物をメチルエチルケトン（ＭＥＫ）に溶解し、不揮発分７０重量％のポリエーテルエステル化合物１を得た。
＜合成例２＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに、アデカポリエーテルＢＰＸ−１１（ＡＤＥＫＡ社製 水酸基価＝３１２ｍｇＫＯＨ／ｇ）５３８重量部、ピロメリット酸二無水物６９重量部を仕込み、テトラブチルチタネート５．０重量部を添加し、１１０℃にて２時間反応させ、ポリエーテルエステル化合物 (酸価＝１０９．５ｍｇＫＯＨ／ｇ、水酸基価=１２０．５ ｍｇＫＯＨ／ｇ)を得た。得られたポリエステルエーテル化合物をメチルエチルケトン（ＭＥＫ）に溶解し、不揮発分７０重量％のポリエーテルエステル化合物２を得た。
＜合成例３＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに、ポリプロピレングリコール１０００（水酸基価＝１１２ｍｇＫＯＨ／ｇ）６３１重量部、ピロメリット酸二無水物１６３重量部を仕込み、テトラブチルチタネート２．１重量部を添加し、１１０℃にて２時間反応させ、ポリエーテルエステル化合物 (酸価＝５０．４ｍｇＫＯＨ／ｇ、水酸基価=５０．９ ｍｇＫＯＨ／ｇ)を得た。得られたポリエステルエーテル化合物をメチルエチルケトン（ＭＥＫ）に溶解し、不揮発分７０重量％のポリエーテルエステル化合物３を得た。
＜合成例４＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに、ニューポールＢＰ−５Ｐ（三洋化成社製 水酸基価＝２０９ ｍｇＫＯＨ／ｇ）５５０重量部、ビフェニルテトラカルボン酸二無水物１５０重量部を仕込み、テトラブチルチタネート３．５重量部を添加し、１１０℃にて２時間反応させ、ポリエーテルエステル化合物 (酸価＝７１．７ｍｇＫＯＨ／ｇ、水酸基価=８４．１ ｍｇＫＯＨ／ｇ)を得た。得られたポリエステルエーテル化合物をメチルエチルケトン（ＭＥＫ）に溶解し、不揮発分７０重量％のポリエーテルエステル化合物４を得た。
＜合成例５＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに、アデカポリエーテルＢＰＸ−１１（ＡＤＥＫＡ社製 水酸基価＝３１２ｍｇＫＯＨ／ｇ）４９８重量部、ビフェニルテトラカルボン酸二無水物２０２重量部を仕込み、テトラブチルチタネート２．１重量部を添加し、１１０℃にて２時間反応させ、ポリエーテルエステル化合物 (酸価＝１００．２ｍｇＫＯＨ／ｇ、水酸基価=１１１．６ ｍｇＫＯＨ／ｇ)を得た。得られたポリエステルエーテル化合物をメチルエチルケトン（ＭＥＫ）に溶解し、不揮発分７０重量％のポリエーテルエステル化合物５を得た。
＜合成例６＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに、ポリプロピレングリコール１０００（水酸基価＝１１２ｍｇＫＯＨ／ｇ）６１１重量部、ビフェニルテトラカルボン酸二無水物８９重量部を仕込み、テトラブチルチタネート２．１重量部を添加し、１１０℃にて２時間反応させ、ポリエーテルエステル化合物 (酸価＝４５．７ｍｇＫＯＨ／ｇ、水酸基価=４９．２ ｍｇＫＯＨ／ｇ)を得た。得られたポリエステルエーテル化合物をメチルエチルケトン（ＭＥＫ）に溶解し、不揮発分７０重量％のポリエーテルエステル化合物６を得た。
<Synthesis Example 1>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 541 parts by weight of Newpol BP-5P (Hydroxyl value = 209 mgKOH / g, manufactured by Sanyo Chemical Co., Ltd.), pyromellitic dianhydride 109 parts by weight, and 3.4 parts by weight of tetrabutyl titanate were added and reacted at 110 ° C. for 2 hours to obtain a polyetherester compound (acid value = 85.8 mgKOH / g, hydroxyl value = 94.0 mgKOH / g). ) The obtained polyester ether compound was dissolved in methyl ethyl ketone (MEK) to obtain a polyether ester compound 1 having a nonvolatile content of 70% by weight.
<Synthesis Example 2>
A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube was charged with 538 parts by weight of Adeka polyether BPX-11 (hydroxy group value = 312 mgKOH / g, manufactured by ADEKA), pyromellitic dianhydride 69. Charge parts by weight, add 5.0 parts by weight of tetrabutyl titanate, and react at 110 ° C. for 2 hours to obtain a polyetherester compound (acid value = 109.5 mgKOH / g, hydroxyl value = 120.5 mgKOH / g) Got. The obtained polyester ether compound was dissolved in methyl ethyl ketone (MEK) to obtain a polyether ester compound 2 having a nonvolatile content of 70% by weight.
<Synthesis Example 3>
A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube was charged with 631 parts by weight of polypropylene glycol 1000 (hydroxyl value = 112 mgKOH / g) and 163 parts by weight of pyromellitic dianhydride. 2.1 parts by weight of butyl titanate was added and reacted at 110 ° C. for 2 hours to obtain a polyether ester compound (acid value = 50.4 mgKOH / g, hydroxyl value = 50.9 mgKOH / g). The obtained polyester ether compound was dissolved in methyl ethyl ketone (MEK) to obtain a polyether ester compound 3 having a nonvolatile content of 70% by weight.
<Synthesis Example 4>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 550 parts by weight of Newpol BP-5P (Hydroxyl value = 209 mgKOH / g, manufactured by Sanyo Chemical Co., Ltd.), biphenyltetracarboxylic dianhydride 150 parts by weight of the product, 3.5 parts by weight of tetrabutyl titanate were added and reacted at 110 ° C. for 2 hours to obtain a polyether ester compound (acid value = 71.7 mgKOH / g, hydroxyl value = 84.1 mgKOH / g) was obtained. The obtained polyester ether compound was dissolved in methyl ethyl ketone (MEK) to obtain a polyether ester compound 4 having a nonvolatile content of 70% by weight.
<Synthesis Example 5>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, ADEKA polyether BPX-11 (ADEKA, hydroxyl value = 312 mgKOH / g), 498 parts by weight, biphenyltetracarboxylic dianhydride Charge 202 parts by weight, add 2.1 parts by weight of tetrabutyl titanate, and react at 110 ° C. for 2 hours to obtain a polyetherester compound (acid value = 100.2 mgKOH / g, hydroxyl value = 111.6 mgKOH / g). ) The obtained polyester ether compound was dissolved in methyl ethyl ketone (MEK) to obtain a polyether ester compound 5 having a nonvolatile content of 70% by weight.
<Synthesis Example 6>
A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube was charged with 611 parts by weight of polypropylene glycol 1000 (hydroxyl value = 112 mgKOH / g) and 89 parts by weight of biphenyltetracarboxylic dianhydride, 2.1 parts by weight of tetrabutyl titanate was added and reacted at 110 ° C. for 2 hours to obtain a polyether ester compound (acid value = 45.7 mgKOH / g, hydroxyl value = 49.2 mgKOH / g). The obtained polyester ether compound was dissolved in methyl ethyl ketone (MEK) to obtain a polyether ester compound 6 having a nonvolatile content of 70% by weight.
＜実施例１＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに＜合成例１＞で得られたポリエーテルエステル化合物１ を３３．３部、ポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）４１．５重量部、トリメチロールプロパン３．１重量部、ジシクロヘキシルメタンジイソシアネート３２．０重量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。次に、この溶液を４５℃まで冷却し、トリエチルアミン３．６重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体にエチレンジアミン２．３重量部を水１０重量部に溶解した水溶液を添加して１時間反応させた後、反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体１を得た。
＜実施例２＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに＜合成例１＞で得られたポリエーテルエステル化合物１ を６６．６部、ポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）１６．８重量部、トリメチロールプロパン３．１重量部、ジシクロヘキシルメタンジイソシアネート３３．５量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。次に、この溶液を４５℃まで冷却し、トリエチルアミン７．１重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体にエチレンジアミン２．３重量部を水１０重量部に溶解した水溶液を添加して１時間反応させた後、反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体２を得た。
＜実施例３＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに＜合成例2＞で得られたポリエーテルエステル化合物２ を２６．１部、ポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）４５．９重量部、トリメチロールプロパン３．１重量部、ジシクロヘキシルメタンジイソシアネート３２．７重量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。次に、この溶液を４５℃まで冷却し、トリエチルアミン３．６重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体にエチレンジアミン２．３重量部を水１０重量部に溶解した水溶液を添加して１時間反応させた後、反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体３を得た。
＜実施例４＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに＜合成例3＞で得られたポリエーテルエステル化合物３ を５６．７部、ポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）２７．６重量部、トリメチロールプロパン３．１重量部、ジシクロヘキシルメタンジイソシアネート２９．６重量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。次に、この溶液を４５℃まで冷却し、トリエチルアミン３．６重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体にエチレンジアミン２．３重量部を水１０重量部に溶解した水溶液を添加して１時間反応させた後、反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体４を得た。
＜実施例５＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに＜合成例4＞で得られたポリエーテルエステル化合物４ ３９．８部、ポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）３７．２重量部、トリメチロールプロパン３．１重量部、ジシクロヘキシルメタンジイソシアネート３１．８重量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。次に、この溶液を４５℃まで冷却し、トリエチルアミン３．６重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体にエチレンジアミン２．３重量部を水１０重量部に溶解した水溶液を添加して１時間反応させた後、反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体５を得た。
＜実施例６＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに＜合成例5＞で得られたポリエーテルエステル化合物５ ２８．５部、ポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）４４．４重量部、トリメチロールプロパン３．８重量部、ジシクロヘキシルメタンジイソシアネート３２．５重量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液の不揮発分３．６重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体にエチレンジアミン２．３重量部を水１０重量部に溶解した水溶液を添加して１時間反応させた後、反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体６を得た。
＜実施例７＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコに＜合成例6＞で得られたポリエーテルエステル化合物６ ６２．５部、ポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）２３．８重量部、トリメチロールプロパン３．１重量部、ジシクロヘキシルメタンジイソシアネート２９．４重量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。次に、この溶液を４５℃まで冷却し、トリエチルアミン３．６重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体にエチレンジアミン２．３重量部を水１０重量部に溶解した水溶液を添加して１時間反応させた後、反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体７を得た。
＜比較例１＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコにポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）３８．９重量部、ポリエーテルポリオール（アデカポリエーテルＢＰＸ−１１、ＡＤＥＫＡ社製）９．７重量部、トリメチロールプロパン３．１重量部、ジメチロールプロピオン酸５．０重量部、ジシクロヘキシルメタンジイソシアネート４３．３重量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。次に、この溶液を４５℃まで冷却し、トリエチルアミン３．８重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体にエチレンジアミン２．３重量部を水１０重量部に溶解した水溶液を添加して１時間反応させた後、反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体８を得た。
＜比較例２＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコにポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）３０．４重量部、ポリエーテルポリオール（アデカポリエーテルＢＰＸ−１１、ＡＤＥＫＡ社製）７．６重量部、トリメチロールプロパン３．１重量部、ジメチロールプロピオン酸５．０重量部、ジシクロヘキシルメタンジイソシアネート４９．３重量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。次に、この溶液を４５℃まで冷却し、トリエチルアミン７．２重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体にエチレンジアミン２．３重量部を水１０重量部に溶解した水溶液を添加して１時間反応させた後、反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体９を得た。
＜比較例３＞
撹拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコにポリエステルポリオール（テスラック２４７７、日立化成ポリマー社製）３８．９重量部、トリメチロールプロパン３．１重量部、ジメチロールプロピオン酸５．０重量部、ジシクロヘキシルメタンジイソシアネート４３．３重量部およびメチルエチルケトン７０重量部を加え、７５℃で４時間反応させてイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。更に、この溶液を４５℃まで冷却し、メチルエチルケトンオキシム４．８重量部を加え５０℃で不揮発分に対する遊離のイソシアネート基含有量は０％になるように反応させた。次にトリエチルアミン３．８重量部を添加した後、水３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体から反応溶媒であるメチルエチルケトンを減圧留去することにより、不揮発分濃度が３０重量％であるポリウレタン樹脂水分散体１０を得た。
<Example 1>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 33.3 parts of the polyether ester compound 1 obtained in <Synthesis Example 1>, polyester polyol (Teslac 2477, Hitachi Chemical) 41.5 parts by weight, 3.1 parts by weight of trimethylolpropane, 32.0 parts by weight of dicyclohexylmethane diisocyanate and 70 parts by weight of methyl ethyl ketone, and reacted at 75 ° C. for 4 hours to be methyl ethyl ketone as an isocyanate group-terminated urethane prepolymer. A solution was obtained. The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%. Next, this solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added, and then emulsified and dispersed using a homogenizer while gradually adding 300 parts by weight of water. An aqueous solution in which 2.3 parts by weight of ethylenediamine was dissolved in 10 parts by weight of water was added to the resulting emulsified dispersion and reacted for 1 hour, and then methyl ethyl ketone as a reaction solvent was distilled off under reduced pressure to reduce the concentration of non-volatile components. A polyurethane resin aqueous dispersion 1 of 30% by weight was obtained.
<Example 2>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 66.6 parts of the polyether ester compound 1 obtained in <Synthesis Example 1>, polyester polyol (Teslac 2477, Hitachi Chemical) 16.8 parts by weight, 3.1 parts by weight of trimethylolpropane, 33.5 parts by weight of dicyclohexylmethane diisocyanate and 70 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain methyl ethyl ketone of an isocyanate group-terminated urethane prepolymer. A solution was obtained. The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%. Next, this solution was cooled to 45 ° C., 7.1 parts by weight of triethylamine was added, and then emulsified and dispersed using a homogenizer while gradually adding 300 parts by weight of water. An aqueous solution in which 2.3 parts by weight of ethylenediamine was dissolved in 10 parts by weight of water was added to the resulting emulsified dispersion and reacted for 1 hour, and then methyl ethyl ketone as a reaction solvent was distilled off under reduced pressure to reduce the concentration of non-volatile components. A polyurethane resin aqueous dispersion 2 of 30% by weight was obtained.
<Example 3>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 26.1 parts of the polyether ester compound 2 obtained in <Synthesis Example 2>, polyester polyol (Teslac 2477, Hitachi Chemical) 45.9 parts by weight, 3.1 parts by weight of trimethylolpropane, 32.7 parts by weight of dicyclohexylmethane diisocyanate and 70 parts by weight of methyl ethyl ketone, and reacted at 75 ° C. for 4 hours to give methyl ethyl ketone as an isocyanate group-terminated urethane prepolymer. A solution was obtained. The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%. Next, this solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added, and then emulsified and dispersed using a homogenizer while gradually adding 300 parts by weight of water. An aqueous solution in which 2.3 parts by weight of ethylenediamine was dissolved in 10 parts by weight of water was added to the resulting emulsified dispersion and reacted for 1 hour, and then methyl ethyl ketone as a reaction solvent was distilled off under reduced pressure to reduce the concentration of non-volatile components. A polyurethane resin aqueous dispersion 3 of 30% by weight was obtained.
<Example 4>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 56.7 parts of the polyether ester compound 3 obtained in <Synthesis Example 3>, polyester polyol (Teslac 2477, Hitachi Chemical) 27.6 parts by weight, 3.1 parts by weight of trimethylolpropane, 29.6 parts by weight of dicyclohexylmethane diisocyanate and 70 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to give methyl ethyl ketone as an isocyanate group-terminated urethane prepolymer. A solution was obtained. The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%. Next, this solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added, and then emulsified and dispersed using a homogenizer while gradually adding 300 parts by weight of water. An aqueous solution in which 2.3 parts by weight of ethylenediamine was dissolved in 10 parts by weight of water was added to the resulting emulsified dispersion and reacted for 1 hour, and then methyl ethyl ketone as a reaction solvent was distilled off under reduced pressure to reduce the concentration of non-volatile components. A polyurethane resin aqueous dispersion 4 of 30% by weight was obtained.
<Example 5>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 39.8 parts of the polyether ester compound 4 obtained in <Synthesis Example 4>, polyester polyol (Teslac 2477, Hitachi Chemical Co., Ltd.) 37.2 parts by weight, 3.1 parts by weight of trimethylolpropane, 31.8 parts by weight of dicyclohexylmethane diisocyanate and 70 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer. Got. The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%. Next, this solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added, and then emulsified and dispersed using a homogenizer while gradually adding 300 parts by weight of water. An aqueous solution in which 2.3 parts by weight of ethylenediamine was dissolved in 10 parts by weight of water was added to the resulting emulsified dispersion and reacted for 1 hour, and then methyl ethyl ketone as a reaction solvent was distilled off under reduced pressure to reduce the concentration of non-volatile components. A polyurethane resin aqueous dispersion 5 of 30% by weight was obtained.
<Example 6>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 28.5 parts of the polyether ester compound 5 obtained in <Synthesis Example 5>, polyester polyol (Teslac 2477, Hitachi Chemical Co., Ltd.) 44.4 parts by weight, 3.8 parts by weight of trimethylolpropane, 32.5 parts by weight of dicyclohexylmethane diisocyanate and 70 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer. Got. After adding 3.6 parts by weight of the nonvolatile content of this solution, emulsification and dispersion were performed using a homogenizer while gradually adding 300 parts by weight of water. An aqueous solution in which 2.3 parts by weight of ethylenediamine was dissolved in 10 parts by weight of water was added to the resulting emulsified dispersion and reacted for 1 hour, and then methyl ethyl ketone as a reaction solvent was distilled off under reduced pressure to reduce the concentration of non-volatile components. A polyurethane resin aqueous dispersion 6 of 30% by weight was obtained.
<Example 7>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 62.5 parts of the polyether ester compound 6 obtained in <Synthesis Example 6>, polyester polyol (Teslac 2477, Hitachi Chemical Co., Ltd.) 23.8 parts by weight, 3.1 parts by weight of trimethylolpropane, 29.4 parts by weight of dicyclohexylmethane diisocyanate and 70 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to give a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer. Got. The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%. Next, this solution was cooled to 45 ° C., 3.6 parts by weight of triethylamine was added, and then emulsified and dispersed using a homogenizer while gradually adding 300 parts by weight of water. An aqueous solution in which 2.3 parts by weight of ethylenediamine was dissolved in 10 parts by weight of water was added to the resulting emulsified dispersion and reacted for 1 hour, and then methyl ethyl ketone as a reaction solvent was distilled off under reduced pressure to reduce the concentration of non-volatile components. A polyurethane resin aqueous dispersion 7 of 30% by weight was obtained.
<Comparative Example 1>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 38.9 parts by weight of polyester polyol (Teslac 2477, manufactured by Hitachi Chemical Co., Ltd.), polyether polyol (ADEKA polyether BPX-11, ADEKA) 9.7 parts by weight, 3.1 parts by weight of trimethylolpropane, 5.0 parts by weight of dimethylolpropionic acid, 43.3 parts by weight of dicyclohexylmethane diisocyanate and 70 parts by weight of methyl ethyl ketone were added, and the mixture was added at 75 ° C. for 4 hours. Reaction was performed to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer. The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%. Next, this solution was cooled to 45 ° C., 3.8 parts by weight of triethylamine was added, and then emulsified and dispersed using a homogenizer while gradually adding 300 parts by weight of water. An aqueous solution in which 2.3 parts by weight of ethylenediamine was dissolved in 10 parts by weight of water was added to the resulting emulsified dispersion and reacted for 1 hour, and then methyl ethyl ketone as a reaction solvent was distilled off under reduced pressure to reduce the concentration of non-volatile components. A polyurethane resin aqueous dispersion 8 of 30% by weight was obtained.
<Comparative example 2>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 30.4 parts by weight of polyester polyol (Teslac 2477, manufactured by Hitachi Chemical Co., Ltd.), polyether polyol (Adeka polyether BPX-11, ADEKA) 7.6 parts by weight, trimethylolpropane 3.1 parts by weight, dimethylolpropionic acid 5.0 parts by weight, dicyclohexylmethane diisocyanate 49.3 parts by weight and methyl ethyl ketone 70 parts by weight were added, and 75 ° C. for 4 hours. Reaction was performed to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer. The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%. Next, this solution was cooled to 45 ° C., 7.2 parts by weight of triethylamine was added, and then emulsified and dispersed using a homogenizer while gradually adding 300 parts by weight of water. An aqueous solution in which 2.3 parts by weight of ethylenediamine was dissolved in 10 parts by weight of water was added to the resulting emulsified dispersion and reacted for 1 hour, and then methyl ethyl ketone as a reaction solvent was distilled off under reduced pressure to reduce the concentration of non-volatile components. A polyurethane resin aqueous dispersion 9 of 30% by weight was obtained.
<Comparative Example 3>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 38.9 parts by weight of polyester polyol (Teslac 2477, manufactured by Hitachi Chemical Co., Ltd.), 3.1 parts by weight of trimethylolpropane, dimethylol 5.0 parts by weight of propionic acid, 43.3 parts by weight of dicyclohexylmethane diisocyanate and 70 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer. Furthermore, this solution was cooled to 45 ° C., 4.8 parts by weight of methyl ethyl ketone oxime was added, and the mixture was reacted at 50 ° C. so that the content of free isocyanate groups with respect to the nonvolatile content was 0%. Next, 3.8 parts by weight of triethylamine was added, and then emulsified and dispersed using a homogenizer while gradually adding 300 parts by weight of water. Methyl ethyl ketone as a reaction solvent was distilled off from the obtained emulsified dispersion under reduced pressure to obtain a polyurethane resin aqueous dispersion 10 having a nonvolatile content concentration of 30% by weight.
（試験板の評価）
＜試験板の作製＞
上記のように得られたポリウレタン樹脂水分散体を、膜厚２００μｍとなるようにテフロン（登録商標）コーティングシャーレに投入し、８０℃で６時間乾燥し、これを所定の大きさ(２ｃｍ×４ｃｍ)に切断することにより評価サンプルを作製した。
（１）耐水性
上記試験皮膜を所定の大きさ(２ｃｍ×４ｃｍ)に切断することにより評価サンプルを作製した。試験液として、蒸留水を使用した。試験片を４０℃の試験液に２４時間浸漬し、初期の面積（２×４ｃｍ２）に対する面積増加率を下記式により求めた。得られた面積増加率が低いほど耐水性が良好であると評価した。
面積増加率＝(浸漬後の面積―初期の面積)／初期の面積×１００
（２）耐溶媒性
上記試験皮膜を所定の大きさ(２ｃｍ×４ｃｍ)に切断することにより評価サンプルを作製した。試験液として、酢酸エチル/トルエン＝1：1の混合溶液を使用した。試験片を４０℃の試験液に２４時間浸漬し、初期の面積（２×４ｃｍ２）に対する面積増加率を下記式により求めた。得られた面積増加率が低いほど耐溶剤性が良好であると評価した。
面積増加率＝(浸漬後の面積―初期の面積)／初期の面積×１００
（３）密着性
基材（ＰＥＴフィルム（コロナ放電処理・未処理）及びＯＰＰフィルム（コロナ放電処理・未処理））をイソプロピルアルコールを用いて脱脂した。次に、上記実施例及び比較例で得られたポリウレタン樹脂水分散体をバーコーターで、乾燥膜厚５μｍになるように塗布し、雰囲気温度２８０℃の熱風乾燥炉を用いて１０分間乾燥し試験片を作製し、１ｍｍ碁盤目試験を実施した。
評価＝１００区画中の残存率
（４）引張特性
上記皮膜を所定の大きさに切断することにより評価サンプルを作製した。
試験条件はＪＩＳ−Ｋ−６３０１に準じて、引張速度１００ｍｍ／ｍｉｎで測定した。
(Evaluation of test plate)
<Preparation of test plate>
The polyurethane resin aqueous dispersion obtained as described above was put into a Teflon (registered trademark) coating petri dish so as to have a film thickness of 200 μm, dried at 80 ° C. for 6 hours, and then dried to a predetermined size (2 cm × 4 cm). The evaluation sample was produced by cutting into 3).
(1) Water resistance An evaluation sample was prepared by cutting the test film into a predetermined size (2 cm × 4 cm). Distilled water was used as a test solution. The test piece was immersed in a test solution at 40 ° C. for 24 hours, and the area increase rate relative to the initial area (2 × 4 cm 2) was determined by the following formula. The lower the area increase rate obtained, the better the water resistance.
Area increase rate = (area after immersion−initial area) / initial area × 100
(2) Solvent resistance An evaluation sample was prepared by cutting the test film into a predetermined size (2 cm × 4 cm). A mixed solution of ethyl acetate / toluene = 1: 1 was used as a test solution. The test piece was immersed in a test solution at 40 ° C. for 24 hours, and the area increase rate relative to the initial area (2 × 4 cm 2) was determined by the following formula. The lower the area increase rate obtained, the better the solvent resistance.
Area increase rate = (area after immersion−initial area) / initial area × 100
(3) Adhesiveness The base materials (PET film (corona discharge treatment / untreated) and OPP film (corona discharge treatment / untreated)) were degreased using isopropyl alcohol. Next, the polyurethane resin aqueous dispersions obtained in the above examples and comparative examples were applied with a bar coater so as to have a dry film thickness of 5 μm, and dried for 10 minutes using a hot air drying furnace with an atmospheric temperature of 280 ° C. A piece was made and a 1 mm cross cut test was performed.
Evaluation = Residual ratio in 100 compartments (4) Tensile properties An evaluation sample was prepared by cutting the film into a predetermined size.
Test conditions were measured according to JIS-K-6301 at a tensile speed of 100 mm / min.
表１から明らかなように、酸価をジメチロールプロピオン酸で調整した比較例１は密着性および引張特性が悪い。ジメチロールプロピオン酸を増やして酸価を上げた比較例２はＰＥＴとの密着性および引張特性が悪い。末端をオキシムでブロックし、分子量を抑制した比較例３は耐水性、耐溶剤性および引張特性が悪い。 As is apparent from Table 1, Comparative Example 1 in which the acid value was adjusted with dimethylolpropionic acid had poor adhesion and tensile properties. Comparative Example 2 in which the acid value was increased by increasing dimethylolpropionic acid has poor adhesion to PET and tensile properties. Comparative Example 3 in which the terminal is blocked with oxime and the molecular weight is suppressed has poor water resistance, solvent resistance and tensile properties.
本発明のポリウレタン樹脂水分散体、該組成物を用いた硬化物は、建築内装、皮革、金属、木材、プラスチックフィルムなどの水性被覆剤として好適に使用できる。 The aqueous polyurethane resin dispersion of the present invention and a cured product using the composition can be suitably used as an aqueous coating agent for architectural interiors, leather, metals, wood, plastic films and the like.
Claims (3)
（Ａ）ポリオキシアルキレン誘導体
（Ｂ）４価のカルボン酸、その塩および４価のカルボン酸無水物から選ばれる１以上の化合物 A polyurethane resin aqueous dispersion obtained by using a polyether polyester compound obtained by reacting at least the following (A) and (B).
(A) One or more compounds selected from (A) polyoxyalkylene derivatives (B) tetravalent carboxylic acids, salts thereof and tetravalent carboxylic anhydrides
A cured product obtained by curing the aqueous polyurethane resin dispersion according to claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018180443A1 (en) * | 2017-03-30 | 2018-10-04 | 旭化成株式会社 | Polyisocyanate curing agent, aqueous coating composition, coating film, and coated article |
| JP2019218536A (en) * | 2018-06-15 | 2019-12-26 | 保土谷化学工業株式会社 | Polyol for crosslinkable polyurethane resin composition, and crosslinkable polyurethane resin |
| WO2020175105A1 (en) * | 2019-02-26 | 2020-09-03 | 東レ株式会社 | Polyalkylene glycol copolymer, method for producing same, and resin composition incorporating polyalkylene glycol copolymer |
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| JPH07165860A (en) * | 1991-12-09 | 1995-06-27 | Basf Ag | Water-base polyurethane dispersion and object coated with it |
| JP2013060582A (en) * | 2011-08-23 | 2013-04-04 | Sanyo Chem Ind Ltd | Polyurethane resin aqueous dispersion |
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| JPH07165860A (en) * | 1991-12-09 | 1995-06-27 | Basf Ag | Water-base polyurethane dispersion and object coated with it |
| JPH06184485A (en) * | 1992-12-18 | 1994-07-05 | Toyo Ink Mfg Co Ltd | Aqueous printing ink |
| JP2013060582A (en) * | 2011-08-23 | 2013-04-04 | Sanyo Chem Ind Ltd | Polyurethane resin aqueous dispersion |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018180443A1 (en) * | 2017-03-30 | 2018-10-04 | 旭化成株式会社 | Polyisocyanate curing agent, aqueous coating composition, coating film, and coated article |
| JP2019218536A (en) * | 2018-06-15 | 2019-12-26 | 保土谷化学工業株式会社 | Polyol for crosslinkable polyurethane resin composition, and crosslinkable polyurethane resin |
| JP7271325B2 (en) | 2018-06-15 | 2023-05-11 | 保土谷化学工業株式会社 | Polyol and crosslinkable polyurethane resin for crosslinkable polyurethane resin composition |
| WO2020175105A1 (en) * | 2019-02-26 | 2020-09-03 | 東レ株式会社 | Polyalkylene glycol copolymer, method for producing same, and resin composition incorporating polyalkylene glycol copolymer |
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