JP3957018B2 - Water-based polyurethane resin composition - Google Patents
Water-based polyurethane resin composition Download PDFInfo
- Publication number
- JP3957018B2 JP3957018B2 JP25723197A JP25723197A JP3957018B2 JP 3957018 B2 JP3957018 B2 JP 3957018B2 JP 25723197 A JP25723197 A JP 25723197A JP 25723197 A JP25723197 A JP 25723197A JP 3957018 B2 JP3957018 B2 JP 3957018B2
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane resin
- polyol
- water
- acid
- resin composition
- 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.)
- Expired - Fee Related
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims description 57
- 239000011342 resin composition Substances 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 39
- 229920005862 polyol Polymers 0.000 claims description 49
- 150000003077 polyols Chemical class 0.000 claims description 49
- -1 ether ester compound Chemical class 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 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 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 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 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012188 paraffin wax Substances 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
- 229920000573 polyethylene Polymers 0.000 description 2
- 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 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical group OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- 229960004418 trolamine Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-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
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-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
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- IKWQWOFXRCUIFT-UHFFFAOYSA-N benzene-1,2-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C(=O)NN IKWQWOFXRCUIFT-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
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- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
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- 239000004917 carbon fiber Substances 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QTBWAKWPKYZSRL-UHFFFAOYSA-N ethenol;phenol Chemical group OC=C.OC1=CC=CC=C1 QTBWAKWPKYZSRL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- NKUJQQWJJANFIN-UHFFFAOYSA-N hepta-1,4,6-trien-3-one Chemical compound C=CC=CC(=O)C=C NKUJQQWJJANFIN-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 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
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940117013 triethanolamine oleate Drugs 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、水系ポリウレタン樹脂組成物に関し、詳しくは、特定のエーテルエステル化合物を配合してなる、水分散物の保存安定性および硬化物物性に優れた水系ポリウレタン樹脂組成物に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
塗料、接着剤、バインダー、コーティング剤、繊維などの処理剤あるいは各種仕上げ加工剤などの分野においてポリウレタン樹脂が用いられているが、斯る分野においても、環境問題や人体への悪影響を考え、有機溶剤の使用が制限されてきており、有機溶剤をほとんど含まない水系ポリウレタン樹脂への移行が進行し、その使用量も増加している。
【０００３】
この水系ポリウレタン樹脂は、一般に、末端にイソシアネート基を有するプレポリマーを、低分子量の鎖延長剤および必要に応じて界面活性剤を含有する水中に加えることによって鎖延長（高分子量化）と水分散を同時に行わせて製造されるため、ポリマー主鎖に多量のウレタン結合またはウレア結合を有することとなり、その構造が剛直化し伸びが小さくなる欠点があった。また、乾燥後に残存する界面活性剤は乾燥塗膜の物性に悪影響を及ぼすことが多いため、界面活性剤の使用量を低減したりあるいは界面活性剤を使用しなくとも水分散性または水溶性を付与するために、分子中にカルボキシル基またはスルホン酸基を有するポリオールまたは分子中に塩基性基を有するポリオールを用いて構造中に親水性基を導入することも行われているが、この場合には、用いられるこれらのポリオールが低分子量の化合物であるため、上記の欠点がより顕著に現れる。
【０００４】
また、繊維処理剤として水系ポリウレタン樹脂を使用した場合にも、上記の欠点によって風合いが不良となることが多かった。
【０００５】
これまで、ポリウレタン樹脂に可塑剤を配合して柔軟性を付与することが行われており、例えば、特開平７−２６１３７号公報にはジオクチルフタレート、ジオクチルアジペート等のエステル系可塑剤、ポリオキシエチレンアルキルエーテル等のポリエーテル系可塑剤、プロピレングリコールモノメチルエーテルアセテート等の低分子量エーテルエステル系可塑剤を配合したポリウレタンエラストマーが記載されている。しかしながら、水系ポリウレタン樹脂にこれらの可塑剤を配合しても物性の改善効果が不十分で、また、クリーニングを繰り返した場合にその効果が失われてしまうばかりでなく、水系ポリウレタン樹脂の保存安定性が低下する欠点もあり、実用上満足できるものではなかった。
【０００６】
従って、本発明の目的は、水分散物の保存安定性および硬化物物性に優れ、特に繊維製品の処理剤として用いた場合において風合いがよく、消臭性、抗菌性および耐洗濯性に優れた繊維製品を提供することが可能な水系ポリウレタン樹脂組成物を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者等は、種々検討を重ねた結果、水系ポリウレタン樹脂に特定のエーテルエステル化合物を配合することによって、上記目的が達成されることを見出し、本発明に到達した。
【０００８】
即ち、本発明は、水系ポリウレタン樹脂の樹脂固形分１００重量部に対し、下記一般式（Ｉ−１）〜（Ｉ−４）で表されるエーテルエステル化合物１〜１００重量部を配合してなる水系ポリウレタン樹脂組成物であって、水系ポリウレタン樹脂が、有機ポリイソシアネート（Ａ）、ポリオール（Ｂ）および分子中にカルボキシル基もしくはスルホン酸基を有するポリオールまたは分子中に塩基性基を有するポリオール（Ｃ）から製造されるポリウレタン樹脂に、中和剤を併用したものである水系ポリウレタン樹脂組成物を提供するものである。
【０００９】
【化２】
【発明の実施の形態】
以下、本発明の水系ポリウレタン樹脂組成物について詳述する。
【００１１】
本発明において用いられる水系ポリウレタン樹脂は、分子中にカチオン性基またはアニオン性基を導入してこれを中和する方法により得られるものである。
【００１２】
上記方法により得られるものは、硬化物の風合いおよび耐水性などの物性が優れ、かつ、水分散物の保存安定性が優れる。具体的には、有機ポリイソシアネート（Ａ）、ポリオール（Ｂ）および分子中にカルボキシル基またはスルホン酸基を有するポリオールまたは分子中に塩基性基を有するポリオール（Ｃ）を、反応に不活性で水との親和性の大きい溶媒中でウレタン化反応させてプレポリマーとし、次いで、プレポリマーを中和、鎖延長し、水を加えて水性ウレタン樹脂とすることによって製造される。
【００１３】
水系ポリウレタン樹脂を製造するために使用される上記有機ポリイソシアネート（Ａ）としては、脂肪族、脂環式および芳香族ポリイソシアネートがあげられ、具体的には、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、４，４−ジフェニルメタンジイソシアネート、フェニレンジイソシアネート、キシリレ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、テトラ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、リジンジイソシアネートエステル、１，４−シクロヘキシ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、３，３’−ジメトキシ−４，４’−ビフェニレンジイソシアネート、１，５−ナフタレンジイソシアネート、１，５−テトラヒドロナフタレンジイソシアネート、イソホロンジイソシアネート等があげられる。
【００１４】
これらの有機ポリイソシアネート（Ａ）は、上記ポリオール（Ｂ）、上記ポリオール（Ｃ）および後述する鎖延長剤の活性水素の合計に対し、好ましくは０．８〜３倍当量、より好ましくは１〜２倍当量となるように使用される。有機ポリイソシアネート（Ａ）の使用量が０．８倍当量未満の場合には過剰のポリオール等が残存することとなり、また、３倍当量より多い場合には水を加えたときに尿素結合を多量に生成することとなり、いずれの場合もその特性を低下させるおそれがある。
【００１５】
水系ポリウレタン樹脂を製造するために使用される上記ポリオール（Ｂ）としては、公知のポリオールがあげられるが、芳香環構造を有するポリオールの少なくとも一種を全ポリオール成分中１０重量％以上、特に５０重量％以上を用いることが、より安定性に優れたものが得られるため好ましい。
【００１６】
上記芳香環構造を有するポリオールとしては、例えば、ハイドロキノン、レゾルシン、ビスフェノールＡのエチレンオキシドおよび／またはプロピレンオキシド付加物等の芳香族環を有する低分子量ポリオールあるいはこれらを開始剤としてエチレンオキシドおよび／またはプロピレンオキシドを付加してなるポリエーテルポリオール；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、１，２−ブチレングリコール、１，３−ブチレングリコール、１，４−ブチレングリコール、ヘキサメチレングリコール、ハイドロキノン、レゾルシン、水添ビスフェノールＡ、ビスフェノールＡのエチレンオキシドおよび／またはプロピレンオキシド付加物等の低分子量ポリオールあるいはこれらを開始剤としてエチレンオキシドおよび／またはプロピレンオキシドを付加して得られるポリエーテルポリオールとフタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ピロメリット酸、ビフェニルテトラカルボン酸等の芳香族多価カルボン酸の少なくとも一種から選ばれる多塩基酸との縮合物あるいはこれら芳香族多価カルボン酸とともにコハク酸、グルタル酸、アジピン酸、セバチン酸等のその他の多塩基酸との縮合物であるポリエステルポリオールなどがあげられるが、特に芳香族多価カルボン酸を用いて得られる芳香族環含有ポリオールを用いることが、水分散物の保存安定性が一層優れたものが得られるため好ましい。
【００１７】
また、上記ポリオール（Ｂ）として用いられるその他の公知のポリオールとしては、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、１，２−ブチレングリコール、１，３−ブチレングリコール、１，４−ブチレングリコール、ヘキサメチレングリコール、水添ビスフェノールＡのエチレンオキシドおよび／またはプロピレンオキシド付加物等の低分子量ポリオール、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレン／プロピレングリコール、ポリテトラメチレングリコール等、または、上記低分子量ポリオールを開始剤としてエチレンオキシドおよび／またはプロピレンオキシドを付加してなるポリエーテルポリオール、上記低分子量ポリオールとコハク酸、グルタル酸、アジピン酸、セバチン酸等の多塩基酸あるいは炭酸との縮合物であるポリエステルポリオール、ポリカーボネートポリオールおよびポリカプロラクトン等があげられる。
【００１８】
水系ポリウレタン樹脂を製造するために使用される上記ポリオール（Ｃ）のうち、分子中にカルボキシル基もしくはスルホン酸基を有するポリオールとしては、例えば、２，２−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、１，４−ブタンジオール−２−スルホン酸等があげられ、また、分子中に塩基性基を有するポリオールとしては、例えば、メチルジエタノールアミン、ブチルジエタノールアミン、トリエタノールアミン、トリイソプロパノールアミンなどがあげられ、特に、カルボキシル基を有するポリオールを用いた場合には分散性に優れる水性ウレタンが得られるので好ましい。
【００１９】
これらのポリオール（Ｃ）の使用量は、用いるポリオールおよびポリイソシアネートの種類にもよるが、通常は、水系ポリウレタン樹脂を構成する全ての反応成分に対して、０．５〜５０重量％、好ましくは１〜３０重量％が用いられる。ポリオール（Ｃ）の使用量が０．５重量％未満では保存安定性が劣り、また、５０重量％を超えて使用すると特性に悪影響を及ぼすことがある。
【００２０】
水系ポリウレタン樹脂を製造するために使用される上記の反応に不活性で水との親和性の大きい溶媒としては、例えば、アセトン、メチルエチルケトン、ジオキサン、テトラヒドロフラン、Ｎ−メチル−２−ピロリドン等をあげることができる。これらの溶媒は、通常、プレポリマーを製造するために用いられる上記原料の合計重量に対して、１０〜１００重量％が用いられる。
【００２１】
また、上記プレポリマーを中和する中和剤としては、上記プレポリマーがアニオン系の場合（ポリオール（Ｃ）として分子中にカルボキシル基もしくはスルホン酸基を有するポリオールを使用した場合）と、上記プレポリマーがカチオン系の場合（ポリオール（Ｃ）として塩基性基を有するポリオールを使用した場合）とによって異なり、上記プレポリマーがアニオン系の場合、例えば、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、トリブチルアミン、Ｎ−メチルジエタノールアミン、トリエタノールアミン等の有機アミン、水酸化ナトリウム、水酸化カリウム、アンモニア等の無機塩基があげられ、これらはカルボキシル基またはスルホン酸基を中和するに十分な量が用いられる。また、上記プレポリマーがカチオン系の場合、例えば、蟻酸、蓚酸、リン酸、硼酸、塩酸、炭酸、酢酸、ジメチロールプロピオン酸等の酸類があげられ、これらはポリオール塩基を中和するのに十分な量が用いられる。
【００２２】
また、上記プレポリマーを鎖延長する鎖延長剤としては、例えば、エチレングリコール、プロピレングリコールなどのポリオール類、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、トリレンジアミン、キシリレンジアミン、ジアミノジフェニルメタン、ジアミノシクロヘキシルメタン、ピペラジン、２−メチルピペラジン、イソホロンジアミン、メラミン、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、フタル酸ジヒドラジド等のアミン類および水等があげられる。これらの鎖延長剤の使用量は、目的とするポリウレタン樹脂の分子量にもよるが、通常は、プレポリマーに対して０．５〜１０重量％が用いられる。
【００２３】
前述のように、これらの原料から水系ポリウレタン樹脂を製造する製造方法自体は周知であり、これらの原料の仕込み順序を適宜変更したり、あるいは分割して仕込むことも可能である。
【００２４】
このようにして得られた水系ポリウレタン樹脂は、通常、樹脂固形分が１〜９０重量％、より好ましくは５〜８０重量％となるように調整される。
【００２５】
また、水系ポリウレタン樹脂としては、市販されている水系ポリウレタン樹脂をそのまま使用することも勿論可能であり、例えば、旭電化工業（株）製の「アデカボンタイター」シリーズ、三井東圧化学（株）製の「オレスター」シリーズ、大日本インキ化学工業（株）製の「ボンディック」シリーズ、「ハイドラン」シリーズ、バイエル社製の「インプラニール」シリーズ、日本ソフラン（株）製の「ソフラネート」シリーズ、花王（株）製の「ポイズ」シリーズ、三洋化成工業（株）製の「サンプレン」シリーズ、保土谷化学工業（株）製の「アイゼラックス」シリーズ、第一工業製薬（株）製の「スーパーフレックス」シリーズ、ゼネカ（株）製の「ネオレッツ」シリーズ等を用いることができる。
【００２６】
また、上記水系ポリウレタン樹脂に配合される上記一般式（Ｉ−１）〜（Ｉ−４）で表されるエーテルエステル化合物において、該一般式中のR1、R3およびR4で示される炭素原子数１〜１８のアルキル基としては、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシルなどの直鎖あるいは分岐の基があげられ、アリール基としては、例えば、フェニル、ナフチルなどがあげられ、アルキルアリール基としては、例えば、上記アルキル基によって置換されてなる上記アリール基などがあげられ、R2で表される炭素原子数１〜１２のアルキレン基としては、例えば、エチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン、ヘプチレン、オクチレン、ノニレン、デシレン、ウンデシレン、ドデシレンなどの直鎖あるいは分岐の基があげられ、アリーレン基としては、例えば、フェニレン、ナフチレンなどの基があげられ、Ａで表される炭素原子数２〜４のアルキレン基としては、エチレン、プロピレン、ブチレンなどの直鎖あるいは分岐の基があげられる。
【００２７】
上記一般式（Ｉ−１）〜（Ｉ−４）で表されるエーテルエステル化合物としては、例えば、下記の化合物１〜４０などがあげられる。ここでｎは１〜２０の数を表す。
【００２８】
【化３】
【化４】
【化５】
【化６】
【化７】
これらエーテルエステル化合物は、水系ポリウレタン樹脂の樹脂固形分１００重量部に対して、１〜１００重量部、より好ましくは５〜５０重量部使用され、１重量部未満の使用ではその使用効果がほとんどみられず、１００重量部を越えて使用した場合には、硬化物の物性を低下するおそれがある。
【００３４】
エーテルエステル化合物を水系ポリウレタン樹脂に配合する方法は、水系ポリウレタン樹脂製造後に配合する方法でもよく、エーテルエステル化合物の存在下で有機ポリイソシアネート（Ａ）、ポリオール（Ｂ）およびポリオール（Ｃ）を反応させることによって最終製品に残存させる方法でもよい。
【００３５】
また、本発明の水系ポリウレタン樹脂組成物には、乳化剤を配合することができ、該乳化剤としては、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、高分子界面活性剤または反応性界面活性剤など全ての界面活性剤を使用することができる。
【００３６】
上記アニオン性界面活性剤としては、例えば、ナトリウムドデシルサルフェート、カリウムドデシルサルフェート、アンモニウムドデシルサルフェートなどのアルキルサルフェート；ナトリウムドデシルポリグリコールエーテルサルフェート；ナトリウムスルホリシノート；スルホン化パラフィンのアルカリ金属塩、スルホン化パラフィンのアンモニウム塩などのアルキルスルホネート；ナトリウムラウレート、トリエタノールアミンオレート、トリエタノールアミンアビエテートなどの脂肪酸塩；ナトリウムベンゼンスルホネート、アルカリフェノールヒドロキシエチレンのアルカリ金属サルフェートなどのアルキルアリールスルホネート；高アルキルナフタレンスルホン酸塩；ナフタレンスルホン酸ホルマリン縮合物；ジアルキルスルホコハク酸塩；ポリオキシエチレンアルキルサルフェート塩；ポリオキシエチレンアルキルアリールサルフェート塩などがあげられる。
【００３７】
上記ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル；ポリオキシエチレンアルキルアリールエーテル；ソルビタン脂肪酸エステル；ポリオキシエチレンソルビタン脂肪酸エステル；脂肪酸モノグリセライド；トリメチロールプロパン脂肪酸エステル；ポリオキシエチレンオキシプロピレン共重合体；エチレンオキサイドの脂肪酸アミン、アミドまたは酸との縮合生成物などがあげられる。
【００３８】
上記カチオン性界面活性剤としては、例えば、第１〜３級アミン塩；ピリジニウム塩；第４級アンモニウム塩などがあげられる。
【００３９】
上記高分子界面活性剤としては、例えば、ポリビニルアルコール；ポリ（メタ）アクリル酸ナトリウム、ポリ（メタ）アクリル酸カリウム、ポリ（メタ）アクリル酸アンモニウム、ポリヒドロキシエチル（メタ）アクリレート；ポリヒドロキシプロピル（メタ）アクリレート；またこれらの重合体構成単位である重合性単量体の２種以上の共重合体または他の単量体との共重合体などがあげられる。また、クラウンエーテル類などの相関移動触媒と称されるものも界面活性を示すものとして有用である。
【００４０】
本発明の水系ポリウレタン樹脂組成物には、必要に応じて他の水性分散体や水分散液、例えば、酢酸ビニル系、エチレン−酢酸ビニル系、アクリル系、アクリル−スチレン系等のエマルジョン；スチレン−ブタジエン系、アクリロニトリル−ブタジエン系、アクリル−ブタジエン系等のラテックス；ポリエチレン系、ポリオレフィン系等のアイオノマー；ポリエステル、ポリアミド、エポキシ樹脂等の各種水性分散体、水分散液を併用することができる。
【００４１】
また、本発明の水系ポリウレタン樹脂組成物には、必要に応じて、フェノール系抗酸化剤、有機ホスファイトまたはホスホナイトなどの有機リン系抗酸化剤、チオエーテル系抗酸化剤、紫外線吸収剤あるいはヒンダードアミン化合物などの光安定剤、フッ素系またはシロキサン系などの帯電防止剤、コロイダルシリカまたはコロイダルアルミナなどの無機質コロイドゾル、シランカップリング剤、着色剤、ワックス類、防腐剤、消泡剤、可塑剤、フィラー、溶剤、造膜助剤、分散剤、増粘剤、香料等の慣用の添加物を加えることもできる。
【００４２】
本発明の水系ポリウレタン樹脂組成物は、塗料、接着剤、バインダー、コーティング剤、繊維などの処理剤あるいは各種仕上げ加工剤などの分野において使用することができ、とりわけ、繊維製品の処理剤として使用する場合、風合いを与え、また、難燃、消臭、抗菌効果もあるので好ましい。
【００４３】
本発明の水系ポリウレタン樹脂組成物を繊維製品の仕上げ剤として使用する場合の繊維基材としては、例えば、綿、麻等の天然繊維、レーヨン、ナイロン、ポリエステル、ポリウレタン、アクリル等の人工・合成繊維、またこれらの混紡繊維あるいはガラス繊維、炭素繊維等の無機繊維などがあげられる。
【００４４】
本発明の水系ポリウレタン樹脂組成物を繊維製品の仕上げ剤として使用する場合には、これを含有する処理浴を予め調製し、この中に繊維基材を浸漬、含浸させ、必要な付着量となるようマングロール等で絞り、乾燥させればよい。
【００４５】
また、本発明の水系ポリウレタン樹脂組成物を塗料などとして使用する場合には、グラビアコート法、リバースロールコート法、エアナイフコート法、バーコート法、ドクターブレードコート法、カーテンロールコート法、ディップコート法、スプレーコート法、ロッドコート法などのコーティング法を用いて、基材に塗布して乾燥することによって、塗膜を形成することができる。
【００４６】
【実施例】
以下、製造例および実施例によって本発明をさらに詳細に説明するが、本発明は下記の実施例によって制限を受けるものではない。尚、製造例および実施例における部は特にことわりのないかぎり重量部を表す。
【００４７】
製造例１
ポリエステルポリオール１（イソフタル酸／アジピン酸〔１：１〕とヘキサンジオールの縮合物、平均分子量１０００）１００部、イソホロンジイソシアネート１０７部、ジメチロールプロピオン酸２０部およびＮ−メチルピロリドン１００部を反応容器にとり、８０〜１００℃に保ちながら反応させて、プレポリマーを製造した。
【００４８】
次いで、トリエチルアミン１８部を加えて中和した後、ヘキサメチレンジアミン５部を加え、水を添加しながら３５℃以下で架橋反応を行い、反応終了までに６５０部の水を加えて樹脂固形分２３重量％の水系ポリウレタン樹脂Ａを製造した。
【００４９】
上記製造例１と同様な操作により、次の〔表１〕の水系ポリウレタン樹脂ＢおよびＣを製造した。
【００５０】
製造例２
ポリエステルポリオール１（イソフタル酸／アジピン酸〔１：１〕とヘキサンジオールの縮合物、平均分子量１０００）１００部、イソホロンジイソシアネート１０７部、ジメチロールプロピオン酸２０部、Ｎ−メチルピロリドン１００部およびエーテルエステル化合物１０（ｎ＝７）１００部を反応容器にとり、８０〜１００℃に保ちながら反応させて、プレポリマーを製造した。
【００５１】
次いで、トリエチルアミン１８部を加えて中和した後、ヘキサメチレンジアミン５部を加え、水を添加しながら３５℃以下で架橋反応を行い、反応終了までに５５０部の水を加えて樹脂固形分３３重量％の水系ポリウレタン樹脂Ｄを製造した。
【００５２】
上記製造例２と同様な操作により、次の〔表１〕の水系ポリウレタン樹脂Ｅ〜Ｇを製造した。
【００５３】
【表１】
実施例１
上記製造例により得られた水系ポリウレタン樹脂を用いて、次の〔表２〕および〔表３〕に示したような水性分散体（水系ポリウレタン樹脂組成物）を調製し、５℃および４０℃で３か月および６か月後の保存安定性を下記基準により評価した。ただし、可塑剤成分を配合する場合は、水系ポリウレタン樹脂の樹脂固形分１００部に対して１０部撹拌混合した。
【００５５】
（保存安定性の評価基準）
１：良好なエマルジョンを保っている。
２：若干分離が見られる。
３：分離が見られる。
４：完全に分離している。
【００５６】
また、型枠をつけたガラス板上にシートの厚さ１ｍｍとなるように上記水性分散体を流し込み、４０℃で２日間乾燥した。これを１００℃で３分間乾燥してＪＩＳ Ｋ ７１１３に準じて１００％モジュラス（Ｋｇ／ｃｍ2 ）および伸び（％）を求めた。
【００５７】
また、上記水性分散体にＴ／Ｃ＝６５／３５綿ブロード布を浸漬し、マングルロールで固形分付着率７０％に絞った後、１００℃で２分さらに１７０℃で１分熱風乾燥処理し、剛軟度、風合いおよび色合いを評価した。また、ドライクリーニングを３回実施したものについても評価した。
【００５８】
ここで剛軟度は、ＪＩＳ Ｌ １０９６に準じてカンチレバー法にて剛軟度を測定し、風合いは手触り、色合いは目視により評価した。
【００５９】
その結果を次の〔表２〕および〔表３〕に示した。
【００６０】
【表２】
【表３】
実施例および比較例から明らかなように、水系ポリウレタン樹脂に可塑剤成分を全く使用しない場合（比較例１−３）には柔軟性が得られず、これで繊維製品を処理した場合にも、風合いは硬く、色合いもくすんだ感じのものしかえられず、これに本発明以外のエーテルエステル化合物を配合した場合（比較例１−１）もこれらの改善効果は小さい。さらに汎用の可塑剤であるジ−２−エチルヘキシルフタレート又はエポキシ化大豆油を配合したもの（比較例１−４および比較例１−２）は、繊維処理剤として使用した場合に初期における風合いや色合いは優れたものを提供するが、クリーニングを繰り返すことによりその性能は低下し、エマルジョンの保存安定性も不十分である。
【００６３】
これに対して、水系ポリウレタン樹脂に特定のエーテルエステル化合物を配合してなる本発明の水系ポリウレタン樹脂組成物を繊維処理剤として使用した場合（実施例１−１〜１−９）には、エマルジョンの安定性に優れ、また柔軟なシートを提供し、さらに繊維に良好な風合いや色合いを付与し、クリーニングをした後においてもその性能は維持される。
【００６４】
【発明の効果】
本発明の水系ポリウレタン樹脂組成物は、水分散物の保存安定性および硬化物物性に優れ、特に繊維製品の処理剤として用いた場合において風合いがよく、消臭性、抗菌性および耐洗濯性に優れた繊維製品を提供することが可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aqueous polyurethane resin composition, and more particularly, to an aqueous polyurethane resin composition excellent in storage stability and cured physical properties of an aqueous dispersion, which is formed by blending a specific ether ester compound.
[0002]
[Prior art and problems to be solved by the invention]
Polyurethane resins are used in the fields of paints, adhesives, binders, coating agents, processing agents such as fibers, and various finishing agents. In these fields as well, considering environmental issues and adverse effects on the human body, The use of solvents has been restricted, and the shift to water-based polyurethane resins containing almost no organic solvent has progressed, and the amount used has also increased.
[0003]
This water-based polyurethane resin generally has a chain extension (high molecular weight) and water dispersion by adding a prepolymer having an isocyanate group at the end to water containing a low molecular weight chain extender and optionally a surfactant. Since the polymer main chain has a large amount of urethane bonds or urea bonds, the structure has a drawback that the structure becomes rigid and elongation is reduced. In addition, since the surfactant remaining after drying often adversely affects the properties of the dried coating film, water dispersibility or water solubility can be reduced even if the amount of the surfactant used is reduced or no surfactant is used. In order to impart, a hydrophilic group is also introduced into the structure using a polyol having a carboxyl group or a sulfonic acid group in the molecule or a polyol having a basic group in the molecule. Since these polyols used are low molecular weight compounds, the above-mentioned defects appear more remarkably.
[0004]
In addition, when a water-based polyurethane resin is used as a fiber treatment agent, the texture is often poor due to the above-described defects.
[0005]
Up to now, it has been performed to add flexibility by adding a plasticizer to a polyurethane resin. For example, JP-A-7-26137 discloses ester plasticizers such as dioctyl phthalate and dioctyl adipate, and polyoxyethylene. A polyurethane elastomer containing a polyether plasticizer such as alkyl ether and a low molecular weight ether ester plasticizer such as propylene glycol monomethyl ether acetate is described. However, even if these plasticizers are added to the water-based polyurethane resin, the effect of improving the physical properties is not sufficient, and not only the effect is lost when cleaning is repeated, but also the storage stability of the water-based polyurethane resin. However, it was not satisfactory for practical use.
[0006]
Therefore, the object of the present invention is excellent in the storage stability and cured product properties of the aqueous dispersion, particularly in the case of being used as a treating agent for textile products, and excellent in deodorizing properties, antibacterial properties and washing resistance. An object of the present invention is to provide an aqueous polyurethane resin composition capable of providing a textile product.
[0007]
[Means for Solving the Problems]
As a result of various studies, the present inventors have found that the above object can be achieved by blending a specific ether ester compound with an aqueous polyurethane resin, and have reached the present invention.
[0008]
That is, the present invention is obtained by blending 1 to 100 parts by weight of an ether ester compound represented by the following general formulas (I-1) to (I-4) with respect to 100 parts by weight of a resin solid content of an aqueous polyurethane resin. A water-based polyurethane resin composition, wherein the water-based polyurethane resin is an organic polyisocyanate (A), a polyol (B), a polyol having a carboxyl group or a sulfonic acid group in the molecule, or a polyol having a basic group in the molecule (C The water-based polyurethane resin composition is a polyurethane resin produced by using a neutralizing agent in combination with the polyurethane resin produced from (1).
[0009]
[Chemical 2]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the water-based polyurethane resin composition of the present invention will be described in detail.
[0011]
Aqueous polyurethane resin used in the present invention are those more obtained how to neutralize this by introducing a cationic group or an anionic group in the molecular.
[0012]
What is obtained by the above method is excellent in the physical properties such as the texture and water resistance of the cured product, and is excellent in the storage stability of the aqueous dispersion . Specifically, the organic polyisocyanate (A), the polyol (B), the polyol having a carboxyl group or a sulfonic acid group in the molecule, or the polyol (C) having a basic group in the molecule are water and inert to the reaction. It is produced by making a urethanation reaction in a solvent having a high affinity with the prepolymer, then neutralizing the chain, extending the chain, and adding water to make an aqueous urethane resin.
[0013]
Examples of the organic polyisocyanate (A) used for producing the water-based polyurethane resin include aliphatic, alicyclic and aromatic polyisocyanates. Specifically, 2,4-tolylene diisocyanate, 2 , 6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1,4-cyclohexylene diisocyanate, 4,4 '-Dicyclohexylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydrona Data diisocyanate, isophorone diisocyanate and the like.
[0014]
These organic polyisocyanates (A) are preferably 0.8 to 3 times equivalent to the total of active hydrogens of the polyol (B), the polyol (C) and the chain extender described below, more preferably 1 to It is used so that it may become 2 times equivalent. If the amount of the organic polyisocyanate (A) used is less than 0.8 times equivalent, excess polyol or the like will remain, and if it is more than 3 times equivalent, a large amount of urea bonds will be formed when water is added. In any case, there is a risk of deteriorating the characteristics.
[0015]
Examples of the polyol (B) used for producing the water-based polyurethane resin include known polyols. At least one polyol having an aromatic ring structure is at least 10% by weight, particularly 50% by weight, based on the total polyol component. It is preferable to use the above because a more excellent stability can be obtained.
[0016]
Examples of the polyol having an aromatic ring structure include low molecular weight polyols having aromatic rings such as hydroquinone, resorcin, ethylene oxide and / or propylene oxide adducts of bisphenol A, and ethylene oxide and / or propylene oxide using these as initiators. Polyether polyol formed by addition; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene Low in glycol, hexamethylene glycol, hydroquinone, resorcin, hydrogenated bisphenol A, bisphenol A ethylene oxide and / or propylene oxide adducts, etc. Low molecular weight polyols or polyether polyols obtained by adding ethylene oxide and / or propylene oxide with these as initiators and aromatics such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid It is a condensate with a polybasic acid selected from at least one of polyvalent carboxylic acids, or a condensate with these polyvalent carboxylic acids and other polybasic acids such as succinic acid, glutaric acid, adipic acid, and sebacic acid. Polyester polyols and the like can be mentioned, and it is particularly preferable to use an aromatic ring-containing polyol obtained by using an aromatic polyvalent carboxylic acid because a storage stability of the aqueous dispersion can be further improved.
[0017]
Examples of other known polyols used as the polyol (B) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, low molecular weight polyols such as hydrogenated bisphenol A ethylene oxide and / or propylene oxide adducts, polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetra Polyether polyol formed by adding ethylene oxide and / or propylene oxide using methylene glycol or the like or the above low molecular weight polyol as an initiator The low molecular weight polyols and succinic acid, glutaric acid, adipic acid, polyester polyol which is a condensate of a polybasic acid or carbonate such as sebacic acid, polycarbonate polyols and polycaprolactone and the like.
[0018]
Among the polyols (C) used for producing the aqueous polyurethane resin, examples of the polyol having a carboxyl group or a sulfonic acid group in the molecule include 2,2-dimethylolpropionic acid and 2,2-dimethylol. Examples include butyric acid, 2,2-dimethylolvaleric acid, 1,4-butanediol-2-sulfonic acid and the like, and examples of the polyol having a basic group in the molecule include methyldiethanolamine, butyldiethanolamine, and triethanol. Examples thereof include amines and triisopropanolamine. Particularly, when a polyol having a carboxyl group is used, an aqueous urethane excellent in dispersibility is obtained, which is preferable.
[0019]
The amount of these polyols (C) used depends on the types of polyol and polyisocyanate used, but is usually 0.5 to 50% by weight, preferably with respect to all reaction components constituting the aqueous polyurethane resin. 1-30% by weight is used. If the amount of the polyol (C) used is less than 0.5% by weight, the storage stability is inferior, and if it exceeds 50% by weight, the properties may be adversely affected.
[0020]
Examples of the solvent that is inert to the above reaction and has a high affinity for water used to produce an aqueous polyurethane resin include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, and the like. Can do. These solvents are usually used in an amount of 10 to 100% by weight based on the total weight of the raw materials used for producing the prepolymer.
[0021]
Further, as a neutralizing agent for neutralizing the prepolymer, when the prepolymer is anionic (when a polyol having a carboxyl group or a sulfonic acid group in the molecule is used as the polyol (C)), the prepolymer is used. When the polymer is cationic (when a polyol having a basic group is used as the polyol (C)), the prepolymer is anionic, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, N -Organic amines such as methyldiethanolamine and triethanolamine, and inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and these are used in an amount sufficient to neutralize carboxyl groups or sulfonic acid groups. When the prepolymer is cationic, for example, acids such as formic acid, oxalic acid, phosphoric acid, boric acid, hydrochloric acid, carbonic acid, acetic acid, dimethylolpropionic acid, and the like are sufficient to neutralize the polyol base. The correct amount is used.
[0022]
Examples of the chain extender that extends the prepolymer include, for example, polyols such as ethylene glycol and propylene glycol, ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diaminodiphenylmethane, and diaminocyclohexylmethane. And amines such as piperazine, 2-methylpiperazine, isophoronediamine, melamine, succinic acid dihydrazide, adipic acid dihydrazide, and phthalic acid dihydrazide, and water. The amount of these chain extenders is usually 0.5 to 10% by weight based on the prepolymer, although it depends on the molecular weight of the target polyurethane resin.
[0023]
As described above, the production method for producing a water-based polyurethane resin from these raw materials is well known, and the order in which these raw materials are charged can be changed as appropriate or can be charged separately.
[0024]
The aqueous polyurethane resin thus obtained is usually adjusted so that the resin solid content is 1 to 90% by weight, more preferably 5 to 80% by weight.
[0025]
Also, as the water-based polyurethane resin, it is of course possible to use a commercially available water-based polyurethane resin as it is. For example, “Adekabon titer” series manufactured by Asahi Denka Kogyo Co., Ltd., Mitsui Toatsu Chemicals, Inc. "Olestar" series manufactured by Dainippon Ink & Chemicals, Inc. "Bondic" series, "Hydran" series, "Imperil" series manufactured by Bayer, "Sofuranate" series manufactured by Soflan Japan "Poise" series manufactured by Kao Corporation, "Samprene" series manufactured by Sanyo Chemical Industry Co., Ltd., "Izerax" series manufactured by Hodogaya Chemical Co., Ltd., " The “Superflex” series, the “Neolet's” series manufactured by Zeneca Corporation, and the like can be used.
[0026]
In the ether ester compounds represented by the general formulas (I-1) to (I-4) blended in the water-based polyurethane resin, carbons represented by R 1 , R 3 and R 4 in the general formula Examples of the alkyl group having 1 to 18 atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like. Examples of the aryl group include phenyl and naphthyl. Examples of the alkylaryl group include the above aryl group substituted with the above alkyl group, and R. Examples of the alkylene group having 1 to 12 carbon atoms represented by 2 include ethylene, Examples include linear or branched groups such as propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene. Examples of arylene groups include groups such as phenylene and naphthylene. Examples of the alkylene group having 2 to 4 carbon atoms include linear or branched groups such as ethylene, propylene, and butylene.
[0027]
Examples of the ether ester compounds represented by the general formulas (I-1) to (I-4) include the following compounds 1 to 40. Here, n represents a number from 1 to 20.
[0028]
[Chemical 3]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
[Chemical 7]
These ether ester compounds are used in an amount of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight , based on 100 parts by weight of the resin solid content of the water-based polyurethane resin. If it is used in excess of 100 parts by weight, the physical properties of the cured product may be reduced.
[0034]
The method of blending the ether ester compound with the water-based polyurethane resin may be a method of blending after the water-based polyurethane resin is produced, and reacting the organic polyisocyanate (A), polyol (B) and polyol (C) in the presence of the ether ester compound. In some cases, it may be left in the final product.
[0035]
The aqueous polyurethane resin composition of the present invention may contain an emulsifier. Examples of the emulsifier include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, All surfactants such as molecular surfactants or reactive surfactants can be used.
[0036]
Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinone; alkali metal salt of sulfonated paraffin, sulfonated paraffin Alkyl sulfonates such as ammonium salts; fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine abiate; alkyl aryl sulfonates such as sodium benzene sulfonate and alkali metal sulfates of alkali phenol hydroxyethylene; high alkyl naphthalene sulfonic acid Salt; naphthalenesulfonic acid formalin condensate; dialkyl sulfone Haq salt; polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfate salts and the like.
[0037]
Examples of the nonionic surfactant include polyoxyethylene alkyl ether; polyoxyethylene alkyl aryl ether; sorbitan fatty acid ester; polyoxyethylene sorbitan fatty acid ester; fatty acid monoglyceride; trimethylolpropane fatty acid ester; Polymers: Condensation products of ethylene oxide with fatty acid amines, amides or acids.
[0038]
Examples of the cationic surfactant include primary to tertiary amine salts; pyridinium salts; quaternary ammonium salts.
[0039]
Examples of the polymer surfactant include polyvinyl alcohol; sodium poly (meth) acrylate, potassium poly (meth) acrylate, ammonium poly (meth) acrylate, polyhydroxyethyl (meth) acrylate; polyhydroxypropyl ( (Meth) acrylates; and copolymers of two or more kinds of polymerizable monomers that are these polymer constituent units or copolymers with other monomers. Moreover, what are called phase transfer catalysts, such as crown ethers, are also useful as those showing surface activity.
[0040]
In the aqueous polyurethane resin composition of the present invention, other aqueous dispersions and aqueous dispersions, for example, vinyl acetate-based, ethylene-vinyl acetate-based, acrylic-based, acrylic-styrene-based emulsions; Latexes such as butadiene, acrylonitrile-butadiene, and acryl-butadiene; ionomers such as polyethylene and polyolefin; various aqueous dispersions such as polyester, polyamide, and epoxy resin, and aqueous dispersions can be used in combination.
[0041]
Further, the water-based polyurethane resin composition of the present invention includes a phenolic antioxidant, an organic phosphorus antioxidant such as an organic phosphite or phosphonite, a thioether antioxidant, an ultraviolet absorber or a hindered amine compound as necessary. Light stabilizers such as antistatic agents such as fluorine or siloxane, inorganic colloidal sols such as colloidal silica or colloidal alumina, silane coupling agents, colorants, waxes, preservatives, antifoaming agents, plasticizers, fillers, Conventional additives such as a solvent, a film-forming aid, a dispersant, a thickener, and a fragrance can be added.
[0042]
The water-based polyurethane resin composition of the present invention can be used in the fields of coating agents, adhesives, binders, coating agents, treating agents such as fibers or various finishing agents, and in particular, it is used as a treating agent for textile products. In this case, it is preferable because it gives a texture and has flame retardancy, deodorization and antibacterial effects.
[0043]
Examples of the fiber base material when the aqueous polyurethane resin composition of the present invention is used as a finishing agent for textile products include natural fibers such as cotton and hemp, and artificial and synthetic fibers such as rayon, nylon, polyester, polyurethane, and acrylic. In addition, these blended fibers or inorganic fibers such as glass fibers and carbon fibers can be used.
[0044]
When the water-based polyurethane resin composition of the present invention is used as a finishing agent for textile products, a treatment bath containing the same is prepared in advance, and the fiber base material is immersed and impregnated therein to obtain a necessary adhesion amount. What is necessary is just to squeeze and dry with mangroll or the like.
[0045]
Further, when the aqueous polyurethane resin composition of the present invention is used as a paint, the gravure coating method, reverse roll coating method, air knife coating method, bar coating method, doctor blade coating method, curtain roll coating method, dip coating method A coating film can be formed by applying to a substrate and drying using a coating method such as spray coating or rod coating.
[0046]
【Example】
Hereinafter, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited by the following examples. In addition, the part in a manufacture example and an Example represents a weight part unless there is particular notice.
[0047]
Production Example 1
100 parts of polyester polyol 1 (condensate of isophthalic acid / adipic acid [1: 1] and hexanediol, average molecular weight 1000), 107 parts of isophorone diisocyanate, 20 parts of dimethylolpropionic acid and 100 parts of N-methylpyrrolidone are taken in a reaction vessel. , While maintaining the temperature at 80 to 100 ° C., a prepolymer was produced.
[0048]
Next, 18 parts of triethylamine was added for neutralization, 5 parts of hexamethylenediamine was added, a crosslinking reaction was performed at 35 ° C. or lower while adding water, and 650 parts of water was added by the end of the reaction to obtain a resin solid content of 23 A weight% aqueous polyurethane resin A was produced.
[0049]
The following aqueous polyurethane resins B and C shown in [Table 1] were produced in the same manner as in Production Example 1.
[0050]
Production Example 2
100 parts of polyester polyol 1 (condensate of isophthalic acid / adipic acid [1: 1] and hexanediol, average molecular weight 1000), 107 parts of isophorone diisocyanate, 20 parts of dimethylolpropionic acid, 100 parts of N-methylpyrrolidone and ether ester compound 10 parts (n = 7) 100 parts were taken in a reaction vessel and reacted while being kept at 80 to 100 ° C. to produce a prepolymer.
[0051]
Next, after neutralizing by adding 18 parts of triethylamine, 5 parts of hexamethylenediamine is added, and a crosslinking reaction is carried out at 35 ° C. or lower while adding water, and 550 parts of water is added until the reaction is completed to obtain a resin solid content of 33 A weight% aqueous polyurethane resin D was produced.
[0052]
The following water-based polyurethane resins E to G shown in [Table 1] were produced in the same manner as in Production Example 2.
[0053]
[Table 1]
Example 1
Using the aqueous polyurethane resin obtained by the above production example, an aqueous dispersion (aqueous polyurethane resin composition) as shown in the following [Table 2] and [Table 3] was prepared, and at 5 ° C. and 40 ° C. The storage stability after 3 months and 6 months was evaluated according to the following criteria. However, when the plasticizer component was blended, 10 parts were stirred and mixed with respect to 100 parts of the resin solid content of the aqueous polyurethane resin.
[0055]
(Evaluation criteria for storage stability)
1: A good emulsion is maintained.
2: Some separation is observed.
3: Separation is observed.
4: Completely separated.
[0056]
The aqueous dispersion was poured onto a glass plate provided with a mold so that the thickness of the sheet was 1 mm, and dried at 40 ° C. for 2 days. This was dried at 100 ° C. for 3 minutes, and 100% modulus (Kg / cm 2 ) and elongation (%) were determined according to JIS K7113.
[0057]
Further, after immersing T / C = 65/35 cotton broad cloth in the above-mentioned aqueous dispersion and narrowing to a solid content adhesion rate of 70% with mangle roll, it was dried with hot air at 100 ° C. for 2 minutes and further at 170 ° C. for 1 minute. The bending resistance, texture, and hue were evaluated. In addition, an evaluation was also made on the dry cleaning performed three times.
[0058]
Here, the bending resistance was measured by a cantilever method according to JIS L 1096, the texture was touched, and the hue was visually evaluated.
[0059]
The results are shown in the following [Table 2] and [Table 3].
[0060]
[Table 2]
[Table 3]
As is apparent from the examples and comparative examples, when no plasticizer component is used in the water-based polyurethane resin (Comparative Example 1-3), no flexibility is obtained, and even when a textile product is treated with this, The texture is hard and the color is dull, and when an ether ester compound other than the present invention is blended (Comparative Example 1-1), these improvement effects are small. Furthermore, what blended di-2-ethylhexyl phthalate which is a general-purpose plasticizer or epoxidized soybean oil (Comparative Example 1-4 and Comparative Example 1-2) has an initial texture and hue when used as a fiber treatment agent. Provides an excellent product, but the performance is lowered by repeated cleaning, and the storage stability of the emulsion is also insufficient.
[0063]
On the other hand, when the aqueous polyurethane resin composition of the present invention obtained by blending a specific ether ester compound with an aqueous polyurethane resin is used as a fiber treatment agent (Examples 1-1 to 1-9), an emulsion The sheet is excellent in stability and provides a flexible sheet. Further, the fiber has a good texture and color, and its performance is maintained even after cleaning.
[0064]
【The invention's effect】
The water-based polyurethane resin composition of the present invention is excellent in storage stability and cured product properties of an aqueous dispersion, has a good texture especially when used as a treating agent for textiles, and has excellent deodorizing properties, antibacterial properties, and washing resistance. It is possible to provide excellent fiber products.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25723197A JP3957018B2 (en) | 1997-09-22 | 1997-09-22 | Water-based polyurethane resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25723197A JP3957018B2 (en) | 1997-09-22 | 1997-09-22 | Water-based polyurethane resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1192654A JPH1192654A (en) | 1999-04-06 |
| JP3957018B2 true JP3957018B2 (en) | 2007-08-08 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25723197A Expired - Fee Related JP3957018B2 (en) | 1997-09-22 | 1997-09-22 | Water-based polyurethane resin composition |
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| Country | Link |
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| JP (1) | JP3957018B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070020214A (en) * | 2004-02-06 | 2007-02-20 | 닛본 페인트 가부시끼가이샤 | Water-based intercoating composition and method of forming multilayered coating film |
| JP2005220255A (en) * | 2004-02-06 | 2005-08-18 | Asahi Denka Kogyo Kk | Water-dispersing type polyurethane composition |
| JP2007269832A (en) * | 2006-03-30 | 2007-10-18 | Arakawa Chem Ind Co Ltd | Method of manufacturing polyurethane resin aqueous dispersion |
| CN102618010B (en) * | 2012-03-08 | 2014-01-15 | 广州聚天化工科技有限公司 | Continuous production device and method for regenerating polyol by depolymerizing waste polyurethane |
| EP3802658A4 (en) * | 2018-06-06 | 2022-01-12 | Dow Global Technologies LLC | Aqueous coating composition |
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1997
- 1997-09-22 JP JP25723197A patent/JP3957018B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH1192654A (en) | 1999-04-06 |
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