JP2008037987A - Aqueous polyurethane composition - Google Patents
Aqueous polyurethane composition Download PDFInfo
- Publication number
- JP2008037987A JP2008037987A JP2006213078A JP2006213078A JP2008037987A JP 2008037987 A JP2008037987 A JP 2008037987A JP 2006213078 A JP2006213078 A JP 2006213078A JP 2006213078 A JP2006213078 A JP 2006213078A JP 2008037987 A JP2008037987 A JP 2008037987A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate diol
- aqueous polyurethane
- formula
- polyurethane composition
- isocyanate
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 19
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 150000002009 diols Chemical class 0.000 claims description 65
- 239000004417 polycarbonate Substances 0.000 claims description 51
- 229920000515 polycarbonate Polymers 0.000 claims description 50
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- -1 coatings Substances 0.000 abstract description 23
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000003973 paint Substances 0.000 abstract description 10
- 230000000704 physical effect Effects 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 5
- 239000000839 emulsion Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 230000007062 hydrolysis Effects 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 229920005749 polyurethane resin Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 5
- 229940046892 lead acetate Drugs 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 238000001577 simple distillation Methods 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 230000000397 acetylating effect Effects 0.000 description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000002649 leather substitute Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- 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
- WRIFCFZXLZGSGD-UHFFFAOYSA-N 1-(dimethylamino)-2-methylpropan-1-ol Chemical compound CC(C)C(O)N(C)C WRIFCFZXLZGSGD-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- ZJWDJIVISLUQQZ-UHFFFAOYSA-N 2,4-dimethylpentane-1,5-diol Chemical compound OCC(C)CC(C)CO ZJWDJIVISLUQQZ-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- AJKXDPSHWRTFOZ-UHFFFAOYSA-N 2-ethylhexane-1,6-diol Chemical compound CCC(CO)CCCCO AJKXDPSHWRTFOZ-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
- XWFCJSXTVSOIDN-UHFFFAOYSA-N 2-propan-2-ylbutane-1,4-diol Chemical compound CC(C)C(CO)CCO XWFCJSXTVSOIDN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JIRLWRUWVNHTQG-UHFFFAOYSA-N 3,4-diaminobutane-1-sulfonic acid Chemical compound NCC(N)CCS(O)(=O)=O JIRLWRUWVNHTQG-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- XJIIBKORMYCKON-UHFFFAOYSA-N 3,6-diamino-2-methylbenzenesulfonic acid Chemical compound CC1=C(N)C=CC(N)=C1S(O)(=O)=O XJIIBKORMYCKON-UHFFFAOYSA-N 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- OVDQEUFSGODEBT-UHFFFAOYSA-N 4-methyl-1,3-dioxan-2-one Chemical compound CC1CCOC(=O)O1 OVDQEUFSGODEBT-UHFFFAOYSA-N 0.000 description 1
- AUXJVUDWWLIGRU-UHFFFAOYSA-N 4-propyl-1,3-dioxolan-2-one Chemical compound CCCC1COC(=O)O1 AUXJVUDWWLIGRU-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- YUEDZVRMWQBEPT-UHFFFAOYSA-N CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O Chemical compound CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O YUEDZVRMWQBEPT-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- ASHMBQUGLGIKAT-UHFFFAOYSA-L [Li+].[OH-].[OH-].[K+] Chemical compound [Li+].[OH-].[OH-].[K+] ASHMBQUGLGIKAT-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- QVFOGJXHRGAFSH-UHFFFAOYSA-N acetic acid;1-dodecoxydodecane Chemical compound CC(O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC QVFOGJXHRGAFSH-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- IVHKZGYFKJRXBD-UHFFFAOYSA-N amino carbamate Chemical class NOC(N)=O IVHKZGYFKJRXBD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-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
- YVIGPQSYEAOLAD-UHFFFAOYSA-L disodium;dodecyl phosphate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOP([O-])([O-])=O YVIGPQSYEAOLAD-UHFFFAOYSA-L 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 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
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Abstract
Description
本発明は、耐薬品性、耐加水分解性、耐候性、柔軟性、密着性など物性バランスに優れた、塗料、コーティング材、接着剤、粘着剤などの用途に使用される、水性ポリウレタン組成物に関する。 The present invention is an aqueous polyurethane composition having excellent physical property balance such as chemical resistance, hydrolysis resistance, weather resistance, flexibility, and adhesion, and used for applications such as paints, coating materials, adhesives, and pressure-sensitive adhesives. About.
ポリウレタンエマルジョンは、耐摩耗性、接着性、非粘着性、ゴム弾性を有する塗膜を与えることより、床剤、壁剤、自動車などに用いられる塗料、あるいは塩化ビニール、ABS樹脂、金属、ガラス、木材などに用いられる接着剤、さらには人工皮革、合成皮革などに用いられるコーティング剤として広く用いられている。 Polyurethane emulsion provides a coating film having abrasion resistance, adhesiveness, non-tackiness, rubber elasticity, floor paint, wall agent, paint used for automobiles, etc., or vinyl chloride, ABS resin, metal, glass, It is widely used as an adhesive used for wood and the like, and further as a coating agent used for artificial leather, synthetic leather and the like.
しかしながら、溶剤系のポリウレタン樹脂から得られる性能と比較して、エマルジョンから得られる塗膜の物性は十分とは言えなかった。特に、ポリエステルポリオールを用いたポリウレタンエマルジョンの場合、塗膜の耐加水分解性に問題があることに加え、エマルジョンの貯蔵中に分子量が低下するという問題も発生した。また、ポリエーテルポリオールを用いた場合、耐熱性が問題になったり、例えば人工皮革に用いた時に耐摩耗性が十分に得られないといった問題があった。耐加水分解、耐熱性、耐摩耗性などの問題を解決するため、ポリカーボネートジオールを用いたポリウレタンエマルジョンが開示されてきた。有機ジイソシアネート、非結晶性ポリカーボネートジオール、および1個の親水性中心と少なくとも2個のイソシアネート反応性の基を有する化合物からなるウレタンプレポリマーと鎖延長剤との反応生成物からなる、耐加水分解性、耐久性、低温風合性に優れた塗膜を与えるポリウレタンディスパージョンが開示されている(特許文献1参照)。数平均分子量500〜5000のポリカーボネートジオール、鎖延長剤、有機ジイソシアネート、中和剤からなる水系ポリウレタン樹脂において、該ポリカーボネートジオールがカルボン酸導入ポリカーボネートジオールを含有することを特徴とする水性ポリウレタン系樹脂組成物を、および該水性ポリウレタン系樹脂組成物を用いた塗料が開示されている(特許文献2参照)。ポリエーテルポリオール、ポリカーボネートジオールから選択されるポリオール、鎖延長剤、カルボキシル基および活性水素基を含有する化合物、有機ポリイソシアネート、中和剤を反応させて得られるポリウレタン系ポリマーの水系エマルジョンであって、該水系エマルジョンの最低成膜温度が35℃未満であり、該ポリマーの測定温度25℃における乾式フィルムの鉛筆引っ掻き値、引張試験における破断時の強度、伸びが、それぞれ2B以上、1〜120MPa、100〜1500%であることを特徴とする水性塗料用ポリウレタン系エマルジョンが開示されている(特許文献3参照)。ジイソシアネートを必須成分とし、他のポリイソシアネート化合物を任意成分としてなるポリイソシアネート成分、平均分子量500〜50000のポリカーボネートジオールとカルボキシル基含有ジオールを必須成分とし、他のポリオール化合物を任意成分としてなるポリオール成分、モノアミン化合物を必須成分とし、ジアミン化合物を任意成分としてなるアミン成分、カルボキシル基中和剤成分および水から得られる水分散型ポリウレタン組成物、および該水分散型ポリウレタン組成物を用いた自動車用塗料が開示されている(特許文献4参照)。末端の少なくとも一部がイソシアネート基であるウレタンプレポリマーから得られるウレタン樹脂、および水性分散媒からなるウレタン樹脂エマルションであって、該ポリウレタン樹脂が、該ポリウレタン樹脂の重量に基づき0.5〜1.0重量%のカルボキシル基、2〜8重量%のウレタン基および0.7〜1.1重量%のウレア基を含有し、該ポリウレタン樹脂の平均粒子径が10〜500nmであるポリウレタン樹脂エマルションが開示されている(特許文献5参照)。 However, the physical properties of the coating film obtained from the emulsion were not sufficient as compared with the performance obtained from the solvent-based polyurethane resin. In particular, in the case of a polyurethane emulsion using a polyester polyol, there is a problem that the molecular weight decreases during storage of the emulsion in addition to the problem of hydrolysis resistance of the coating film. In addition, when polyether polyol is used, there is a problem that heat resistance becomes a problem, or wear resistance cannot be sufficiently obtained when used for, for example, artificial leather. In order to solve problems such as hydrolysis resistance, heat resistance and abrasion resistance, polyurethane emulsions using polycarbonate diol have been disclosed. Hydrolysis resistance comprising a reaction product of an organic diisocyanate, an amorphous polycarbonate diol, and a urethane prepolymer comprising a compound having one hydrophilic center and at least two isocyanate-reactive groups and a chain extender A polyurethane dispersion that gives a coating film excellent in durability and low-temperature texture is disclosed (see Patent Document 1). An aqueous polyurethane resin composition comprising a polycarbonate diol having a number average molecular weight of 500 to 5,000, a chain extender, an organic diisocyanate, and a neutralizing agent, wherein the polycarbonate diol contains a carboxylic acid-introduced polycarbonate diol. And a paint using the aqueous polyurethane resin composition is disclosed (see Patent Document 2). Water-based emulsion of polyurethane polymer obtained by reacting polyether polyol, polyol selected from polycarbonate diol, chain extender, compound containing carboxyl group and active hydrogen group, organic polyisocyanate, neutralizing agent, The minimum film-forming temperature of the water-based emulsion is less than 35 ° C., the pencil scratch value of the dry film at the measurement temperature of 25 ° C., the strength and elongation at break in the tensile test are 2B or more, 1 to 120 MPa, 100 A polyurethane-based emulsion for water-based paints characterized by ˜1500% is disclosed (see Patent Document 3). Polyisocyanate component comprising diisocyanate as an essential component and other polyisocyanate compound as an optional component, a polycarbonate diol having an average molecular weight of 500 to 50000 and a carboxyl group-containing diol as essential components, and a polyol component comprising other polyol compound as an optional component, A water-dispersed polyurethane composition obtained from an amine component having a monoamine compound as an essential component and a diamine compound as an optional component, a carboxyl group neutralizing agent component and water, and an automotive paint using the water-dispersed polyurethane composition It is disclosed (see Patent Document 4). A urethane resin emulsion comprising a urethane resin obtained from a urethane prepolymer in which at least a part of the terminal is an isocyanate group and an aqueous dispersion medium, wherein the polyurethane resin is 0.5 to 1. A polyurethane resin emulsion containing 0% by weight of carboxyl groups, 2-8% by weight of urethane groups and 0.7-1.1% by weight of urea groups, and having an average particle size of the polyurethane resin of 10 to 500 nm is disclosed. (See Patent Document 5).
しかしながら、上記に示すポリウレタンエマルジョンを用いた場合、耐油性、耐汗性、耐加水分解性、耐候性、柔軟性、密着性などの物性をバランス良く付与することは出来なかった。
本発明は、耐油性、耐汗性、耐加水分解性、耐候性、柔軟性、密着性など物性バランスに優れた、塗料、コーティング材、接着剤、粘着剤などの用途に使用される水性ポリウレタン組成物を提供することを目的とする。 The present invention is a water-based polyurethane used for applications such as paints, coating materials, adhesives, pressure-sensitive adhesives, etc., which has an excellent balance of physical properties such as oil resistance, sweat resistance, hydrolysis resistance, weather resistance, flexibility and adhesion. An object is to provide a composition.
本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、特定のポリカーボネートジオールを用いることにより上記の問題点を解決できることを見出し、本発明をなすに至った。 As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by using a specific polycarbonate diol, and has led to the present invention.
すなわち本発明は、
(1)(a)有機イソシアネート、(b)ポリカーボネートジオール、および(c)1個の親水性中心と少なくとも2個のイソシアネート反応性の基を有する化合物からなるウレタンプレポリマーと鎖延長剤との反応生成物からなり、(b)のポリカーボネートジオールが、下記式(A)と下記式(B)の繰り返し単位を含み、末端基が水酸基であり、(A)と(B)の割合がモル比率で99:1〜1:99で、数平均分子量が300〜10000のポリカーボネートジオールであることを特徴とする水性ポリウレタン組成物、
(式中、R1は、2−メチル−1,3プロパンジオールに由来するアルキレン基を除く、炭素数2〜20のアルキレン基を表す。)
(2)上記式(B)中のR1が下記式(C)で表されることを特徴とする(1)に記載の水性ポリウレタン組成物。
(CH2)n (C)
(式中、nは、2〜10の整数を表す。)
(3)上記式(B)中のR1が下記式(D)で表されることを特徴とする(1)に記載の水性ポリウレタン組成物。
(CH2)m (D)
(式中、mは、4または6の整数を表す。)に関するものである。
That is, the present invention
Reaction of urethane prepolymer comprising (1) (a) organic isocyanate, (b) polycarbonate diol, and (c) a compound having one hydrophilic center and at least two isocyanate-reactive groups with a chain extender The polycarbonate diol of (b) contains a repeating unit of the following formula (A) and the following formula (B), the terminal group is a hydroxyl group, and the ratio of (A) and (B) is a molar ratio. 99: 1-1: 99, an aqueous polyurethane composition characterized in that it is a polycarbonate diol having a number average molecular weight of 300-10000,
(In the formula, R 1 represents an alkylene group having 2 to 20 carbon atoms excluding an alkylene group derived from 2-methyl-1,3-propanediol.)
(2) The aqueous polyurethane composition as described in (1), wherein R 1 in the formula (B) is represented by the following formula (C).
(CH 2 ) n (C)
(In the formula, n represents an integer of 2 to 10.)
(3) The aqueous polyurethane composition as described in (1), wherein R 1 in the formula (B) is represented by the following formula (D).
(CH 2 ) m (D)
(Wherein m represents an integer of 4 or 6).
本発明は、耐油性、耐汗性、耐加水分解性、耐候性、柔軟性、密着性など物性バランスに優れた塗料、コーティング材、接着剤、粘着剤などの用途に使用される水性ポリウレタン組成物を提供することが出来る。 The present invention is an aqueous polyurethane composition used for applications such as paints, coating materials, adhesives, and pressure-sensitive adhesives, which have excellent physical property balance such as oil resistance, sweat resistance, hydrolysis resistance, weather resistance, flexibility and adhesion. You can provide things.
以下、本願発明について具体的に説明する。 Hereinafter, the present invention will be specifically described.
本発明で用いる有機イソシアネートは、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およびその混合物、ジフェニルメタン−4,4´−ジイソシアネート(MDI)、ナフタレン−1,5−ジイソシアネート(NDI)、3,3´−ジメチル−4,4´ビフェニレンジイソシアネート(TODI)、粗製TDI、ポリメチレンポリフェニレンポリイソシアネート(PMDI)、粗製MDI、ジアニジンジイソシアネート、テトラメチルキシリレンジイソシアネートなどの芳香族ジイソシアネート、キシリレンジイソシアネート(XDI)、p−フェニレンジイソシアネートなどの芳香脂肪族ジイソシアネート、4−4´−メチレンビスシクロヘキシルジイソシアネート(水添MDI)、イソホロンジイソシアネート(IPDI)、シクロヘキサンジイソシアネート(水添XDI)、ノルボルネンジイソシアネートなどの脂環式ジイソシアネート、ヘキサメチレンジイソシアネート(HDI)、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、リシジンイソシアネートなどの脂肪族ジイソシアネートを挙げることができる。耐光性が低下するなどの観点より、脂環式ジイソシアネートまたは脂肪族ジイソシアネートを用いることが好ましく、それに加え耐加水分解性の観点より脂環式ジイソシアネートを用いることがさらに好ましい。上記の有機イソシアネートは、カルボジイミド変性、イソシアヌレート変性、ビウレット変性などの変性物の形で用いても良く、各種のブロッキング剤によりブロックされたブロックドイソシアネートでも良い。通常は1種の有機イソシアネートを選択して用いるが、これらの有機イソシアネートから2種類以上を選択しそれらを混合して、または逐次追加して用いても構わない。さらに、1分子中にイソシアネート基を3個以上有するポリイソシアネートを用いることも出来る。1分子中にイソシアネート基を3個以上有するポリイソシアネートとしては、上記のジイソシアネートのイソシアヌレート三量体、ビウレット三量体、トリメチロールプロパンアダクト化合物などに加え、トリフェニルメタントリイソシアネート、1−メチルベンゾール−2,4,6−トリイソシアネート、ジメチルトリフェニルメタンテトライソシアネートなどが挙げられる。さらに、これらのイソシアヌレート変性やビウレット変性などの変性物の形で用いても良く、各種のブロッキング剤によりブロックされたブロックドイソシアネートの形で用いても良い。 The organic isocyanate used in the present invention is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof, diphenylmethane-4,4′-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), Aromatic diisocyanates such as 3,3′-dimethyl-4,4′biphenylene diisocyanate (TODI), crude TDI, polymethylene polyphenylene polyisocyanate (PMDI), crude MDI, dianidin diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate (XDI), aromatic aliphatic diisocyanates such as p-phenylene diisocyanate, 4-4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), isophorone diisocyanate IPDI), cycloaliphatic diisocyanate (hydrogenated XDI), cycloaliphatic diisocyanates such as norbornene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Mention may be made of aliphatic diisocyanates such as cidin isocyanate. It is preferable to use an alicyclic diisocyanate or an aliphatic diisocyanate from the viewpoint of reducing light resistance, and it is more preferable to use an alicyclic diisocyanate from the viewpoint of hydrolysis resistance. The organic isocyanate may be used in the form of a modified product such as carbodiimide modification, isocyanurate modification, biuret modification or the like, or may be blocked isocyanate blocked with various blocking agents. Usually, one type of organic isocyanate is selected and used, but two or more types may be selected from these organic isocyanates, and these may be mixed or sequentially added. Furthermore, a polyisocyanate having 3 or more isocyanate groups in one molecule can also be used. Examples of polyisocyanates having 3 or more isocyanate groups in one molecule include triphenylmethane triisocyanate, 1-methylbenzol, in addition to the above-mentioned isocyanurate trimers, biuret trimers, and trimethylolpropane adduct compounds of diisocyanate. -2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate and the like. Further, these may be used in the form of modified products such as isocyanurate modification and biuret modification, or may be used in the form of blocked isocyanate blocked with various blocking agents.
本発明において、有機イソシアネートの配合量は、ポリカーボネートジオールの水酸基と1個の親水性中心と少なくとも2個のイソシアネート反応性の基を有する化合物のイソシアネート反応性の基の合計に対して、70〜100%当量、好ましくは80〜98%当量である。有機イソシアネートの配合量が70%当量未満の場合、ウレタンの分子量が小さく、硬化後の強度が不足する場合が多く、100%当量を超える場合、過剰のイソシアネート基が残存するため、貯蔵中にゲルを生成するなど貯蔵安定性などに問題が発生するので好ましくない。 In the present invention, the compounding amount of the organic isocyanate is 70 to 100 based on the total of the isocyanate-reactive groups of the compound having a hydroxyl group, one hydrophilic center and at least two isocyanate-reactive groups of the polycarbonate diol. % Equivalent, preferably 80-98% equivalent. When the blending amount of organic isocyanate is less than 70% equivalent, the molecular weight of urethane is small and the strength after curing is often insufficient, and when it exceeds 100% equivalent, excess isocyanate groups remain, so gel during storage This causes a problem in storage stability and the like, and is not preferable.
本発明で用いるポリカーボネートジオールは、ジオールと炭酸エステルを原料に用い、エステル交換に付することで得ることができる。 The polycarbonate diol used in the present invention can be obtained by subjecting it to transesterification using diol and carbonate as raw materials.
本発明で用いるポリカーボネートジオールは、下記式(E)と下記式(F)で表されるジオールを原料に用いる。 The polycarbonate diol used in the present invention uses a diol represented by the following formula (E) and the following formula (F) as a raw material.
(式中、R1は、2−メチル−1,3プロパンジオールに由来するアルキレン基を除く、炭素数2〜20のアルキレン基を示す。)
上記式(F)で表されるジオールは、2−メチルー1,3−プロパンジオールを除くジオールであって、その例としては、エチレングリコール、1,3−プロパンジオール、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、1,7−ヘプタンジオール、1,8−オクタンジオール、1,9−ノナンジオール、1,10−デカンジオール、1,5−ヘキサンジオール、2−メチル−1,8−オクタンジオール、ネオペンチルグリコール、2−イソプロピル−1,4−ブタンジオール、2−エチル−1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、2,4−ジメチル−1,5−ペンタンジオール、2,4−ジエチル−1,5−ペンタンジオール、1,3−ブタンジオール、2−エチルー1,3−ヘキサンジオール、2−ブチル−2−エチル−1,3−プロパンジオール、1,3−シクロヘキサンジオール、1,4−シクロヘキサンジオール、1,4−シクロヘキサンジメタノール、2−ビス(4−ヒドロキシシクロヘキシル)−プロパンなどを挙げることができる。上記式(F)で表されるジオールは、1種類のみを用いても2種以上を併用しても良い。なかでも、炭素数2〜10の直鎖アルキレンジオールを用いるのが好ましい。1,3−プロパンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオールを用いることがより好ましい。さらに、強度に優れるという観点では、1,4−ブタンジオール、1,6−ヘキサンジオールを用いることが好ましい。
(In the formula, R 1 represents an alkylene group having 2 to 20 carbon atoms excluding an alkylene group derived from 2-methyl-1,3-propanediol.)
The diol represented by the above formula (F) is a diol excluding 2-methyl-1,3-propanediol, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,5-hexanediol, 2 -Methyl-1,8-octanediol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4 -Dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,3-butanediol, 2-ethyl-1 3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-bis (4-hydroxycyclohexyl) ) -Propane and the like. The diol represented by the above formula (F) may be used alone or in combination of two or more. Especially, it is preferable to use a C2-C10 linear alkylene diol. More preferably, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are used. Furthermore, from the viewpoint of excellent strength, it is preferable to use 1,4-butanediol and 1,6-hexanediol.
本発明で用いるポリカーボネートジオールは、上記式(A)と上記式(B)との割合がモル比率で99:1〜1:99である。好ましくは、80:20〜20:80である。より好ましくは、70:30〜30:70である。 As for the polycarbonate diol used by this invention, the ratio of the said Formula (A) and the said Formula (B) is 99: 1 to 1:99 by molar ratio. Preferably, it is 80: 20-20: 80. More preferably, it is 70: 30-30: 70.
また、本発明で用いられるポリカーボネートジオールには、(E)と(F)の他に、1分子に3個以上のヒドロキシル基を持つ化合物、例えば、トリメチロールエタン、トリメチロールプロパン、ヘキサントリオール、ペンタエリスリトールなどを少量用いることにより、多官能化したポリカーボネートも含まれる。1分子中に3以上のヒドロキシル基を持つ化合物を余り多く用いると、架橋してゲル化が起きてしまうので、ジオールの合計モル数に対して、5モル%以下にする。好ましくは、2モル%以下にする。 In addition to (E) and (F), the polycarbonate diol used in the present invention includes compounds having three or more hydroxyl groups per molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, penta Polyfunctionalized polycarbonates by using a small amount of erythritol and the like are also included. If too many compounds having three or more hydroxyl groups in one molecule are used, gelation occurs due to crosslinking, so the amount is made 5 mol% or less with respect to the total number of moles of diol. Preferably, it is 2 mol% or less.
本発明で用いられるポリカーボネートの平均分子量の範囲は、数平均分子量で300〜10000、好ましくは400〜5000、さらに好ましくは400〜2500である。 The range of the average molecular weight of the polycarbonate used in the present invention is 300 to 10,000, preferably 400 to 5000, and more preferably 400 to 2500 in terms of number average molecular weight.
本発明で用いるポリカーボネートジオールは、アルキレンカーボネート、ジアルキルカーボネート、ジアリールカーボネートなどの炭酸エステルを原料に用いる。アルキレンカーボネートとしては、エチレンカーボネート、トリメチレンカーボネート、1,2−プロピレンカーボネート、1,2−ブチレンカーボネート、1,3−ブチレンカーボネート、1,2−ペンチレンカーボネートなどがある。また、ジアルキルカーボネートとしては、ジメチルカーボネート、ジエチルカーボネート、ジ−n−ブチルカーボネートなどが、ジアルキレンカーボネートとしては、ジフェニルカーボネートなどがある。そのなかでも、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネートを用いるのが好ましい。エチレンカーボネートを用いるのがより好ましい。 The polycarbonate diol used in the present invention uses a carbonate ester such as alkylene carbonate, dialkyl carbonate, diaryl carbonate or the like as a raw material. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, and di-n-butyl carbonate, and examples of the dialkylene carbonate include diphenyl carbonate. Among these, it is preferable to use ethylene carbonate, dimethyl carbonate, or diethyl carbonate. More preferably, ethylene carbonate is used.
本発明では、エステル交換を行う際の反応温度は、120℃〜280℃である。好ましくは、130℃〜230℃である。 In this invention, the reaction temperature at the time of performing transesterification is 120 to 280 degreeC. Preferably, it is 130 degreeC-230 degreeC.
本発明で用いるポリカーボネートジオールを得る場合、反応を速めたい場合は触媒を用いることが望ましい。触媒としては、通常用いられるエステル交換反応触媒から選択して用いることが出来る。エステル交換反応触媒としては、テトライソプロポキシチタン、テトラ−n−ブトキシチタンなどのチタン化合物、ジ−n−ブチルスズジラウレート、ジ−n−ブチルスズオキサイド、ジブチルスズジアセテートなどのスズ化合物、酢酸マグネシウム、酢酸カルシウム、酢酸亜鉛などの酢酸の金属塩などが挙げられる。なかでもチタン化合物を用いるのが好ましい。これらの触媒は、反応物に対し1〜300ppmとなるように用いるのが好ましい。30〜200ppmとなるように用いるのがより好ましい。 When obtaining the polycarbonate diol used in the present invention, it is desirable to use a catalyst when it is desired to accelerate the reaction. As a catalyst, it can select and use from the transesterification catalyst used normally. Examples of the transesterification reaction catalyst include titanium compounds such as tetraisopropoxy titanium and tetra-n-butoxy titanium, tin compounds such as di-n-butyltin dilaurate, di-n-butyltin oxide and dibutyltin diacetate, magnesium acetate, and calcium acetate. And metal salts of acetic acid such as zinc acetate. Of these, it is preferable to use a titanium compound. These catalysts are preferably used in an amount of 1 to 300 ppm based on the reaction product. It is more preferable to use it so that it may become 30-200 ppm.
本発明で用いるポリカーボネートジオールは、柔軟性を向上させる目的で、その分子内にエーテル結合を有しても良い。エーテル結合の含有量は、本発明の効果に影響しない範囲であれば特に限定はしないが、その量が増えると耐熱性や耐薬品性が低下する。よって、エーテル結合の含有量は、0.05〜5モル%であることが好ましく、0.05〜3モル%であることが更に好ましい。
また、本発明の水性ポリウレタン組成物には、本発明の効果を損なわない範囲で、ポリエーテルポリオールまたはポリエステルポリオールを併用することも出来る。但し、ポリエステルポリオール添加すると、耐加水分解性が著しく低下する場合が多いので、その使用は制限される。
The polycarbonate diol used in the present invention may have an ether bond in the molecule for the purpose of improving flexibility. The content of the ether bond is not particularly limited as long as it does not affect the effects of the present invention, but heat resistance and chemical resistance decrease as the amount increases. Therefore, the content of the ether bond is preferably 0.05 to 5 mol%, and more preferably 0.05 to 3 mol%.
Moreover, polyether polyol or polyester polyol can also be used together in the aqueous polyurethane composition of the present invention as long as the effects of the present invention are not impaired. However, when the polyester polyol is added, the hydrolysis resistance is often remarkably lowered, so that its use is limited.
本発明で用いる、1個の親水性中心と少なくとも2個のイソシアネート反応性の基を有する化合物は、ポリウレタンエマルジョンの乳化安定性を保つことを目的として、アニオン性の親水性基を導入するため用いられる成分である。
例えば、2−ジメチロールプロピオン酸、2,2−ジメチロール酪酸、2,2−ジメチロール吉草酸などのジヒドロキシカルボン酸、3,4−ジアミノブタンスルホン酸、3,6−ジアミノ−2−トルエンスルホン酸などのジアミノカルボン酸類を用いることが出来る。
1個の親水性中心と少なくとも2個のイソシアネート反応性の基を有する化合物を用いる場合、乳化安定性の観点から、通常は中和剤で中和して用いる。中和剤の例としては、トリメチルアミン、トリエチルアミン、トリ−n−プロピルアミン、トリブチルアミンなどのトリアルキルアミン、N,N−ジメチルエタノールアミン、N,N−ジメチルプロパノールアミン、N,N−ジプロピルエタノールアミン、1−ジメチルアミノ−2−メチル−プロパノールなどのN,N−ジアルキルアルカノールアミン、N−アルキル−N,N−ジアルカノールアミン、トリエタノールアミンなどのトリアルカノールアミン、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、アンモニア、トリメチルアンモニウムヒドロキシドなどが挙げられる。中和剤の量は、親水性中心のモル数に対し、0.5〜2.0当量、好ましくは0.7〜1.2当量である。
The compound having one hydrophilic center and at least two isocyanate-reactive groups used in the present invention is used to introduce an anionic hydrophilic group for the purpose of maintaining the emulsion stability of the polyurethane emulsion. Component.
For example, 2-hydroxylpropionic acid, 2,2-dimethylolbutyric acid, dihydroxycarboxylic acid such as 2,2-dimethylolvaleric acid, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, etc. The diaminocarboxylic acids can be used.
When a compound having one hydrophilic center and at least two isocyanate-reactive groups is used, it is usually neutralized with a neutralizing agent from the viewpoint of emulsion stability. Examples of neutralizing agents include trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dipropylethanol. Amines, N, N-dialkylalkanolamines such as 1-dimethylamino-2-methyl-propanol, N-alkyl-N, N-dialkanolamines, trialkanolamines such as triethanolamine, sodium hydroxide, potassium hydroxide Lithium hydroxide, ammonia, trimethylammonium hydroxide, and the like. The amount of the neutralizing agent is 0.5 to 2.0 equivalents, preferably 0.7 to 1.2 equivalents, relative to the number of moles of the hydrophilic center.
本発明で用いる鎖延長剤としては、水、エチレングリコール、1,4−ブタンジオールなどの短鎖ジオール、ヒドラジン、エチレンジアミン、ジエチルトリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、プロピレンジアミン、ヘキサメチレンジアミン、シクロヘキシレンジアミン、ピペラジン、2−メチルピペラジン、フェニレンジアミン、トリレンジアミン、キシレンジアミン、α,α’−メチレンビス(2−クロリアニリン)、3,3’−ジクロル−α,α’−ビフェニルアミン、m−キシレンジアミン、イソホロンジアミン、N−メチル−3,3’−ジアミノプロピルアミン、およびジエチレントリアミンとアクリレートのアダクトまたはその加水分解生成物などのポリアミン類が挙げられる。鎖延長剤の量は、通常は有機イソシアネート、ポリカーボネートジオール、および1個の親水性中心と少なくとも2個のイソシアネート反応性の基を有する化合物からなるウレタンプレポリマー中のイソシアネート基1モルに対し、0〜0.95モル、好ましくは0.1〜0.6モルである。 Examples of the chain extender used in the present invention include water, short-chain diols such as ethylene glycol and 1,4-butanediol, hydrazine, ethylenediamine, diethyltriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, Hexamethylenediamine, cyclohexylenediamine, piperazine, 2-methylpiperazine, phenylenediamine, tolylenediamine, xylenediamine, α, α'-methylenebis (2-chloranilin), 3,3'-dichloro-α, α'- And polyamines such as biphenylamine, m-xylenediamine, isophoronediamine, N-methyl-3,3′-diaminopropylamine, and adducts of diethylenetriamine and acrylate or hydrolysis products thereof. . The amount of chain extender is usually 0 per mole of isocyanate groups in a urethane prepolymer comprising an organic isocyanate, a polycarbonate diol, and a compound having one hydrophilic center and at least two isocyanate-reactive groups. -0.95 mol, preferably 0.1-0.6 mol.
乳化安定性を確保するため、エマルジョンに一般に用いられるアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、高分子系界面活性剤、反応性界面活性剤などを使用することが出来る。ノニオン性界面活性剤としては、例えば、脂肪族アルコールアルキレンオキサイド付加物、アルキルフェノールのアルキレンオキサイド付加物、ソルビタンモノラウレートなどの多価アルコール脂肪酸エステル、ヤシ油脂肪酸ジエタノールアミドなどの脂肪酸アルカノールアミド、(ポリ)オキシアルキレンアルキルフェニルエーテル、(ポリ)オキシアルキレンアルキルアミン、ラウリルジメチルアミンオキシドなどのジアルキルアミンオキシドが挙げられる。アニオン性界面活性剤としては、ラウリルエーテル酢酸ナトリウムなどのエーテルカルボン酸またはその塩、ラウリル硫酸ナトリウムなどの硫酸エステルまたはその塩、(ポリ)オキシエチレンラウリル硫酸ナトリウム、(ポリ)オキシエチレンラウリル酸トリエタノールアミン、ドデシルベンゼンスルホン酸ナトリウムなどのスルホン酸塩、ラウリルリン酸ナトリウムなどのリン酸エステルまたはその塩、ラウリン酸ナトリウムなどの脂肪酸塩などが挙げられる。カチオン活性剤としては、1級から3級アミン塩、ピリジニウム塩、アルキルピリジニウム塩などが挙げられる。上記の界面活性剤は、必要に応じて任意の量を使用することが出来るが、通常は、通常は有機イソシアネート、ポリカーボネートジオール、および1個の親水性中心と少なくとも2個のイソシアネート反応性の基を有する化合物からなるウレタンプレポリマーと鎖延長剤の合わせた重量に対し0.1〜30重量%、好ましくは3〜20重量%用いられる。 To ensure emulsion stability, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymeric surfactants, reactive surfactants, etc., commonly used in emulsions Can be used. Examples of nonionic surfactants include aliphatic alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, polyhydric alcohol fatty acid esters such as sorbitan monolaurate, fatty acid alkanolamides such as coconut oil fatty acid diethanolamide, (poly And dialkylamine oxides such as (oxy) alkylene alkylphenyl ether, (poly) oxyalkylene alkylamine, and lauryldimethylamine oxide. Anionic surfactants include ether carboxylic acids or salts thereof such as sodium lauryl ether acetate, sulfate esters or salts thereof such as sodium lauryl sulfate, (poly) oxyethylene sodium lauryl sulfate, (poly) oxyethylene lauric acid triethanol Examples include amines, sulfonates such as sodium dodecylbenzenesulfonate, phosphate esters such as sodium lauryl phosphate or salts thereof, and fatty acid salts such as sodium laurate. Examples of the cationic activator include primary to tertiary amine salts, pyridinium salts, alkylpyridinium salts, and the like. The above surfactants can be used in any amount as required, but are usually usually organic isocyanates, polycarbonate diols, and one hydrophilic center and at least two isocyanate-reactive groups. It is used in an amount of 0.1 to 30% by weight, preferably 3 to 20% by weight, based on the combined weight of the urethane prepolymer composed of the compound having a chain extender.
本発明の水性ポリウレタン組成物を製造する過程で、必要に応じて有機溶剤を用いても構わない。有機溶剤としては、イソシアネートに対して不活性な溶剤であればよく、例えば、メチルエチルケトン、アセトンなどのケトン、酢酸メチル、酢酸エチルなどのケトン、アセトニトリル、テトラヒドロフラン、トルエン、ジオキサン、N−メチルピロリドンなどを、単独でまたは2種類以上を混合して用いることが出来る。有機溶剤の沸点が100℃以上、すなわち水の沸点を超えると、有機溶剤のみを完全に除去することが困難となり、エマルジョン中または塗膜中に残存しやすくなることにより、塗膜物性が経時的に変化するなど問題が生じる。よって、沸点は100℃以下の有機溶剤を用いる方が好ましい。有機溶剤を使用する場合は、有機イソシアネート、ポリカーボネートジオール、および1個の親水性中心と少なくとも2個のイソシアネート反応性の基を有する化合物と鎖延長剤の重量に対し、3〜100重量%使用される。 In the process of producing the aqueous polyurethane composition of the present invention, an organic solvent may be used as necessary. The organic solvent may be any solvent inert to the isocyanate. Examples include ketones such as methyl ethyl ketone and acetone, ketones such as methyl acetate and ethyl acetate, acetonitrile, tetrahydrofuran, toluene, dioxane, and N-methylpyrrolidone. These can be used alone or in admixture of two or more. When the boiling point of the organic solvent exceeds 100 ° C., that is, exceeds the boiling point of water, it becomes difficult to completely remove only the organic solvent, and it tends to remain in the emulsion or the coating film. Problems such as change to. Therefore, it is preferable to use an organic solvent having a boiling point of 100 ° C. or lower. When an organic solvent is used, it is used in an amount of 3 to 100% by weight based on the weight of the organic isocyanate, polycarbonate diol, compound having one hydrophilic center and at least two isocyanate-reactive groups and the chain extender. The
本発明の水性ポリウレタン組成物を製造する過程で、必要に応じて公知の触媒を用いても構わない。触媒としては、トリエチルアミン、N−エチルモルホリン、トリエチレンジアミンなどのアミン類、ジブチル錫ジラウレート、ジオクチル錫ジラウレート、オクチル酸錫などの錫化合物、テトラブチルチタネートなどのチタン化合物が挙げられる。 In the process of producing the aqueous polyurethane composition of the present invention, a known catalyst may be used as necessary. Examples of the catalyst include amines such as triethylamine, N-ethylmorpholine, and triethylenediamine, tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, and tin octylate, and titanium compounds such as tetrabutyltitanate.
本発明の水性ポリウレタン組成物は、その用途に応じ、一般に用いられる添加剤を必要量添加することが出来る。添加剤としては、顔料、染料、光安定剤、補助バインダー、増粘剤、レベリング剤、チキソトロピー付与剤、消泡剤、発泡剤、紫外線吸収剤、酸化防止剤、減粘剤、成膜助剤、硬化剤、シランカップリング剤、ブロッキング防止剤、ゲル化防止剤、分散安定剤、ラジカル補足剤、無機または有機充填剤、可塑剤、滑剤、帯電防止剤、抗菌剤、防かび剤、防腐剤などが挙げられる。 In the aqueous polyurethane composition of the present invention, a necessary amount of commonly used additives can be added depending on the application. Additives include pigments, dyes, light stabilizers, auxiliary binders, thickeners, leveling agents, thixotropy imparting agents, antifoaming agents, foaming agents, ultraviolet absorbers, antioxidants, thickeners, film forming aids. , Curing agent, silane coupling agent, anti-blocking agent, anti-gelling agent, dispersion stabilizer, radical scavenger, inorganic or organic filler, plasticizer, lubricant, antistatic agent, antibacterial agent, fungicide, antiseptic Etc.
本発明の水性ポリウレタン組成物の状態は、エマルジョン、サスペンジュン、コロイダル分散液などである。エマルジョン、サスペンジュン、コロイダル分散液の場合、その粒径は特に限定されないが、良好な分散状態を保つ目的では、1μm以下であることが好ましく、500nm以下であることがさらに好ましい。 The state of the aqueous polyurethane composition of the present invention is an emulsion, suspension, colloidal dispersion or the like. In the case of an emulsion, suspension, or colloidal dispersion, the particle size is not particularly limited, but is preferably 1 μm or less and more preferably 500 nm or less for the purpose of maintaining a good dispersion state.
本発明の水性ポリウレタン組成物において、その固形分は特に限定する物でない。通常は、10〜70重量%、好ましくは20〜60重量%である。 In the aqueous polyurethane composition of the present invention, the solid content is not particularly limited. Usually, it is 10 to 70% by weight, preferably 20 to 60% by weight.
本発明の水性ポリウレタン組成物を製造する方法は、特に限定されるものでないが、例えば以下に示す方法を挙げることが出来る。有機溶媒の存在下、ポリカーボネートジオール、1個の親水性中心と少なくとも2個のイソシアネート反応性を有する化合物と有機イソシアネートを反応させて、末端がイソシアネートであるウレタンプレポリマーを製造する。上記のウレタンプレポリマーを鎖伸長剤含有水溶液に投入し乳化、鎖延長反応を行った後、系内に含有する有機溶媒を蒸留などの方法で除去し、ウレタンエマルジョンを得る。中和剤は、ウレタンプレポリマーを製造する過程で用いても良く、ウレタンプレポリマーを製造後、鎖伸長剤含有水溶液に投入する前に加えても良く、鎖伸長剤含有水溶液に加えても良い。反応は、通常は20〜90℃で行われる。 The method for producing the aqueous polyurethane composition of the present invention is not particularly limited, and examples thereof include the following methods. In the presence of an organic solvent, a polycarbonate diol, one hydrophilic center and at least two isocyanate-reactive compounds are reacted with an organic isocyanate to produce a urethane prepolymer whose terminal is an isocyanate. The urethane prepolymer is put into a chain extender-containing aqueous solution, emulsified and subjected to a chain extension reaction, and then the organic solvent contained in the system is removed by a method such as distillation to obtain a urethane emulsion. The neutralizing agent may be used in the process of producing the urethane prepolymer, may be added before the urethane prepolymer is produced, and before being added to the chain extender-containing aqueous solution, or may be added to the chain extender-containing aqueous solution. . The reaction is usually carried out at 20 to 90 ° C.
次に、実施例および比較例によって、本発明を説明する。 Next, the present invention will be described with reference to examples and comparative examples.
以下の実施例および比較例において示す値は下記の方法測定した。
a)ポリカーボネートジオールの水酸基価
メスフラスコを用い、無水酢酸12.5gにピリジンを加えて50mlとし、アセチル化試薬を調整する。100mlのナスフラスコに、サンプルを2.5〜5.0g精秤する。アセチル化試薬5mlとトルエン10mlをホールピペットで添加後、冷却管を取り付けて、100℃で1hr撹拌加熱する。蒸留水2.5mlをホールピペットで添加、さらに10min加熱撹拌する。2〜3min冷却後、エタノールを12.5ml添加し、指示薬としてフェノールフタレインを2〜3滴入れた後に、0.5mol/lエタノール性水酸化カリウムで滴定する。アセチル化試薬5ml、トルエン10ml、蒸留水2.5mlを100mlナスフラスコに入れ、10分間加熱撹拌した後、同様に滴定を行う(空試験)。この結果をもとに、下記式(1)で水酸基価を計算した。
Values shown in the following examples and comparative examples were measured by the following methods.
a) Hydroxyl value of polycarbonate diol Using a measuring flask, pyridine is added to 12.5 g of acetic anhydride to make 50 ml, and an acetylating reagent is prepared. A sample is accurately weighed in an amount of 2.5 to 5.0 g in a 100 ml eggplant flask. Add 5 ml of acetylating reagent and 10 ml of toluene with a whole pipette, attach a condenser, and stir and heat at 100 ° C. for 1 hr. Add 2.5 ml of distilled water with a whole pipette and stir for 10 min. After cooling for 2 to 3 minutes, 12.5 ml of ethanol is added, and after adding 2-3 drops of phenolphthalein as an indicator, titration is performed with 0.5 mol / l ethanolic potassium hydroxide. 5 ml of an acetylating reagent, 10 ml of toluene, and 2.5 ml of distilled water are placed in a 100 ml eggplant flask and stirred for 10 minutes, and then titrated in the same manner (blank test). Based on this result, the hydroxyl value was calculated by the following formula (1).
水酸基価(mg−KOH/g)={(B−A)×28.05×f}/C (1)
A:サンプルの滴定量(ml)
B:空試験の滴定量(ml)
C:サンプル重量(g)
f:滴定液のファクター
実施例、比較例中のポリマーの末端は、13C−NMR(270MHz)の測定により、実質的に全てがヒドロキシル基であった。さらに、ポリマー中の酸価をKOHによる滴定で測定したが、実施例、比較例のポリマー全てが0.01以下であった。従って、得られたポリマーの数平均分子量は、上記の水酸基価を用い、下式(2)により求められる。
数平均分子量=2/(水酸基価×10―3/56.11) (2)
b)ポリカーボネートジオールの組成比
組成比は、以下のように測定した。100mlのナスフラスコにサンプルを1g取り、エタノール30g、水酸化カリウム4gを入れて、100℃で1hr反応する。室温まで冷却後、指示薬にフェノールフタレインを2〜3滴添加し、塩酸で中和する。冷蔵庫で1hr冷却後、沈殿した塩を濾過で除去し、ガスクロマトグラフィーにより分析を行った。分析は、カラムとしてDB−WAX(J&W製)をつけたガスクロマトグラフィーGC−14B(島津製作所製)を用い、ジエチレングリコールジエチルエステルを内標として、検出器をFIDとして行った。なお、カラムの昇温プロファイルは、60℃で5分保持した後、10℃/minで250℃まで昇温した。得られた結果をもとに、下式(3)を用いて、組成比を求めた。
組成比(mol%)= (D/E)×100 (3)
D:2−メチル−1.3−プロパンジオールのモル数
E:全てのジオールのモル数
尚、ポリカーボネートジオールの分子内にエーテル結合を有する場合、その含有量は、上記の方法で得られた、全てのジオールのモル数に対する、エーテル結合を有するジオールのモル%として現される。
c)フィルム調製
エマルジョンを40℃で1ヶ月保管した後、ガラス板上で成膜し、24時間室温で放置した後120℃で30分熱処理を行い、厚さ100μm、幅10mm、長さ60mmの試料フィルムを得た。上記の方法で得たフィルムを用い、耐油性、耐加水分解性、耐候性、柔軟性を評価した。
d)機械的強度
恒温室において、テンシロン引張試験器(ORIENTEC製、RTC−1250A)を用いて、チャック間50mm、引張速度100mm/minで測定した。破断時の強度を機械的強度(以降、強度と称する。)とした。
e)耐油性
試料を45℃のオレイン酸(試薬1級)中に1週間浸漬後の膨潤率を測定した。膨潤率は、下記式(4)を用いて求めた。
Hydroxyl value (mg-KOH / g) = {(BA) × 28.05 × f} / C (1)
A: Titration volume of sample (ml)
B: Titrate of blank test (ml)
C: Sample weight (g)
f: Factor of titrant The polymer ends in Examples and Comparative Examples were substantially all hydroxyl groups as determined by 13 C-NMR (270 MHz). Furthermore, although the acid value in a polymer was measured by titration with KOH, all of the polymers of Examples and Comparative Examples were 0.01 or less. Therefore, the number average molecular weight of the obtained polymer is obtained by the following formula (2) using the above hydroxyl value.
Number average molecular weight = 2 / (hydroxyl value × 10 −3 /56.11) (2)
b) Composition ratio of polycarbonate diol The composition ratio was measured as follows. Take 1 g of a sample in a 100 ml eggplant flask, add 30 g of ethanol and 4 g of potassium hydroxide, and react at 100 ° C. for 1 hr. After cooling to room temperature, add 2-3 drops of phenolphthalein to the indicator and neutralize with hydrochloric acid. After cooling in the refrigerator for 1 hr, the precipitated salt was removed by filtration and analyzed by gas chromatography. The analysis was performed by using gas chromatography GC-14B (manufactured by Shimadzu Corporation) with DB-WAX (manufactured by J & W) as a column, diethylene glycol diethyl ester as an internal standard, and a detector as FID. The temperature rising profile of the column was maintained at 60 ° C. for 5 minutes and then heated to 250 ° C. at 10 ° C./min. Based on the obtained results, the composition ratio was determined using the following formula (3).
Composition ratio (mol%) = (D / E) × 100 (3)
D: Number of moles of 2-methyl-1.3-propanediol
E: Number of moles of all diols When the polycarbonate diol has an ether bond in the molecule, the content is the number of moles of diol having an ether bond with respect to the number of moles of all diols obtained by the above method. Expressed as a percentage.
c) Film preparation After storing the emulsion at 40 ° C. for 1 month, the film was formed on a glass plate, allowed to stand at room temperature for 24 hours, and then heat-treated at 120 ° C. for 30 minutes, having a thickness of 100 μm, a width of 10 mm, and a length of 60 mm. A sample film was obtained. The film obtained by the above method was used to evaluate oil resistance, hydrolysis resistance, weather resistance, and flexibility.
d) Mechanical strength Measurement was performed in a constant temperature room using a Tensilon tensile tester (manufactured by ORIENTEC, RTC-1250A) at a chuck distance of 50 mm and a tensile speed of 100 mm / min. The strength at break was defined as mechanical strength (hereinafter referred to as strength).
e) Oil resistance The swelling ratio after the sample was immersed in 45 ° C. oleic acid (reagent grade 1) for 1 week was measured. The swelling rate was determined using the following formula (4).
膨潤率=(試験後の重量−試験前の重量)/試験前の重量×100(4)
f)耐加水分解性
試料を100℃の熱水中に2週間浸漬後、上記d)に示した方法で機械的強度を測定した。試験前の試料で求められた値に比べ試験後の測定値が、80%以上である場合を○、60%以上80%未満である場合を△、60%未満である場合を×として、耐加水分解性を評価した。
g)耐候性
試料をサンシャイン型ウエザオメーター(スガ試験機製、WEL−SUN−DC)中で、1サイクル60分、内12分の降水の繰り返しで所定時間(200時間)経過した後、上記d)に示した方法で機械的強度を測定した。試験前の値と比較して測定後の値が、80%以上である場合を○、60%以上80%未満である場合を△、60%未満である場合を×として、耐候性を評価した。
h)柔軟性
上記d)で示した方法で機械的強度を測定し、試料を100%伸長した時の応力(MPa)で柔軟性を評価した。
[ポリカーボネートジオールの合成例1]
Swelling ratio = (weight after test−weight before test) / weight before test × 100 (4)
f) Hydrolysis resistance After immersing the sample in hot water at 100 ° C. for 2 weeks, the mechanical strength was measured by the method shown in d) above. When the measured value after the test is 80% or more compared to the value obtained from the sample before the test, the case where the measured value is 60% or more and less than 80% is Δ, and the case where the measured value is less than 60% is ×. The hydrolyzability was evaluated.
g) Weather resistance After a predetermined time (200 hours) has elapsed in a sunshine type weatherometer (WEL-SUN-DC, manufactured by Suga Test Instruments Co., Ltd.) and repeated precipitation for 12 minutes within 60 minutes, d above ) Was used to measure the mechanical strength. When the value after measurement was 80% or more compared to the value before the test, the weather resistance was evaluated with ◯ when the value was 60% or more and less than 80%, and x when the value was less than 60%. .
h) Flexibility The mechanical strength was measured by the method shown in d) above, and the flexibility was evaluated by the stress (MPa) when the sample was stretched 100%.
[Synthesis Example 1 of Polycarbonate Diol]
攪拌機、温度計、頭頂に還流ヘッドを有する真空ジャッケト付きオルダーショウを備えた2lセパラブルフラスコに、2−メチル−1,3−プロパンジオール355g、1,4−ブタンジオール305g、エチレンカーボネート650gを仕込み、70℃で撹拌溶解したあと、触媒として酢酸鉛三水和物を0.015g入れた。165℃に設定したオイルバスで加熱し、フラスコの内温135℃、真空度1.0〜1.5kPaで、還流ヘッドから還流比4で留分の一部を抜きながら、24hr反応した。その後、オルダーショウを単蒸留装置に取り替え、180℃に設定したオイルバスで加熱し、フラスコの内温140〜150℃、真空度を0.5kPaまで落として、セパラブルフラスコ内に残った、ジオールとエチレンカーボネートを除去した。その後、オイルバスの設定を175℃に上げ、フラスコの内温150〜155℃で、生成するジオールを除去しながら、さらに12hr反応した。この反応により、常温で粘ちょうな液体が得られた。得られた反応物の水酸基価は55.7であり、組成比は50mol%であった。該ポリカーボネートジオールをPC1と称する。
[ポリカーボネートジオールの合成例2]
A 2 l separable flask equipped with a stirrer, thermometer, Oldershaw with vacuum jacket having a reflux head at the top was charged with 355 g of 2-methyl-1,3-propanediol, 305 g of 1,4-butanediol, and 650 g of ethylene carbonate, After stirring and dissolving at 70 ° C., 0.015 g of lead acetate trihydrate was added as a catalyst. The mixture was heated in an oil bath set at 165 ° C., and the reaction was carried out for 24 hr while removing a part of the fraction from the reflux head at a reflux ratio of 4 at an internal temperature of the flask of 135 ° C. and a degree of vacuum of 1.0 to 1.5 kPa. Thereafter, the Oldershaw was replaced with a simple distillation apparatus, heated in an oil bath set at 180 ° C., the internal temperature of the flask was reduced to 140 to 150 ° C., the degree of vacuum was reduced to 0.5 kPa, and the diol remaining in the separable flask and Ethylene carbonate was removed. Then, the setting of the oil bath was raised to 175 ° C., and the reaction was further performed for 12 hours while removing the diol produced at an internal temperature of the flask of 150 to 155 ° C. By this reaction, a viscous liquid was obtained at room temperature. The obtained reaction product had a hydroxyl value of 55.7 and a composition ratio of 50 mol%. This polycarbonate diol is referred to as PC1.
[Synthesis Example 2 of Polycarbonate Diol]
合成例1の装置を用い、1,6−ヘキサンジオール702g、エチレンカーボネート524g、酢酸鉛三水和物0.012g仕込んだ。180℃に設定したオイルバスで加熱し、フラスコの内温155℃、真空度3.0〜4.2kPaで、還流ヘッドから還流比4で留分の一部を抜きながら、20hr反応した。その後、オルダーショウを単蒸留装置に取り替えた後、190℃に設定したオイルバスで加熱し、フラスコの内温160〜170℃、真空度を0.5kPaまで落として、セパラブルフラスコ内に残った、ジオールとエチレンカーボネートを除去した。その後、生成するジオールを除去しながら、さらに12hr反応した。この反応により、常温で白色の固体が得られた。得られた反応物の水酸基価は56.3であった。該ポリカーボネートジオールをPC2と称する。
[ポリカーボネートジオールの合成例3]
Using the apparatus of Synthesis Example 1, 702 g of 1,6-hexanediol, 524 g of ethylene carbonate, and 0.012 g of lead acetate trihydrate were charged. The mixture was heated in an oil bath set at 180 ° C., and the reaction was carried out for 20 hours while extracting a part of the fraction from the reflux head at a reflux ratio of 4 at an internal temperature of the flask of 155 ° C. and a degree of vacuum of 3.0 to 4.2 kPa. Thereafter, the Oldershaw was replaced with a simple distillation apparatus, and then heated in an oil bath set at 190 ° C., and the flask was left in a separable flask with an internal temperature of 160 to 170 ° C. and a vacuum reduced to 0.5 kPa. Diol and ethylene carbonate were removed. Thereafter, the reaction was further carried out for 12 hours while removing the produced diol. By this reaction, a white solid was obtained at room temperature. The obtained reaction product had a hydroxyl value of 56.3. This polycarbonate diol is referred to as PC2.
[Synthesis Example 3 of Polycarbonate Diol]
1,6ヘキサンジオール530g、1,5−ペンタンジオール150g、エチレンカーボネート524g、酢酸鉛三水和物0.011gとした以外は、合成例2の条件で重合を行った。この反応により、常温で粘ちょうな液体が得られた。得られた反応物の水酸基価は56.8であった。該ポリカーボネートジオールをPC3と称する。
[ポリカーボネートジオールの合成例4]
Polymerization was performed under the conditions of Synthesis Example 2 except that 530 g of 1,6 hexanediol, 150 g of 1,5-pentanediol, 524 g of ethylene carbonate, and 0.011 g of lead acetate trihydrate were used. By this reaction, a viscous liquid was obtained at room temperature. The obtained reaction product had a hydroxyl value of 56.8. This polycarbonate diol is referred to as PC3.
[Synthesis Example 4 of Polycarbonate Diol]
合成例1の装置を用い、1,6−ヘキサンジオール178g、2−メチル−1,3−プロパンジオール394g、エチレンカーボネート520g、酢酸鉛三水和物0.012g仕込んだ。185℃に設定したオイルバスで加熱し、フラスコの内温160℃、真空度3.2〜4.5kPaで、還流ヘッドから還流比4で留分の一部を抜きながら、20hr反応した。その後、オルダーショウを単蒸留装置に取り替えた後、190℃に設定したオイルバスで加熱し、フラスコの内温160〜170℃、真空度を0.5kPaまで落として、セパラブルフラスコ内に残った、ジオールとエチレンカーボネートを除去した。その後、生成するジオールを除去しながら、さらに11hr反応した。この反応により、常温で粘ちょうな液体が得られた。得られた反応物の水酸基価は55.8であり、組成比は69mol%であった。該ポリカーボネートジオールをPC4と称する
[ポリカーボネートジオールの合成例5]
Using the apparatus of Synthesis Example 1, 178 g of 1,6-hexanediol, 394 g of 2-methyl-1,3-propanediol, 520 g of ethylene carbonate, and 0.012 g of lead acetate trihydrate were charged. The mixture was heated in an oil bath set at 185 ° C., and the reaction was carried out for 20 hours while removing a part of the fraction from the reflux head at a reflux ratio of 4 at an internal temperature of the flask of 160 ° C. and a degree of vacuum of 3.2 to 4.5 kPa. Thereafter, the Oldershaw was replaced with a simple distillation apparatus, and then heated in an oil bath set at 190 ° C., and the flask was left in a separable flask with an internal temperature of 160 to 170 ° C. and a vacuum reduced to 0.5 kPa. Diol and ethylene carbonate were removed. Thereafter, the reaction was further carried out for 11 hours while removing the diol produced. By this reaction, a viscous liquid was obtained at room temperature. The obtained reaction product had a hydroxyl value of 55.8 and a composition ratio of 69 mol%. The polycarbonate diol is referred to as PC4 [Polycarbonate diol synthesis example 5]
1,5−ペンタンジオール358g、2−メチル−1,3−プロパンジオール104g、エチレンカーボネート405g、酢酸鉛三水和物0.010gとした以外は、合成例4の条件で重合を行った。この反応により、常温で粘ちょうな液体が得られた。得られた反応物の水酸基価は57.0であり、組成比は21mol%であった。該ポリカーボネートジオールをPC5と称する。 Polymerization was performed under the conditions of Synthesis Example 4 except that 358 g of 1,5-pentanediol, 104 g of 2-methyl-1,3-propanediol, 405 g of ethylene carbonate, and 0.010 g of lead acetate trihydrate. By this reaction, a viscous liquid was obtained at room temperature. The obtained reaction product had a hydroxyl value of 57.0 and a composition ratio of 21 mol%. This polycarbonate diol is referred to as PC5.
実施例1
還流冷却器、温度計、撹拌装置を備えた反応容器に、ポリカーボネートジオールPC1200g、4,4’−ジフェニルメタンジイソシアネート(以降、MDIと称す。)74.5g、トリエチルアミン(以降、TMAと称す。)で中和したジメチロールプロピオン酸(以降、DMPAと称す。)23.5g、メチルエチルケトン(以降、MEKと称す。)730gを入れ、50℃で2時間反応を行い、末端がイソシアネートのウレタンプレポリマーを得た。反応容器内の温度を30℃とした後、撹拌しながら該ウレタンプレポリマーに680gの蒸留水を20g/分の速度で添加して、ウレタンプレポリマー溶液のエマルジョンを得た。さらに、鎖延長剤として、イソホロンジアミン(以降、IPDAと称す。)の20重量%水溶液67.5gを、撹拌しながら30分かけて添加した。その後、反応容器内の温度を40℃としさらに30分反応した。還流冷却管を単蒸留装置に変えた後、減圧下で3時間かけて反応容器の内温を80℃まで昇温しながら溶媒であるMEKを留去して、固形分が約30重量%の水性ポリウレタン組成物を得た。該水性ポリウレタン組成物をPUD1と称する。
Example 1
In a reaction vessel equipped with a reflux condenser, a thermometer, and a stirrer, polycarbonate diol PC (1200 g), 4,4′-diphenylmethane diisocyanate (hereinafter referred to as MDI) 74.5 g, and triethylamine (hereinafter referred to as TMA). 23.5 g of summed dimethylolpropionic acid (hereinafter referred to as DMPA) and 730 g of methyl ethyl ketone (hereinafter referred to as MEK) were added and reacted at 50 ° C. for 2 hours to obtain a urethane prepolymer having a terminal isocyanate. . After setting the temperature in the reaction vessel to 30 ° C., 680 g of distilled water was added to the urethane prepolymer at a rate of 20 g / min while stirring to obtain an emulsion of a urethane prepolymer solution. Furthermore, 67.5 g of a 20 wt% aqueous solution of isophoronediamine (hereinafter referred to as IPDA) was added as a chain extender over 30 minutes with stirring. Thereafter, the temperature in the reaction vessel was set to 40 ° C., and the reaction was continued for 30 minutes. After changing the reflux condenser to a simple distillation apparatus, MEK as a solvent was distilled off while raising the internal temperature of the reaction vessel to 80 ° C. under reduced pressure over 3 hours, and the solid content was about 30% by weight. An aqueous polyurethane composition was obtained. This aqueous polyurethane composition is referred to as PUD1.
比較例1〜2
実施例1に示す方法で、ポリカーボネートジオールPC2およびポリカーボネートジオールPC3を用い、水性ポリウレタン組成物を得た。ポリカーボネートジオールPC2を用いた水性ポリウレタン組成物をPUD2と、ポリカーボネートジオールPC3を用いた水性ポリウレタン組成物をPUD3とそれぞれ称する。
Comparative Examples 1-2
By the method shown in Example 1, an aqueous polyurethane composition was obtained using polycarbonate diol PC2 and polycarbonate diol PC3. The aqueous polyurethane composition using polycarbonate diol PC2 is referred to as PUD2, and the aqueous polyurethane composition using polycarbonate diol PC3 is referred to as PUD3.
実施例2〜3
実施例1に示す方法で、ポリカーボネートジオールPC4およびポリカーボネートジオールPC5を用い、水性ポリウレタン組成物を得た。ポリカーボネートジオールPC4を用いた水性ポリウレタン組成物をPUD4と、ポリカーボネートジオールPC5を用いた水性ポリウレタン組成物をPUD5とそれぞれ称する。
Examples 2-3
By the method shown in Example 1, an aqueous polyurethane composition was obtained using polycarbonate diol PC4 and polycarbonate diol PC5. The aqueous polyurethane composition using polycarbonate diol PC4 is referred to as PUD4, and the aqueous polyurethane composition using polycarbonate diol PC5 is referred to as PUD5.
上記の実施例と比較例で使用したイソシアネートなどの仕込み量を下記表1に示す。 Table 1 below shows the amounts of the isocyanate and the like used in the above examples and comparative examples.
耐薬品性、耐加水分解性、耐候性、柔軟性、密着性など物性バランスに優れた、塗料、コーティング材、接着剤、粘着剤などの用途に利用することが出来る。 It can be used for applications such as paints, coating materials, adhesives, and pressure-sensitive adhesives that have excellent balance of physical properties such as chemical resistance, hydrolysis resistance, weather resistance, flexibility, and adhesion.
Claims (3)
(式中、R1は、2−メチル−1,3プロパンジオールに由来するアルキレン基を除く、炭素数2〜20のアルキレン基を表す) From a reaction product of a urethane prepolymer and a chain extender comprising (a) an organic isocyanate, (b) a polycarbonate diol, and (c) a compound having one hydrophilic center and at least two isocyanate-reactive groups. The polycarbonate diol of (b) contains repeating units of the following formula (A) and the following formula (B), the terminal group is a hydroxyl group, and the ratio of (A) and (B) is 99: 1 in molar ratio. An aqueous polyurethane composition characterized by being a polycarbonate diol having a number average molecular weight of 300 to 10,000 at ˜1: 99.
(In the formula, R 1 represents an alkylene group having 2 to 20 carbon atoms, excluding an alkylene group derived from 2-methyl-1,3-propanediol)
(CH2)n (C)
(式中、nは、2〜10の整数を表す。) The aqueous polyurethane composition according to claim 1, wherein R 1 in the formula (B) is represented by the following formula (C).
(CH 2 ) n (C)
(In the formula, n represents an integer of 2 to 10.)
(CH2)m (D)
(式中、mは、4または6の整数を表す。) The aqueous polyurethane composition according to claim 1, wherein R 1 in the formula (B) is represented by the following formula (D).
(CH 2 ) m (D)
(In the formula, m represents an integer of 4 or 6.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006213078A JP5071958B2 (en) | 2006-08-04 | 2006-08-04 | Aqueous polyurethane composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006213078A JP5071958B2 (en) | 2006-08-04 | 2006-08-04 | Aqueous polyurethane composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2008037987A true JP2008037987A (en) | 2008-02-21 |
JP5071958B2 JP5071958B2 (en) | 2012-11-14 |
Family
ID=39173388
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2006213078A Active JP5071958B2 (en) | 2006-08-04 | 2006-08-04 | Aqueous polyurethane composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5071958B2 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010159367A (en) * | 2009-01-09 | 2010-07-22 | Asahi Kasei Chemicals Corp | Curable composition for use in water-based soft-feel coating whose coated film is improved in flexibility and resistance balance |
WO2010098317A1 (en) * | 2009-02-26 | 2010-09-02 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and method for producing same |
WO2010098318A1 (en) * | 2009-02-26 | 2010-09-02 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and method for producing same |
US8552109B2 (en) | 2008-05-29 | 2013-10-08 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion, preparation method of the same, and coating composition containing the same |
US8841381B2 (en) | 2009-08-20 | 2014-09-23 | Ube Industries Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
US8859676B2 (en) | 2009-02-26 | 2014-10-14 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
JPWO2019225540A1 (en) * | 2018-05-21 | 2021-01-07 | 旭化成株式会社 | Polycarbonate diol |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05171091A (en) * | 1991-12-18 | 1993-07-09 | Sakata Corp | Aqueous polyurethane resin, its production, and its use |
JP3201532B2 (en) * | 1991-08-06 | 2001-08-20 | 旭化成株式会社 | Polyurethane emulsion |
-
2006
- 2006-08-04 JP JP2006213078A patent/JP5071958B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3201532B2 (en) * | 1991-08-06 | 2001-08-20 | 旭化成株式会社 | Polyurethane emulsion |
JPH05171091A (en) * | 1991-12-18 | 1993-07-09 | Sakata Corp | Aqueous polyurethane resin, its production, and its use |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8552109B2 (en) | 2008-05-29 | 2013-10-08 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion, preparation method of the same, and coating composition containing the same |
JP2010159367A (en) * | 2009-01-09 | 2010-07-22 | Asahi Kasei Chemicals Corp | Curable composition for use in water-based soft-feel coating whose coated film is improved in flexibility and resistance balance |
WO2010098317A1 (en) * | 2009-02-26 | 2010-09-02 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and method for producing same |
WO2010098318A1 (en) * | 2009-02-26 | 2010-09-02 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and method for producing same |
JPWO2010098318A1 (en) * | 2009-02-26 | 2012-08-30 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and method for producing the same |
US8859676B2 (en) | 2009-02-26 | 2014-10-14 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
US8912280B2 (en) | 2009-02-26 | 2014-12-16 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
JP5716662B2 (en) * | 2009-02-26 | 2015-05-13 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and method for producing the same |
US8841381B2 (en) | 2009-08-20 | 2014-09-23 | Ube Industries Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
JPWO2019225540A1 (en) * | 2018-05-21 | 2021-01-07 | 旭化成株式会社 | Polycarbonate diol |
Also Published As
Publication number | Publication date |
---|---|
JP5071958B2 (en) | 2012-11-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5797954B2 (en) | Water-dispersible urethane prepolymer, water-dispersed polyurethane resin and water-based coating composition using the same | |
JP5457039B2 (en) | Curable composition for water-based soft-feel coatings with improved coating flexibility and resistance balance | |
JP5071958B2 (en) | Aqueous polyurethane composition | |
EP2281848A1 (en) | Aqueous polyurethane resin dispersion, manufacturing method thereof, and paint composition containing the same | |
JP6129681B2 (en) | Polycarbonate diol, thermoplastic polyurethane, coating composition and coating film | |
KR101791283B1 (en) | Aqueous anionic polyurethane dispersions | |
JP6578636B2 (en) | Aqueous polyurethane resin emulsion composition, synthetic leather using the composition, and surface treatment agent for artificial leather | |
JP5570043B2 (en) | Curable composition for soft feel coatings with fast drying speed and improved resistance | |
US20160376438A1 (en) | Urea-free polyurethane dispersions | |
EP3674341B1 (en) | Polyisocyanate mixture, coating composition, and coating film | |
JP2019123871A (en) | Highly branched polycarbonate polyol composition | |
JP5344365B2 (en) | Aqueous polyurethane dispersion and method for producing the same | |
JP2008038281A (en) | Polyurethane emulsion for artificial leather and artificial leather | |
JP4969175B2 (en) | Coating agent composition | |
JP2011162643A (en) | Aqueous polyurethane composition | |
JP6329457B2 (en) | Copolycarbonate diol, thermoplastic polyurethane, coating composition and coating film | |
JP2017137406A (en) | Polycarbonate diol | |
JP6590671B2 (en) | Water-based urethane resin, method for producing water-based urethane resin, and antirust treatment agent | |
JP2010241990A (en) | Polycarbonate diol | |
JP6492491B2 (en) | Aqueous polyurethane resin emulsion composition, artificial leather using the composition, and surface treatment agent for synthetic leather | |
JPH11228654A (en) | Polyurethane-based emulsion for water-based coating material and water-based coating material using the same | |
JP2021075632A (en) | Coating composition | |
JP3560108B2 (en) | Aqueous polyurethane-acryl emulsion composition and aqueous emulsion paint using the same | |
JPH11323252A (en) | Polyurethane-based emulsion for water-based coating material and water-based coating using the same | |
JP7167446B2 (en) | Aqueous polyurethane resin composition, artificial leather using said composition, surface treatment agent for leather |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090731 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111212 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111222 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120815 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120816 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5071958 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150831 Year of fee payment: 3 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |