JP5413360B2 - Polyurethane elastic yarn - Google Patents
Polyurethane elastic yarn Download PDFInfo
- Publication number
- JP5413360B2 JP5413360B2 JP2010277891A JP2010277891A JP5413360B2 JP 5413360 B2 JP5413360 B2 JP 5413360B2 JP 2010277891 A JP2010277891 A JP 2010277891A JP 2010277891 A JP2010277891 A JP 2010277891A JP 5413360 B2 JP5413360 B2 JP 5413360B2
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane
- weight
- elastic yarn
- solution
- yarn
- 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.)
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- 229920002635 polyurethane Polymers 0.000 title claims description 97
- 239000004814 polyurethane Substances 0.000 title claims description 97
- 239000003242 anti bacterial agent Substances 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 40
- 150000002009 diols Chemical class 0.000 claims description 30
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 29
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 28
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 18
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- -1 diol compound Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 60
- 238000009987 spinning Methods 0.000 description 34
- 230000000844 anti-bacterial effect Effects 0.000 description 33
- 238000011156 evaluation Methods 0.000 description 31
- 238000000034 method Methods 0.000 description 30
- 230000001877 deodorizing effect Effects 0.000 description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 16
- 238000005406 washing Methods 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 239000002781 deodorant agent Substances 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000011164 primary particle Substances 0.000 description 9
- 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 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 6
- 239000004970 Chain extender Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- TUFYVOCKVJOUIR-UHFFFAOYSA-N alpha-Thujaplicin Natural products CC(C)C=1C=CC=CC(=O)C=1O TUFYVOCKVJOUIR-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229930007845 β-thujaplicin Natural products 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004332 deodorization Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920003226 polyurethane urea Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000578 dry spinning Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- JGFDZZLUDWMUQH-UHFFFAOYSA-N Didecyldimethylammonium Chemical compound CCCCCCCCCC[N+](C)(C)CCCCCCCCCC JGFDZZLUDWMUQH-UHFFFAOYSA-N 0.000 description 3
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 3
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XHJGXOOOMKCJPP-UHFFFAOYSA-N 2-[tert-butyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(C(C)(C)C)CCO XHJGXOOOMKCJPP-UHFFFAOYSA-N 0.000 description 2
- RFBYVFZNDZQJKN-UHFFFAOYSA-N CS(O)(=O)=O.F.F.F Chemical compound CS(O)(=O)=O.F.F.F RFBYVFZNDZQJKN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- 229920001577 copolymer Polymers 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 229940078672 didecyldimethylammonium Drugs 0.000 description 2
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- 229940043279 diisopropylamine Drugs 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 210000004177 elastic tissue Anatomy 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
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- 235000019645 odor Nutrition 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
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- 150000003077 polyols Chemical class 0.000 description 2
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- 238000012805 post-processing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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- 150000003871 sulfonates Chemical class 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
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- 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 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- GKNWQHIXXANPTN-UHFFFAOYSA-M 1,1,2,2,2-pentafluoroethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-M 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-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
- GHXPTDPKJYFMOE-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCCC1CN=C=O GHXPTDPKJYFMOE-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
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- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- NPEIGRBGMUJNFE-UHFFFAOYSA-N 1-aminohexan-1-ol Chemical compound CCCCCC(N)O NPEIGRBGMUJNFE-UHFFFAOYSA-N 0.000 description 1
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- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 description 1
- QHTUMQYGZQYEOZ-UHFFFAOYSA-N 2-(4-methylpiperazin-1-yl)ethanol Chemical compound CN1CCN(CCO)CC1 QHTUMQYGZQYEOZ-UHFFFAOYSA-N 0.000 description 1
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 description 1
- IAXFZZHBFXRZMT-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(OCCO)=C1 IAXFZZHBFXRZMT-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- TYNNEOUATWMCIY-UHFFFAOYSA-N 4-(4-aminophenyl)phosphonoylaniline Chemical compound C1=CC(N)=CC=C1P(=O)C1=CC=C(N)C=C1 TYNNEOUATWMCIY-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- 235000011130 ammonium sulphate Nutrition 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
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- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- WDWNYZFJIQCTPI-UHFFFAOYSA-M didecyl(dimethyl)azanium;1,1,2,2,2-pentafluoroethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)F.CCCCCCCCCC[N+](C)(C)CCCCCCCCCC WDWNYZFJIQCTPI-UHFFFAOYSA-M 0.000 description 1
- KNGKMSNSHKRXOJ-UHFFFAOYSA-M didecyl(dimethyl)azanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCCCCCCC[N+](C)(C)CCCCCCCCCC KNGKMSNSHKRXOJ-UHFFFAOYSA-M 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
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- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- QKYWADPCTHTJHQ-UHFFFAOYSA-N n,2-dimethylpropan-1-amine Chemical compound CNCC(C)C QKYWADPCTHTJHQ-UHFFFAOYSA-N 0.000 description 1
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- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- XFLSMWXCZBIXLV-UHFFFAOYSA-N n,n-dimethyl-2-(4-methylpiperazin-1-yl)ethanamine Chemical compound CN(C)CCN1CCN(C)CC1 XFLSMWXCZBIXLV-UHFFFAOYSA-N 0.000 description 1
- PMHXGHYANBXRSZ-UHFFFAOYSA-N n,n-dimethyl-2-morpholin-4-ylethanamine Chemical compound CN(C)CCN1CCOCC1 PMHXGHYANBXRSZ-UHFFFAOYSA-N 0.000 description 1
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- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
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- 239000004632 polycaprolactone Substances 0.000 description 1
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- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- QYWVQMLYIXYLRE-SEYXRHQNSA-N trimethyl-[(z)-octadec-9-enyl]azanium Chemical compound CCCCCCCC\C=C/CCCCCCCC[N+](C)(C)C QYWVQMLYIXYLRE-SEYXRHQNSA-N 0.000 description 1
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Landscapes
- Artificial Filaments (AREA)
Description
本発明は、抗菌性および消臭性に優れたポリウレタン弾性糸に関するものであり、抗菌性および消臭性を有する布帛を得るのに好適なポリウレタン弾性糸に関する。 The present invention relates to a polyurethane elastic yarn excellent in antibacterial properties and deodorizing properties, and relates to a polyurethane elastic yarn suitable for obtaining a fabric having antibacterial properties and deodorizing properties.
弾性繊維は、その優れた伸縮特性からレッグウエア、インナーウエア、スポーツウエアなどの伸縮性衣料用途、紙おむつや生理用ナプキンなどのサニタリー用途（衛材用途）、産業資材用途に幅広く使用されている。 Elastic fibers are widely used for elastic clothing applications such as leg wear, inner wear, and sports wear, sanitary applications such as disposable diapers and sanitary napkins, and industrial material applications due to their excellent elastic properties.
近年、より快適な住環境が求められる中で、抗菌性塗料、抗菌性フィルム・シート、抗菌性フィラメント、抗菌性トイレタリー製品、抗菌性台所用品、抗菌性文房具、抗菌砂、抗菌ティシュ、抗菌繊維、抗菌性化粧品などのいわゆる「抗菌性商品」が広く出回るようになってきた。また、同様に、加齢臭などに対する消臭機能を具備する、衣類、寝具などの「消臭性製品」も出回るようになってきた。 In recent years, a more comfortable living environment has been demanded. Antibacterial paints, antibacterial films and sheets, antibacterial filaments, antibacterial toiletries, antibacterial kitchen utensils, antibacterial stationery, antibacterial sand, antibacterial tissue, antibacterial fibers, So-called “antibacterial products” such as antibacterial cosmetics have become widely available. Similarly, “deodorant products” such as clothes and bedding that have a deodorizing function against aging odors and the like have come to the market.
このような機能を付与するために繊維製品においては、これらの機能を付与する後加工方法が提案されている（特許文献１）。しかしながら、このような後加工による方法では、一時的に抗菌性や消臭性といった機能を持つ製品はえられるものの、伸縮性布帛の場合においては機能剤を付着させるためのバインダーにより風合いが損なわれる。また、加工工程が長くなることによる生産性の低下や洗濯耐久性が著しく低下するといった問題が生じていた。 In order to impart such functions, a post-processing method for imparting these functions has been proposed for fiber products (Patent Document 1). However, with such post-processing methods, products having functions such as antibacterial properties and deodorizing properties can be obtained temporarily, but in the case of stretchable fabrics, the texture is impaired by the binder for attaching the functional agent. . In addition, there has been a problem in that productivity is lowered due to a long processing step and washing durability is remarkably lowered.
そこで、繊維に直接、抗菌剤や消臭剤を繊維に含有させる方法も提案されている。 Therefore, a method in which an antibacterial agent or deodorant is directly contained in the fiber has been proposed.
これらに利用されている抗菌剤としては、無機系抗菌剤、特に銀系抗菌剤が多く見受けられる。また消臭剤としては活性炭、銀含有ゼオライト、ゼオライト、微粒子酸化亜鉛などが挙げられる。 As antibacterial agents used for these, inorganic antibacterial agents, particularly silver antibacterial agents, are often found. Examples of the deodorizer include activated carbon, silver-containing zeolite, zeolite, and fine zinc oxide.
上記無機系抗菌剤は、有機抗菌剤に比べて、耐候性・耐薬品性に優れ、急性経口毒性が低いという優れた特性を有している。加えて、耐熱性が有機系抗菌剤に比べて著しく高いため、合成樹脂に添加して多分野で使われるようになってきた。しかしながら、無機系抗菌剤を合成樹脂に添加して成形すると、無機抗菌剤に含有される金属の作用と、成形時の熱や成形物に照射される光の影響で成形品が変色して、製品価値が著しく低下するという問題が生じ易い。 The inorganic antibacterial agent has excellent characteristics such as excellent weather resistance and chemical resistance and low acute oral toxicity as compared with the organic antibacterial agent. In addition, heat resistance is remarkably higher than that of organic antibacterial agents, so it has been added to synthetic resins and used in many fields. However, when an inorganic antibacterial agent is added to a synthetic resin and molded, the molded product discolors due to the effect of the metal contained in the inorganic antibacterial agent and the effect of heat and light irradiated on the molded product. The problem that the product value is significantly reduced is likely to occur.
また、有機系の抗菌剤として天然抗菌剤であるヒノキチオールとＺ ｎ 、Ｓ ｉ 、Ｃ ｕ 、Ｎ ｉ 、Ｆｅ 、Ａ ｌ 及びＭ ｇ から選ばれた少なくとも１ 種の元素を含む金属酸化物及び／ 複合金属酸化物とを含有する抗菌消臭ポリウレタン弾性繊維（特許文献２）が提案されており、ポリウレタン弾性糸の抗菌性と消臭性に一定の性能は認められている。しかし、乾式紡糸中の受熱により抗菌剤であるヒノキチオールが昇華することが認められるため、予め多めに紡糸原液に含有させておく必要がある。また、ヒノキチオールは紡糸の熱量条件などによって残存量が変化するため、安定した抗菌性を保有したポリウレタン弾性糸を生産することが難しい。また、天然抗菌剤であるヒノキチオールが高価であることからコスト面でも課題がある。 Further, hinokitiol which is a natural antibacterial agent as an organic antibacterial agent and a metal oxide containing at least one element selected from Zn, Si, Cu, Ni, Fe, Al and Mg, and / or An antibacterial and deodorant polyurethane elastic fiber (Patent Document 2) containing a composite metal oxide has been proposed, and certain performance is recognized for the antibacterial and deodorant properties of the polyurethane elastic yarn. However, since it is recognized that hinokitiol, which is an antibacterial agent, is sublimated by heat reception during dry spinning, it is necessary to add a large amount to the spinning dope beforehand. Further, since the remaining amount of hinokitiol changes depending on the calorific condition of spinning, it is difficult to produce a polyurethane elastic yarn having stable antibacterial properties. Moreover, since hinokitiol which is a natural antibacterial agent is expensive, there is a problem in terms of cost.
さらに有機系の合成抗菌剤の使用（特許文献３）なども提案されている。しかしながら、これは、単独での使用では消臭性に効果がなく、抗菌性と消臭性の両立という面では課題があった。 Further, the use of organic synthetic antibacterial agents (Patent Document 3) has been proposed. However, this has no effect on deodorizing properties when used alone, and has a problem in terms of both antibacterial properties and deodorizing properties.
本発明は、繰り返し洗濯後の抗菌性および消臭性に優れたポリウレタン弾性糸を提供することを目的とする。 An object of the present invention is to provide a polyurethane elastic yarn having excellent antibacterial and deodorizing properties after repeated washing.
前記の課題を解決するための本発明は、以下のいずれかの手段を採用する。
（１）ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸であって、金属リン酸塩を１重量％以上１０重量％以下の範囲で含有し、かつ下記構造を有する４級アンモニウム塩系抗菌剤を含有することを特徴とするポリウレタン弾性糸。
（２）前記金属リン酸塩が、リン酸チタン、リン酸ジルコニウム、およびトリポリリン酸二水素アルミニウムからなる群から選ばれる少なくとも１種であることを特徴とする、前記（１）に記載のポリウレタン弾性糸。
The present invention for solving the above problems employs any of the following means.
(1) A quaternary ammonium salt system comprising a polyurethane having a polymer diol and a diisocyanate as starting materials and containing a metal phosphate in a range of 1 wt% to 10 wt% and having the following structure: A polyurethane elastic yarn containing an antibacterial agent.
(2) The polyurethane elasticity according to (1), wherein the metal phosphate is at least one selected from the group consisting of titanium phosphate, zirconium phosphate, and aluminum dihydrogen phosphate. yarn.
（３）前記４級アンモニウム塩系抗菌剤の含有量が０．１重量％以上５重量％以下の範囲であることを特徴とする、前記（１）または（２）に記載のポリウレタン弾性糸。
（４）前記ポリウレタンが、分子量３００以下のジオール化合物によって鎖伸長されたものであることを特徴とする、前記（１）〜（３）のいずれかに記載のポリウレタン弾性糸。
( 3 ) The polyurethane elastic yarn according to (1) or (2) above, wherein the content of the quaternary ammonium salt antibacterial agent is in the range of 0.1 wt% to 5 wt%.
( 4 ) The polyurethane elastic yarn according to any one of (1) to ( 3 ), wherein the polyurethane is chain-extended with a diol compound having a molecular weight of 300 or less.
本発明によれば、繰り返し洗濯後における、消臭性、抗菌性に優れたポリウレタン弾性糸を得ることができる。そのため、かかるポリウレタン弾性糸を使用した布帛は伸縮性、繰り返し洗濯後における消臭性、抗菌性に優れたものになる。 According to the present invention, after Repetitive returns washing, it is possible to obtain deodorant, an excellent polyurethane elastic yarn antimicrobial. Therefore, a fabric using such polyurethane elastic yarn has excellent stretchability, deodorization after repeated washing, and antibacterial properties.
以下本発明について、さらに詳細に述べる。 The present invention is described in further detail below.
まず本発明で使用するポリウレタンについて述べる。 First, the polyurethane used in the present invention will be described.
本発明に使用されるポリウレタンは、ポリマージオールおよびジイソシアネートを出発物質とするものであれば任意のものでよく、特に限定されるものではない。また、その合成法も特に限定されるものではない。すなわち、例えば、ポリマージオールとジイソシアネートと低分子量ジアミンからとなるポリウレタンウレアであってもよく、また、ポリマージオールとジイソシアネートと低分子量ジオールとからなるポリウレタンウレタンであってもよい。また、鎖伸長剤として水酸基とアミノ基を分子内に有する化合物を使用したポリウレタンウレアであってもよい。本発明の効果を妨げない範囲で３官能性以上の多官能性のグライコールやイソシアネート等が使用されることも好ましい。 The polyurethane used in the present invention may be any as long as it uses a polymer diol and diisocyanate as starting materials, and is not particularly limited. Also, the synthesis method is not particularly limited. That is, for example, it may be a polyurethane urea composed of a polymer diol, diisocyanate and a low molecular weight diamine, or may be a polyurethane urethane composed of a polymer diol, diisocyanate and a low molecular weight diol. Moreover, the polyurethane urea which uses the compound which has a hydroxyl group and an amino group in a molecule | numerator as a chain extender may be used. It is also preferable to use trifunctional or higher polyfunctional glycol or isocyanate or the like as long as the effects of the present invention are not hindered.
ポリマージオールはポリエーテル系、ポリエステル系ジオール、ポリカーボネートジオール等が好ましい。そして、特に柔軟性、伸度を糸に付与する観点からポリエーテル系ジオールが使用されることが好ましい。 The polymer diol is preferably a polyether-based, polyester-based diol, polycarbonate diol or the like. In particular, a polyether diol is preferably used from the viewpoint of imparting flexibility and elongation to the yarn.
ポリエーテル系ジオールとしては、例えば、ポリエチレンオキシド、ポリエチレングリコール、ポリエチレングリコールの誘導体、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール（以下、ＰＴＭＧと略す）、テトラヒドロフラン（ＴＨＦ）および３−メチルテトラヒドロフランの共重合体である変性ＰＴＭＧ（以下、３Ｍ−ＰＴＭＧと略する）、ＴＨＦおよび２，３−ジメチルＴＨＦの共重合体である変性ＰＴＭＧ、特許第２６１５１３１号公報などに開示される側鎖を両側に有するポリオール、ＴＨＦとエチレンオキサイドおよび／またはプロピレンオキサイドが不規則に配列したランダム共重合体等が好ましく使用される。これらポリエーテル系ジオールを１種または２種以上混合もしくは共重合して使用してもよい。 Examples of the polyether diol include polyethylene oxide, polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (THF) and 3-methyltetrahydrofuran copolymer. A modified PTMG (hereinafter abbreviated as 3M-PTMG), a modified PTMG which is a copolymer of THF and 2,3-dimethyl THF, a polyol having side chains on both sides as disclosed in Japanese Patent No. 2615131, THF Random copolymers in which ethylene oxide and / or propylene oxide are randomly arranged are preferably used. These polyether diols may be used alone or in combination of two or more.
また、ポリウレタン弾性糸として耐摩耗性や耐光性を得る観点からは、ブチレンアジペート、ポリカプロラクトンジオール、特開昭６１−２６６１２号公報などに開示されている側鎖を有するポリエステルポリオールなどのポリエステル系ジオールや、特公平２−２８９５１６号公報などに開示されているポリカーボネートジオール等が好ましく使用される。 From the viewpoint of obtaining abrasion resistance and light resistance as a polyurethane elastic yarn, polyester-based diols such as butylene adipate, polycaprolactone diol, and polyester polyols having side chains disclosed in JP-A No. 61-26612, etc. Polycarbonate diols disclosed in JP-B-2-289516 and the like are preferably used.
また、こうしたポリマージオールは単独で使用してもよいし、２種以上混合もしくは共重合して使用してもよい。 These polymer diols may be used alone or in combination of two or more.
ポリマージオールの分子量は、糸にした際の伸度、強度、耐熱性などを得る観点から、数平均分子量が１０００以上８０００以下のものが好ましく、１５００以上６０００以下がより好ましい。この範囲の分子量のポリオールが使用されることにより、伸度、強度、弾性回復力、耐熱性に優れた弾性糸を容易に得ることができる。 The molecular weight of the polymer diol is preferably a number average molecular weight of 1000 or more and 8000 or less, and more preferably 1500 or more and 6000 or less, from the viewpoint of obtaining elongation, strength, heat resistance and the like when formed into a yarn. By using a polyol having a molecular weight within this range, an elastic yarn excellent in elongation, strength, elastic recovery, and heat resistance can be easily obtained.
次に、ジイソシアネートとしては、ジフェニルメタンジイソシアネート（以下、ＭＤＩと略す）、トリレンジイソシアネート、１，４−ジイソシアネートベンゼン、キシリレンジイソシアネート、２，６−ナフタレンジイソシアネートなどの芳香族ジイソシアネートが、特に耐熱性や強度の高いポリウレタンを合成するのに好適である。さらに脂環族ジイソシアネートとして、例えば、メチレンビス（シクロヘキシルイソシアネート）（以下、Ｈ１２ＭＤＩと称する。）、イソホロンジイソシアネート、メチルシクロヘキサン２，４−ジイソシアネート、メチルシクロヘキサン２，６−ジイソシアネート、シクロヘキサン１，４−ジイソシアネート、ヘキサヒドロキシリレンジイソシアネート、ヘキサヒドロトリレンジイソシアネート、オクタヒドロ１，５−ナフタレンジイソシアネートなどが好ましい。脂肪族ジイソシアネートは、特にポリウレタン弾性糸の黄変を抑制する際に有効に使用できる。そして、これらのジイソシアネートは単独で使用してもよいし、２種以上を併用してもよい。 Next, as the diisocyanate, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate, particularly heat resistance and strength. It is suitable for synthesizing a high polyurethane. Further, as the alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate) (hereinafter referred to as H12MDI), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexa Hydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro 1,5-naphthalene diisocyanate and the like are preferable. Aliphatic diisocyanates can be used effectively particularly in suppressing yellowing of polyurethane elastic yarns. And these diisocyanates may be used independently and may use 2 or more types together.
次にポリウレタンを合成するにあって用いられる鎖伸長剤は、分子量３００以下の低分子量ジアミンおよび低分子量ジオールのうちの少なくとも１種を使用するのが好ましい。なお、エタノールアミンのような水酸基とアミノ基を分子中に有するものであってもよい。 Next, it is preferable to use at least one of a low molecular weight diamine having a molecular weight of 300 or less and a low molecular weight diol as the chain extender used in synthesizing the polyurethane. In addition, you may have a hydroxyl group and amino groups in a molecule like ethanolamine.
好ましい低分子量ジアミンとしては、例えば、エチレンジアミン、１，２−プロパンジアミン、１，３−プロパンジアミン、ヘキサメチレンジアミン、ｐ−フェニレンジアミン、ｐ−キシリレンジアミン、ｍ−キシリレンジアミン、ｐ，ｐ’−メチレンジアニリン、１，３−シクロヘキシルジアミン、ヘキサヒドロメタフェニレンジアミン、２−メチルペンタメチレンジアミン、ビス（４−アミノフェニル）フォスフィンオキサイドなどが挙げられる。これらの中から１種または２種以上が使用されることが好ましい。特に好ましくはエチレンジアミンである。エチレンジアミンを用いることにより伸度および弾性回復性、さらに耐熱性に優れた糸を容易に得ることができる。これらの鎖伸長剤に架橋構造を形成することのできるトリアミン化合物、例えば、ジエチレントリアミン等を効果が失わない程度に加えてもよい。 Preferred low molecular weight diamines include, for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p, p ′. -Methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis (4-aminophenyl) phosphine oxide and the like. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred is ethylenediamine. By using ethylenediamine, a yarn excellent in elongation, elastic recovery, and heat resistance can be easily obtained. You may add the triamine compound which can form a crosslinked structure in these chain extenders, for example, diethylenetriamine, etc. to such an extent that an effect is not lost.
また、分子量３００以下の低分子量ジオールとしては、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、ビスヒドロキシエトキシベンゼン、ビスヒドロキシエチレンテレフタレート、１−メチル−１，２−エタンジオールなどが代表的なものである。これらの中から１種または２種以上が使用されることが好ましい。特に好ましくはエチレングリコール、１，３プロパンジオール、１，４ブタンジオールである。これらを用いると、ジオール伸長のポリウレタンとしては耐熱性がより高くなり、また、より強度の高い糸を得ることができるのである。 Representative examples of the low molecular weight diol having a molecular weight of 300 or less include ethylene glycol, 1,3 propanediol, 1,4 butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol and the like. Is something. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred are ethylene glycol, 1,3 propanediol, and 1,4 butanediol. When these are used, the diol-extended polyurethane has higher heat resistance, and a yarn having higher strength can be obtained.
また、本発明においてポリウレタンの分子量は、耐久性や強度の高い繊維を得る観点から、数平均分子量として３００００以上１５００００以下の範囲であることが好ましい。なお、分子量はＧＰＣで測定し、ポリスチレンにより換算する。 In the present invention, the molecular weight of the polyurethane is preferably in the range of 30000 to 150,000 as the number average molecular weight from the viewpoint of obtaining a fiber having high durability and strength. The molecular weight is measured by GPC and converted by polystyrene.
ポリウレタンには、末端封鎖剤が１種または２種以上混合使用されることも好ましい。末端封鎖剤としては、ジメチルアミン、ジイソプロピルアミン、エチルメチルアミン、ジエチルアミン、メチルプロピルアミン、イソプロピルメチルアミン、ジイソプロピルアミン、ブチルメチルアミン、イソブチルメチルアミン、イソペンチルメチルアミン、ジブチルアミン、ジアミルアミンなどのモノアミン、エタノール、プロパノール、ブタノール、イソプロパノール、アリルアルコール、シクロペンタノールなどのモノオール、フェニルイソシアネートなどのモノイソシアネートなどが好ましい。 It is also preferable that one or more terminal blocking agents are used in the polyurethane. As end-capping agents, monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, Monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.
本発明においては、以上のような基本構成を有するポリウレタンからなるポリウレタン弾性糸に、金属リン酸塩を含有させることで、ポリウレタン弾性糸が元来保有している酢酸ガス、ノネナールガス、イソ吉草酸ガスに対する消臭性を阻害することなく、アンモニアガスに対しても消臭性を向上させることが可能となる。また、同時に、４級アンモニウム塩系抗菌剤をポリウレタン弾性糸に含有させることで繰り返し洗濯後においても優れた抗菌性を保有させることが可能となる。 In the present invention, by containing a metal phosphate in a polyurethane elastic yarn made of polyurethane having the above basic structure, acetic acid gas, nonenal gas, isovaleric acid originally possessed by the polyurethane elastic yarn It is possible to improve the deodorizing property for ammonia gas without inhibiting the deodorizing property for the gas. At the same time, by including a quaternary ammonium salt antibacterial agent in the polyurethane elastic yarn, it becomes possible to retain excellent antibacterial properties even after repeated washing.
金属リン酸塩としては、ジルコニウム、チタン、アルミニウム、カルシウムからなる金属リン酸塩などを用いることができる。中でも、アンモニアに対する消臭性という観点から層状構造を有するリン酸ジルコニウム、リン酸チタン、トリポリリン酸二水素アルミニウムからなる群から選ばれる少なくとも１種を用いることが好ましい。 As the metal phosphate, a metal phosphate composed of zirconium, titanium, aluminum, calcium, or the like can be used. Especially, it is preferable to use at least 1 sort (s) chosen from the group which consists of zirconium phosphate which has a layered structure from a viewpoint of deodorizing property with respect to ammonia, titanium phosphate, and a tripoly aluminum phosphate.
また、リン酸ジルコニウムなどの金属リン酸塩は、アンモニアに対する消臭性という観点から銀イオンや銅イオンといった金属イオンを担持していない物が好ましい。 In addition, the metal phosphate such as zirconium phosphate is preferably a metal phosphate that does not carry metal ions such as silver ions and copper ions from the viewpoint of deodorization with respect to ammonia.
リン酸ジルコニウムなどの金属リン酸塩の含有量は、ポリウレタン弾性糸全重量に対して１重量％以上１０重量％以下の範囲である。リン酸ジルコニウムの含有量が１重量％未満だと、布帛とした際に十分なアンモニアガスの消臭性が得られにくくなるので、好ましくない。より好ましくは１．５重量％以上である。一方、含有量が１０重量％を越えると、伸縮特性の悪化やコスト面で好ましくない。より好ましくは７．０重量％以下である。アンモニアガスに対する消臭性と物性面、コスト面というバランスを考慮すると、１．５重量％以上５．０重量％以下の範囲が特に好ましい。 Content of metal phosphates, such as a zirconium phosphate, is the range of 1 to 10 weight% with respect to the total weight of a polyurethane elastic yarn. When the content of zirconium phosphate is less than 1% by weight, it is difficult to obtain a sufficient deodorizing property of ammonia gas when used as a fabric. More preferably, it is 1.5% by weight or more. On the other hand, if the content exceeds 10% by weight, it is not preferable in terms of deterioration of stretchability and cost. More preferably, it is 7.0 weight% or less. In consideration of the balance of deodorizing property with respect to ammonia gas, physical properties, and cost, a range of 1.5 wt% or more and 5.0 wt% or less is particularly preferable.
また、本発明においてリン酸ジルコニウムなどの金属リン酸塩は、紡糸原液の紡糸口金への詰まりを抑えるという観点から、平均一次粒子径が３．０μｍ以下のものが好ましい。より好ましくは１．５μｍ以下である。また、分散性の観点から平均一次粒子径が０．０５μｍより小さい場合、凝集力が高まり紡糸原液中に均一に混合することが困難になるため、平均一次粒子径が０．０５μｍ以上のものが好ましい。 In the present invention, the metal phosphate such as zirconium phosphate preferably has an average primary particle size of 3.0 μm or less from the viewpoint of suppressing clogging of the spinning dope into the spinneret. More preferably, it is 1.5 μm or less. Also, from the viewpoint of dispersibility, when the average primary particle size is smaller than 0.05 μm, the cohesive force increases and it becomes difficult to mix uniformly into the spinning dope, so that the average primary particle size is 0.05 μm or more. preferable.
ポリウレタン弾性糸中の金属リン酸塩の同定方法としては、ポリウレタン弾性糸を一旦溶媒に溶解して希釈溶液とし、遠心分離等で沈降物を得る。得られた沈降物について十分に水洗後、デシケーター内で乾燥させ、ＩＲ、原糸吸光光度法、Ｘ線回折法、固体ＮＭＲ等の種々の分析方法によって同定する。また、定量方法については、前記方法によって物質を同定した上で、原糸吸光光度法によってポリウレタン弾性糸中のＡｌ、Ｚｒ、Ｔｉ、Ｐといった元素量を定量して求めることができる。 As a method for identifying the metal phosphate in the polyurethane elastic yarn, the polyurethane elastic yarn is once dissolved in a solvent to obtain a diluted solution, and a precipitate is obtained by centrifugation or the like. The obtained precipitate is sufficiently washed with water, dried in a desiccator, and identified by various analytical methods such as IR, raw yarn absorptiometry, X-ray diffractometry, solid state NMR and the like. As for the quantification method, after identifying the substance by the above method, the amount of elements such as Al, Zr, Ti and P in the polyurethane elastic yarn can be quantified and determined by the raw yarn absorptiometry.
本発明において、４級アンモニウム塩系抗菌剤としては、アンモニウムイオン中のアルキル基の鎖長により抗菌力に差があり、抗菌力の強いものが望ましいが、ポリウレタン弾性糸の製造上にかかる受熱等からもアルキル基等の鎖種、鎖長を選ぶことが好ましい。この観点から特に好ましいアンモニウムイオンは、ステアリルトリメチルアンモニウムイオン、セチルトリメチルアンモニウムイオン、ジデシルジメチルアンモニウムイオン、オレイルトリメチルアンモニウムイオンなどである。これらは通常、下記のような構造を有するスルホン酸塩、リン酸塩等の有機酸塩や塩化物、臭化物、ヨウ化物などの塩により供給され、中でも、変色や耐熱性等の安定性の観点からスルホン酸塩が好ましい。 In the present invention, the quaternary ammonium salt antibacterial agent has a difference in antibacterial activity depending on the chain length of the alkyl group in the ammonium ion, and preferably has a strong antibacterial activity. Therefore, it is preferable to select a chain type such as an alkyl group and a chain length. Particularly preferred ammonium ions from this viewpoint are stearyl trimethyl ammonium ion, cetyl trimethyl ammonium ion, didecyl dimethyl ammonium ion, oleyl trimethyl ammonium ion, and the like. These are usually supplied by organic acid salts such as sulfonates and phosphates having the following structures, and salts such as chlorides, bromides, and iodides. Among them, in terms of stability such as discoloration and heat resistance To sulfonates are preferred.
上記構造を有する塩の具体例としては、ジデシルジメチルアンモニウム３フッ化メチルスルホン酸塩、ジ−ｎ−デシルジメチルアンモニウムトリフルオロメタンスルホン酸塩、ジ−ｎ−デシルジメチルアンモニウムペンタフルオロエタンスルホン酸塩、ｎ−ヘキサデシルトリメチルアンモニウムトリフルオロメタンスルホン酸塩、及びベンジルジメチルヤシ油アルキルアンモニウムペンタフルオロエタンスルホン酸塩である。 Specific examples of the salt having the above structure include didecyldimethylammonium trifluoride methylsulfonate, di-n-decyldimethylammonium trifluoromethanesulfonate, di-n-decyldimethylammonium pentafluoroethanesulfonate, n-hexadecyltrimethylammonium trifluoromethanesulfonate and benzyldimethylcoconut alkylammonium pentafluoroethanesulfonate.
４級アンモニウム塩系抗菌剤は、抗菌性を発現し、変色や伸縮特性のバランスを保つという観点から、ポリウレタン弾性糸全重量に対して０．１重量％以上５重量％以下の範囲で含有することが好ましい。 The quaternary ammonium salt antibacterial agent is contained in the range of 0.1% by weight to 5% by weight with respect to the total weight of the polyurethane elastic yarn from the viewpoint of exhibiting antibacterial properties and maintaining a balance between discoloration and stretchability. It is preferable.
本発明のポリウレタン弾性糸には、各種安定剤や顔料などが含有されていてもよい。例えば、耐光剤、酸化防止剤などにＢＨＴや住友化学工業株式会社製の“スミライザー”（登録商標）ＧＡ−８０などのヒンダードフェノール系薬剤、各種のチバガイギー社製“チヌビン”（登録商標）などのベンゾトリアゾール系、ベンゾフェノン系薬剤、住友化学工業株式会社製の“スミライザー”（登録商標）Ｐ−１６などのリン系薬剤、各種のヒンダードアミン系薬剤、酸化鉄、酸化チタンなどの各種顔料、酸化亜鉛、酸化セリウム、酸化マグネシウム、炭酸カルシウム、カーボンブラックなどの無機物、フッ素系またはシリコーン系樹脂粉体、ステアリン酸マグネシウムなどの金属石鹸、また、シリコーン、鉱物油などの滑剤、酸化セリウム、ベタインやリン酸系などの各種の帯電防止剤などが含まれることも好ましく、またこれらがポリマと反応させられることも好ましい。そして、特に光や各種の酸化窒素などへの耐久性をさらに高めるには、例えば、日本ヒドラジン株式会社製のＨＮ−１５０などの酸化窒素補足剤、住友化学工業株式会社製の“スミライザー”（登録商標）ＧＡ−８０などの熱酸化安定剤、住友化学工業株式会社製の“スミソーブ”（登録商標）３００♯６２２などの光安定剤が使用されることも好ましい。 The polyurethane elastic yarn of the present invention may contain various stabilizers, pigments and the like. For example, hindered phenolic agents such as BHT and “Sumilyzer” (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd., various types of “Chinubin” (registered trademark) manufactured by Ciba Geigy Co., Ltd. Benzotriazoles, benzophenone drugs, phosphorus-based drugs such as “Sumilyzer” (registered trademark) P-16 manufactured by Sumitomo Chemical Co., Ltd., various hindered amine drugs, various pigments such as iron oxide and titanium oxide, zinc oxide , Inorganic substances such as cerium oxide, magnesium oxide, calcium carbonate, carbon black, fluorine or silicone resin powders, metal soaps such as magnesium stearate, lubricants such as silicone and mineral oil, cerium oxide, betaine and phosphoric acid It is also preferable to include various antistatic agents such as It is also preferred but which is reacted with the polymer. In order to further enhance the durability to light and various nitric oxides in particular, for example, nitric oxide supplements such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., “Sumilyzer” manufactured by Sumitomo Chemical Co., Ltd. (registered) It is also preferred to use a thermal oxidation stabilizer such as trade mark GA-80 and a light stabilizer such as “SUMISOB” (registered trademark) 300 # 622 manufactured by Sumitomo Chemical Co., Ltd.
次に本発明のポリウレタン弾性糸の製造方法について詳細に説明する。 Next, the method for producing the polyurethane elastic yarn of the present invention will be described in detail.
本発明においては、出発物質としてポリマージオールおよびジイソシアネートを用い、それらから得られるポリウレタンの紡糸原液に、リン酸ジルコニウムなどの金属リン酸塩および４級アンモニウム塩系抗菌剤とを含有させて紡糸する。重合を安定化させるという観点から、予めポリウレタン溶液を作製しておき、それにリン酸ジルコニウムと４級アンモニウム塩とを添加することが好ましい。また、溶液の溶質であるポリウレタンの製法は、溶融重合法でも溶液重合法のいずれであってもよく、他の方法であってもよい。しかし、より好ましいのは溶液重合法である。溶液重合法の場合には、ポリウレタンにゲルなどの異物の発生が少なく、紡糸しやすく、低繊度のポリウレタン弾性糸を得やすい。また、当然のことであるが、溶液重合の場合、溶液にする操作が省けるという利点がある。 In the present invention, a polymer diol and a diisocyanate are used as starting materials, and a spinning solution of polyurethane obtained therefrom is spun into a metal phosphate such as zirconium phosphate and a quaternary ammonium salt antibacterial agent. From the viewpoint of stabilizing the polymerization, it is preferable to prepare a polyurethane solution in advance and add zirconium phosphate and a quaternary ammonium salt thereto. Further, the method for producing the polyurethane as the solute of the solution may be either a melt polymerization method or a solution polymerization method, or may be another method. However, the solution polymerization method is more preferable. In the case of the solution polymerization method, there is little generation of foreign substances such as gel in the polyurethane, it is easy to spin, and it is easy to obtain a polyurethane elastic yarn having a low fineness. Of course, in the case of solution polymerization, there is an advantage that the operation of making a solution can be omitted.
そして本発明に特に好適なポリウレタンとしては、ポリマージオールとして分子量が１５００以上６０００以下のＰＴＭＧ、ジイソシアネートとしてＭＤＩ、鎖伸長剤としてエチレンジアミン、１，２−プロパンジアミン、１，３−プロパンジアミン、ヘキサメチレンジアミンのうちの少なくとも１種を使用して合成されたものが挙げられる。 The polyurethane particularly suitable for the present invention includes PTMG having a molecular weight of 1500 to 6000 as a polymer diol, MDI as a diisocyanate, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, and hexamethylenediamine as a chain extender. And those synthesized using at least one of them.
ポリウレタンは、例えば、ＤＭＡｃ、ＤＭＦ、ＤＭＳＯ、ＮＭＰなどやこれらを主成分とする溶剤の中で、上記の原料を用い合成することにより得られる。例えば、こうした溶剤中に、各原料を投入、溶解させ、適度な温度に加熱し反応させてポリウレタンとする、いわゆるワンショット法、また、ポリマージオールとジイソシアネートを、まず溶融反応させ、しかる後に、反応物を溶剤に溶解し、前述の鎖伸長剤と反応させてポリウレタンとする方法などが、特に好適な方法として採用され得る。 Polyurethane can be obtained, for example, by synthesizing using the above-mentioned raw materials in DMAc, DMF, DMSO, NMP or the like or a solvent containing these as main components. For example, each raw material is charged in such a solvent, dissolved, heated to an appropriate temperature and reacted to form polyurethane, a so-called one-shot method, or polymer diol and diisocyanate are first melt-reacted and then reacted. A particularly preferable method is a method in which a product is dissolved in a solvent and reacted with the above-described chain extender to form polyurethane.
鎖伸長剤にジオールを用いる場合、耐熱性に優れたものを得るという観点から、ポリウレタンの高温側の融点を２００℃以上２６０℃以下の範囲に調節することが好ましい。代表的な方法は、ポリマージオール、ＭＤＩ、ジオールの種類と比率をコントロールすることにより達成され得る。ポリマージオールの分子量が低い場合には、ＭＤＩの割合を相対的に多くすることにより、高温の融点が高いポリウレタンを得ることができ、同様にジオールの分子量が低いときはポリマージオールの割合を相対的に少なくすることにより、高温の融点が高いポリウレタンを得ることができる。 When a diol is used as the chain extender, it is preferable to adjust the melting point on the high temperature side of the polyurethane to a range of 200 ° C. or higher and 260 ° C. or lower from the viewpoint of obtaining a product having excellent heat resistance. Exemplary methods can be achieved by controlling the type and ratio of polymer diol, MDI, diol. When the molecular weight of the polymer diol is low, a polyurethane having a high melting point at a high temperature can be obtained by relatively increasing the proportion of MDI. Similarly, when the molecular weight of the diol is low, the proportion of the polymer diol is relatively By reducing the amount of the polyurethane, a polyurethane having a high temperature melting point can be obtained.
ポリマージオールの分子量が１８００以上の場合、高温側の融点を２００℃以上にするには、（ＭＤＩのモル数）/（ポリマージオールのモル数）＝１．５以上の割合で、重合を進めることが好ましい。 In the case where the molecular weight of the polymer diol is 1800 or more, in order to make the melting point on the high temperature side 200 ° C. or more, the polymerization is advanced at a ratio of (number of moles of MDI) / (number of moles of polymer diol) = 1.5 or more. Is preferred.
なお、かかるポリウレタンの合成に際し、アミン系触媒や有機金属触媒等の触媒が１種もしくは２種以上混合して使用されることも好ましい。 In the synthesis of such polyurethane, it is also preferable to use one or a mixture of two or more catalysts such as amine catalysts and organometallic catalysts.
アミン系触媒としては、例えば、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、Ｎ，Ｎ−ジメチルベンジルアミン、トリエチルアミン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−プロパンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサンジアミン、ビス−２−ジメチルアミノエチルエーテル、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ’−ペンタメチルジエチレントリアミン、テトラメチルグアニジン、トリエチレンジアミン、Ｎ，Ｎ’−ジメチルピペラジン、Ｎ−メチル−Ｎ’−ジメチルアミノエチル−ピペラジン、Ｎ−（２−ジメチルアミノエチル)モルホリン、１−メチルイミダゾール、１，２−ジメチルイミダゾール、Ｎ，Ｎ−ジメチルアミノエタノール、Ｎ，Ｎ，Ｎ’−トリメチルアミノエチルエタノールアミン、Ｎ−メチル−Ｎ’−（２−ヒドロキシエチル）ピペラジン、２，４，６−トリス(ジメチルアミノメチル)フェノール、Ｎ，Ｎ−ジメチルアミノヘキサノール、トリエタノールアミン等が挙げられる。 Examples of the amine catalyst include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N ′ , N ′, N′-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N′-dimethylpiperazine, N-methyl-N′-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N, N-dimethylamido Noethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethyl Examples include aminohexanol and triethanolamine.
また、有機金属触媒としては、オクタン酸スズ、二ラウリン酸ジブチルスズ、オクタン酸鉛ジブチル等が挙げられる。 Examples of organometallic catalysts include tin octoate, dibutyltin dilaurate, and lead dibutyl octoate.
こうして得られるポリウレタン溶液におけるポリウレタンの濃度は、通常、３０重量％以上８０重量％以下の範囲が好ましい。 The concentration of polyurethane in the polyurethane solution thus obtained is usually preferably in the range of 30% by weight to 80% by weight.
本発明においては、かかるポリウレタン溶液に金属リン酸塩および４級アンモニウム塩系抗菌剤を含有せしめる。金属リン酸塩および４級アンモニウム塩系抗菌剤をポリウレタン溶液へ添加する場合、任意の方法が採用できる。その代表的な方法としては、スタティックミキサーによる方法、攪拌による方法、ホモミキサーによる方法、２軸押し出し機を用いる方法など各種の手段が採用できる。 In the present invention, the polyurethane solution contains a metal phosphate and a quaternary ammonium salt antibacterial agent. When adding a metal phosphate and a quaternary ammonium salt antibacterial agent to the polyurethane solution, any method can be adopted. As typical methods, various means such as a method using a static mixer, a method using stirring, a method using a homomixer, a method using a biaxial extruder, and the like can be adopted.
そして、本発明においては、アンモニアガスに対する消臭性を向上させるため、金属リン酸塩を１重量％以上１０重量％以下の範囲でポリウレタン弾性糸に含有させることが好ましい。そのためには、紡糸前のポリウレタン紡糸原液に、金属リン酸塩を斑なく分散させる必要があり、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等を溶媒とするポリウレタンの紡糸原液に、上述の金属リン酸塩を加え、斑なく分散するよう攪拌、混合処理することが好ましい。具体的には、金属リン酸塩を、あらかじめＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等の溶媒に分散し金属リン酸塩分散液とし、その分散液をポリウレタン紡糸原液に混合することが好ましい。ここで、添加される金属リン酸塩分散液の溶媒は、ポリウレタン溶液への均一な添加を行う観点から、ポリウレタン溶液と同一の溶剤を用いることが好ましい。また、金属リン酸塩のポリウレタン溶液への添加の際には、前記した、例えば、耐光剤、耐酸化防止剤などの薬剤や顔料などを同時に添加してもよい。 And in this invention, in order to improve the deodorizing property with respect to ammonia gas, it is preferable to make a polyurethane elastic yarn contain metal phosphate in the range of 1 to 10 weight%. For this purpose, it is necessary to disperse the metal phosphate completely in the polyurethane spinning stock solution before spinning, and in the polyurethane spinning stock solution using N, N-dimethylformamide, N, N-dimethylacetamide or the like as a solvent, It is preferable to add a metal phosphate and stir and mix so as to disperse it completely. Specifically, the metal phosphate is previously dispersed in a solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, etc. to form a metal phosphate dispersion, and the dispersion is mixed with the polyurethane spinning dope. Is preferred. Here, the solvent of the metal phosphate dispersion to be added is preferably the same solvent as the polyurethane solution from the viewpoint of uniform addition to the polyurethane solution. In addition, when the metal phosphate is added to the polyurethane solution, for example, the above-mentioned chemicals such as a light-proofing agent and an antioxidant and a pigment may be added simultaneously.
また、本発明においては、各種細菌への抗菌性を高めるために４級アンモニウム塩系抗菌剤を含有させる。そのためには、紡糸前のポリウレタン紡糸原液に４級アンモニウム塩系抗菌剤を含有させ、紡糸を行う。４級アンモニウム塩系抗菌剤を紡糸原液に含有させる方法としては単独で紡糸原液と混合しても良いし、前記金属リン酸塩分散液に予め混合しておいても良い。 In the present invention, a quaternary ammonium salt antibacterial agent is contained in order to enhance antibacterial properties against various bacteria. For this purpose, spinning is performed by adding a quaternary ammonium salt antibacterial agent to the polyurethane spinning dope before spinning. As a method for adding the quaternary ammonium salt antibacterial agent to the spinning dope, it may be mixed with the spinning dope alone or may be mixed in advance with the metal phosphate dispersion.
以上のように構成した紡糸原液を、たとえば乾式紡糸、湿式紡糸、もしくは溶融紡糸し、巻き取ることで、本発明のポリウレタン弾性糸を得ることができる。中でも、細物から太物まであらゆる繊度において安定に紡糸できるという観点から、乾式紡糸が好ましい。 The polyurethane elastic yarn of the present invention can be obtained by, for example, dry-spinning, wet-spinning, or melt-spinning and winding up the spinning stock solution configured as described above. Of these, dry spinning is preferred from the viewpoint of stable spinning at all finenesses from fine to thick.
本発明のポリウレタン弾性糸の繊度、断面形状などは特に限定されるものではない。例えば、糸の断面形状は円形であってもよく、また扁平であってもよい。 The fineness and cross-sectional shape of the polyurethane elastic yarn of the present invention are not particularly limited. For example, the cross-sectional shape of the yarn may be circular or flat.
そして、乾式紡糸方式についても特に限定されるものではなく、所望する特性や紡糸設備に見合った紡糸条件等を適宜選択して紡糸すればよい。 Also, the dry spinning method is not particularly limited, and spinning may be performed by appropriately selecting a spinning condition or the like suitable for desired characteristics and spinning equipment.
たとえば、本発明のポリウレタン弾性糸の永久歪率と応力緩和は、特にゴデローラーと巻取機の速度比の影響を受けやすいので、糸の使用目的に応じて適宜決定されるのが好ましい。すなわち、所望の永久歪率と応力緩和を有するポリウレタン弾性糸を得る観点から、ゴデローラーと巻取機の速度比は１．１０以上１．６５以下の範囲として巻き取ることが好ましい。 For example, the permanent set rate and stress relaxation of the polyurethane elastic yarn of the present invention are particularly susceptible to the speed ratio of the godet roller and the winder, and therefore are preferably determined as appropriate according to the intended use of the yarn. That is, from the viewpoint of obtaining a polyurethane elastic yarn having a desired permanent set rate and stress relaxation, it is preferable that the speed ratio between the godet roller and the winder is 1.10 to 1.65.
また、紡糸速度は、得られるポリウレタン弾性糸の強度を向上させる観点から、２５０ｍ／分以上であることが好ましい。 The spinning speed is preferably 250 m / min or more from the viewpoint of improving the strength of the obtained polyurethane elastic yarn.
本発明について実施例を用いてさらに詳細に説明する。 The present invention will be described in more detail with reference to examples.
［消臭性、抗菌性評価用編み地の作成］
３３ｄｔｅｘのポリウレタン弾性糸を３．５倍に延伸し、これに鞘糸としてポリアミド加工糸（商標キュープ、東レ（株）製、３３デシテックス２６フィラメント）を撚り数８００Ｔ／ｍでカバーリングして、Ｓ撚りとＺ撚りのシングルカバリング糸（ＳＣＹ）を作製した。
[Creation of knitted fabric for deodorant and antibacterial evaluation]
A polyurethane elastic yarn of 33 dtex was stretched 3.5 times, and a polyamide processed yarn (trademark Cupe, manufactured by Toray Industries, Inc., 33 dtex 26 filament) as a sheath yarn was covered at a twist number of 800 T / m. Twisted and Z-twisted single covering yarn (SCY) was produced.
さらに、パンスト編機（ロナティ社製、針数４００本）の給糸口１、３口に上記Ｓ撚りＳＣＹを、２、４口に上記Ｚ撚りＳＣＹを、編み込み張力１．０ ｇ で給糸し、編地を編成した。編地中のポリウレタン弾性糸の含有率は２１％であった。 Further, the S twist SCY was fed into the yarn feeders 1 and 3 of the pantyhose knitting machine (Ronati Corp., 400 needles), and the Z twist SCY was fed into the yarn feeders 2 and 4 with a weaving tension of 1.0 g. Knitted fabric. The content of polyurethane elastic yarn in the knitted fabric was 21%.
次いで、編地の染色加工を以下の通り実施し、タイツ編地を得た。
（１）プレセット：真空乾燥機使用、９０℃×１０分
（２）染色： チバ・スペシャルティ・ケミカルズ（株）製の染料“Ｌａｎａｓｅｔ”（登録商標） Ｂｌａｃｋ Ｂを２．０ｏｗｆ％使用して９ ０℃で６０分間処理し黒色に染めた。染色時のｐＨ調整は酢酸と硫安で実施した。
（３）最後に柔軟処理を行い、セット工程（パンストセット機使用、セット：１１５℃×１０秒、乾燥：１２０℃×３ ０秒） を通して仕上げた。
Subsequently, the dyeing | staining process of the knitted fabric was implemented as follows and the tights knitted fabric was obtained.
(1) Preset: using a vacuum dryer, 90 ° C. × 10 minutes (2) Dyeing: 9% using 2.0 ow% of dye “Lanaset” (registered trademark) Black B manufactured by Ciba Specialty Chemicals Co., Ltd. It was treated at 0 ° C. for 60 minutes and dyed black. The pH adjustment during dyeing was performed with acetic acid and ammonium sulfate.
(3) Finally, a softening treatment was performed and finished through a setting process (using a pantyhose setting machine, setting: 115 ° C. × 10 seconds, drying: 120 ° C. × 30 seconds).
［洗濯方法］
繊維製品新機能評価評議会が制定している、洗濯方法マニュアルに準拠した（ＪＩＳ Ｌ０２１７：１９９５の付表１、洗い方１０３）。すなわち、ＪＩＳ Ｌ０２１７：１９９５の付表１、洗い方１０３に規定される家庭電気洗濯機を使用し、４０℃の水３０リットルに対しＪＡＦＥＴ標準洗剤（繊維製品新機能評価評議会製）４０ミリリットルを溶解して洗濯液とし、この洗濯液に１ｋｇの試料である被洗濯物を入れた。５分間洗濯、脱水、２分間濯ぎ洗い、脱水、２分間濯ぎ洗い、脱水の工程を１回とし、洗濯を行った。
[How to wash]
It conformed to the washing method manual established by the Council for Evaluation of New Functionality of Textile Products (Appendix 1 of JIS L0217: 1995, Washing Method 103). That is, using a household electric washing machine specified in Appendix 1 of JIS L0217: 1995, washing method 103, 40 ml of JAFET standard detergent (manufactured by the Council for New Functional Evaluation of Textile Products) is dissolved in 30 liters of water at 40 ° C. Then, the laundry was used as a washing liquid, and a 1 kg sample to be washed was put into the washing liquid. Washing was carried out with 5 minutes of washing, dehydration, 2 minutes of rinsing, dehydration, 2 minutes of rinsing and dehydration once.
［消臭性］
消臭試験は、消臭加工繊維製品認証基準（制定者：社団法人繊維評価技術協議会 製品認証部、制定日：平成１４年９月１日） に準拠し、以下のように機器試験により臭気成分の消臭性評価を行なった。なお、社団法人繊維評価技術協議会で、該機器分析試験による各臭気成分の減少率について「消臭効果有り」とする合格基準を、表１に示す。
（検知管法）
１．サンプル（１０ｃ ｍ×１０ｃｍ）をテドラーバッグに入れる。
２．表１に示す所定量の試験ガスを注入し、２時間後の残存ガス濃度（ｐｐｍ）を成分対応検知管（ ガステック社製）で測定する。尚ガス充填量は３Ｌ、希釈ガスは乾燥空気または窒素ガスとする。
[Deodorization]
The deodorization test conforms to the deodorant processed fiber product certification standard (established by: Product Evaluation Department, Japan Textile Evaluation Technology Council, established date: September 1, 2002). The deodorant evaluation of the component was performed. In addition, Table 1 shows the acceptance criteria for “deodorizing effect” for the rate of reduction of each odor component by the instrumental analysis test at the Japan Fiber Evaluation Technology Council.
(Detection tube method)
1. A sample (10 cm × 10 cm) is placed in a Tedlar bag.
2. A predetermined amount of test gas shown in Table 1 is injected, and the residual gas concentration (ppm) after 2 hours is measured with a component-compatible detector tube (manufactured by Gastec). The gas filling amount is 3 L, and the dilution gas is dry air or nitrogen gas.
３．サンプルを用いずに同様の評価を行い、空試験とする。
４．評価は下記の式に従って、残存ガス濃度の減少率を算出し、消臭率として表記する。
3. The same evaluation is performed without using a sample, and a blank test is performed.
4). In the evaluation, the reduction rate of the residual gas concentration is calculated according to the following formula and expressed as the deodorization rate.
なお、測定値はｎ＝３の平均値で求めた。 The measured value was determined as an average value of n = 3.
［抗菌性］
抗菌試験は、社団法人繊維評価技術協議会が指定した抗菌性試験手順（ＪＩＳ Ｌ１９０２：２００８、菌液吸収法）に準拠して実施した。Ｘを無加工試料の１８時間培養後の生菌数（個）、Ｙを試験生地の１８時間培養後の生菌数（個）として、静菌活性値を下記の式から算出して抗菌力を評価した。なお、測定値はｎ＝３の平均値で求めた。
[Antimicrobial]
The antibacterial test was performed in accordance with the antibacterial test procedure (JIS L1902: 2008, bacterial solution absorption method) designated by the Japan Fiber Evaluation Technology Council. The antibacterial activity is calculated by calculating the bacteriostatic activity value from the following formula, where X is the number of viable bacteria after culturing the untreated sample (18) and Y is the number of viable bacteria after culturing the test dough for 18 hours. Evaluated. In addition, the measured value was calculated | required by the average value of n = 3.
また、社団法人繊維評価技術協議会では、黄色ブドウ球菌の静菌活性値が２．２以上の時、抗菌に「効果有り」と認める。 In addition, the Japan Fiber Evaluation Technology Council recognizes that “effective” for antibacterial activity when the bacteriostatic activity value of Staphylococcus aureus is 2.2 or more.
［平均一次粒子径］
無機粒子を日立製作所（株）製 電解放射型走査電子顕微鏡（ＦＥ−ＳＥＭ）Ｓ−８００にて撮影を行い、画像処理ソフトＩｍａｇｅ−Ｐｒｏ Ｖｅｒｓｉｏｎ４．０にて解析して求めた。なお、測定パラメーターは投影面積円相当径で行い、１サンプル当たりｎ＝２０の個数平均により平均一次粒子径を求めた。
[Average primary particle size]
The inorganic particles were photographed with an electrolytic emission scanning electron microscope (FE-SEM) S-800 manufactured by Hitachi, Ltd., and analyzed and obtained with image processing software Image-Pro Version 4.0. The measurement parameter was a projected area equivalent circle diameter, and the average primary particle diameter was determined by the number average of n = 20 per sample.
［ポリウレタン弾性糸中の金属リン酸塩の含有量］
ポリウレタン弾性糸を原糸吸光光度法によって分析し、金属リン酸塩の濃度を測定した。測定は、金属リン酸塩中の金属（Ａｌ、Ｚｒ、Ｔｉ）について行った。なお、測定値はｎ＝３の平均より求め、金属リン酸塩の含有量を以下の式より求めた。
[Content of metal phosphate in polyurethane elastic yarn]
The polyurethane elastic yarn was analyzed by raw yarn absorptiometry, and the concentration of metal phosphate was measured. The measurement was performed on the metal (Al, Zr, Ti) in the metal phosphate. In addition, the measured value was calculated | required from the average of n = 3, and content of the metal phosphate was calculated | required from the following formula | equation.
［４級アンモニウム塩の含有量］
試料（ポリウレタン糸）１ｇを秤量し、メタノール１００ｍｌに入れ、４級アンモニウム塩を抽出した。抽出液について、液体クロマトグラフィーにて予め作成しておいた標準液から定量を行った。以下に分析条件を示す。なお、測定はｎ＝２の平均より求めた。
カラム：ＬｉＣｈｒｏｓｐｈｅｒ １００ ＲＰ−１８（５μｍ）、内径４．６ｍｍ、 長さ１５０ｍｍ、カラム温度：３５℃
検出：ＵＶ２１０ｎｍ
移動相：メタノール／水混合溶液（６０／４０容量％）、流速：１ｍｌ／分、注入量：２μｌ
［実施例１］
分子量１８００のＰＴＭＧ、ＭＤＩ、エチレンジアミンおよび末端封鎖剤としてジエチルアミンからなるポリウレタンウレア重合体のＤＭＡＣ溶液（３５重量％）を調整した。次に、酸化防止剤として、ｔ−ブチルジエタノールアミンとメチレン−ビス−（４−シクロヘキシルイソシアネ−ト）の反応によって生成せしめたポリウレタン溶液（デュポン社製“メタクロール”（登録商標）２４６２）と、ｐ−クレゾ−ルおよびジビニルベンゼンの縮合重合体（デュポン社製“メタクロール”（登録商標）２３９０）とを２対１（重量比）で混合し、酸化防止剤ＤＭＡｃ溶液（濃度３５重量％）を調整し、前記ポリウレタンウレア重合体のＤＭＡｃ溶液９６重量部と酸化防止剤溶液４重量部を混合し、ポリマ溶液Ａ１とした。次に、東亞合成社製のリン酸ジルコニウム系消臭剤“ケスモン”（登録商標）ＮＳ−１０（平均一次粒子径０．９μｍ）をホモミキサーによりＤＭＡｃに分散し、リン酸ジルコニウム分散液Ｂ１（３５重量％）とした。次に４級アンモニウム系抗菌剤である三洋化成(株)社製の“ネオジャーミＤＦＳ”（ジデシルジメチルアンモニウム３フッ化メチルスルホン酸塩）をＤＭＡｃに３５重量％に調製し、抗菌剤溶液Ｃ１とした。ポリマ溶液Ａ１、Ｂ１、Ｃ１を９６重量％、３重量％、１重量％で均一に混合し、紡糸溶液Ｄ１とした。これをゴデローラーと巻取機の速度比１．３として７２０ｍ/分のスピードで乾式紡糸し、３３デシテックス、２フィラメント、リン酸ジルコニウムの含有量が３重量％、４級アンモニウム塩系抗菌剤ネオジャーミＤＦＳの含有量が１重量％であるポリウレタン糸の２００ｇ巻糸体を得た。
[Quaternary ammonium salt content]
A sample (polyurethane yarn) 1 g was weighed and placed in 100 ml of methanol to extract a quaternary ammonium salt. The extract was quantified from a standard solution prepared in advance by liquid chromatography. The analysis conditions are shown below. The measurement was obtained from the average of n = 2.
Column: LiChrosphere 100 RP-18 (5 μm), inner diameter 4.6 mm, length 150 mm, column temperature: 35 ° C.
Detection: UV210nm
Mobile phase: methanol / water mixed solution (60/40% by volume), flow rate: 1 ml / min, injection volume: 2 μl
[Example 1]
A DMAC solution (35% by weight) of a polyurethane urea polymer comprising PTMG, MDI, ethylenediamine having a molecular weight of 1800 and diethylamine as a terminal blocking agent was prepared. Next, as an antioxidant, a polyurethane solution ("Megachlor" (registered trademark) 2462 manufactured by DuPont) produced by a reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), 2: 1 (weight ratio) was mixed with a condensation polymer of p-cresol and divinylbenzene (“METACROL” (registered trademark) 2390, manufactured by DuPont), and an antioxidant DMAc solution (concentration 35% by weight). Then, 96 parts by weight of the polyurethane urea polymer DMAc solution and 4 parts by weight of the antioxidant solution were mixed to obtain a polymer solution A1. Next, zirconium phosphate-based deodorant “Kesmon” (registered trademark) NS-10 (average primary particle size 0.9 μm) manufactured by Toagosei Co., Ltd. was dispersed in DMAc with a homomixer, and zirconium phosphate dispersion B1 ( 35% by weight). Next, “Neogermi DFS” (didecyldimethylammonium trifluoride methylsulfonate) manufactured by Sanyo Kasei Co., Ltd., which is a quaternary ammonium antibacterial agent, was prepared in DMAc to 35% by weight, and antibacterial agent solution C1 did. Polymer solutions A1, B1, and C1 were uniformly mixed at 96 wt%, 3 wt%, and 1 wt% to obtain spinning solution D1. This was dry-spun at a speed ratio of 720 m / min at a speed ratio of 1.3 between the godet roller and the winder, and the content of 33 dtex, 2 filaments, zirconium phosphate was 3% by weight, quaternary ammonium salt antibacterial agent Neo-Jami DFS A 200 g roll of polyurethane yarn having a content of 1 wt% was obtained.
得られたポリウレタン弾性糸について、評価用編み地を作成し、消臭性と抗菌性を測定した。各種評価結果について表２に示す。 About the obtained polyurethane elastic yarn, the knitted fabric for evaluation was created and deodorant property and antibacterial property were measured. Various evaluation results are shown in Table 2.
［実施例２］
リン酸ジルコニウム分散液Ｂ１に代えて、テイカ(株)社製のトリポリリン酸二水素アルミニウム系消臭剤“Ｋ−ＦＲＥＳＨ”（登録商標）＃１００Ｐ（平均一次粒子径１．０μｍ）をホモミキサーによりＤＭＡｃに分散し、トリポリリン酸二水素アルミニウム分散液Ｂ２（３５重量％）とした。
[Example 2]
In place of zirconium phosphate dispersion B1, aluminum dihydrogen phosphate-based deodorizer “K-FRESH” (registered trademark) # 100P (average primary particle size 1.0 μm) manufactured by Teika Co., Ltd. was used with a homomixer. Dispersed in DMAc, aluminum dihydrogen phosphate tridispersion B2 (35% by weight) was obtained.
ポリマ溶液Ａ１、Ｂ２、Ｃ１を９６重量％、３重量％、１重量％で均一に混合し、紡糸溶液Ｄ２とし、これを実施例１と同様に乾式紡糸して、３３デシテックス、２フィラメント、トリポリリン酸二水素アルミニウムの含有量が３重量％、４級アンモニウム塩系抗菌剤ネオジャーミＤＦＳの含有量が１重量％であるポリウレタン糸の２００ｇ巻糸体を得た。 The polymer solutions A1, B2, and C1 were uniformly mixed at 96% by weight, 3% by weight, and 1% by weight to obtain a spinning solution D2, which was dry-spun in the same manner as in Example 1 to obtain 33 decitex, 2-filament, tripolyline. A 200 g roll of polyurethane yarn having a content of aluminum dihydrogen aluminum of 3% by weight and a content of quaternary ammonium salt antibacterial agent neo-germi DFS of 1% by weight was obtained.
各種評価結果について表２に示す。 Various evaluation results are shown in Table 2.
［実施例３］
リン酸ジルコニウム分散液Ｂ１に代えて、合成したリン酸チタン（平均一次粒子径１．１μｍ）をホモミキサーによりＤＭＡｃに分散し、リン酸チタン分散液Ｂ３（３５重量％）とした。
[Example 3]
Instead of zirconium phosphate dispersion B1, synthesized titanium phosphate (average primary particle size 1.1 μm) was dispersed in DMAc by a homomixer to obtain titanium phosphate dispersion B3 (35 wt%).
ポリマ溶液Ａ１、Ｂ３、Ｃ１を９６重量％、３重量％、１重量％で均一に混合し、紡糸溶液Ｄ３とし、これを実施例１と同様に乾式紡糸して、３３デシテックス、２フィラメント、リン酸チタンの含有量が３重量％、４級アンモニウム塩系抗菌剤ネオジャーミＤＦＳの含有量が１重量％であるポリウレタン糸の２００ｇ巻糸体を得た。 The polymer solutions A1, B3, and C1 were uniformly mixed at 96% by weight, 3% by weight, and 1% by weight to obtain a spinning solution D3, which was dry-spun in the same manner as in Example 1 to obtain 33 dtex, 2 filaments, phosphorus A 200 g roll of polyurethane yarn having a titanium acid content of 3% by weight and a quaternary ammonium salt antibacterial agent neo-germi DFS content of 1% by weight was obtained.
各種評価結果について表２に結果を示す。
［実施例４］
分子量２１００のＰＴＭＧ、ＭＤＩ、エチレングリコールおよび末端封鎖剤として１−ブタノールからなるポリウレタンウレタン重合体のＤＭＡＣ溶液（３５重量％）を調整した。次に、酸化防止剤として、ｔ−ブチルジエタノールアミンとメチレン−ビス−（４−シクロヘキシルイソシアネ−ト）の反応によって生成せしめたポリウレタン溶液（デュポン社製“メタクロール”（登録商標）２４６２）と、ｐ−クレゾ−ルおよびジビニルベンゼンの縮合重合体（デュポン社製“メタクロール”（登録商標）２３９０）とを２対１（重量比）で混合し、酸化防止剤ＤＭＡｃ溶液（濃度３５重量％）を調整し、前記ポリウレタンウレア重合体のＤＭＡｃ溶液９６重量部と酸化防止剤溶液４重量部を混合し、ポリマ溶液Ａ２とした。さらに三洋化成(株)社製の“ネオジャーミＤＦＳ”溶液Ｃ１に代えて、ロンザジャパン(株)社製４級アンモニウム塩系抗菌剤“ＢＡＲＱＵＡＴ”（登録商標）ＭＳ−１００（ベンジルジメチルテトラデシルアンモニウムクロリド）をＤＭＡｃに３５重量％に調製し、抗菌剤溶液Ｃ２とした。
Table 2 shows the results of various evaluation results.
[Example 4]
A DMAC solution (35% by weight) of a polyurethane urethane polymer having a molecular weight of 2,100, PTMG, MDI, ethylene glycol and 1-butanol as a terminal blocking agent was prepared. Next, as an antioxidant, a polyurethane solution ("Megachlor" (registered trademark) 2462 manufactured by DuPont) produced by a reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), 2: 1 (weight ratio) was mixed with a condensation polymer of p-cresol and divinylbenzene (“METACROL” (registered trademark) 2390, manufactured by DuPont), and an antioxidant DMAc solution (concentration 35% by weight). And 96 parts by weight of the polyurethane urea polymer DMAc solution and 4 parts by weight of the antioxidant solution were mixed to obtain a polymer solution A2. Furthermore, instead of “Neogermi DFS” solution C1 manufactured by Sanyo Chemical Co., Ltd., quaternary ammonium salt antibacterial agent “BARQUAT” (registered trademark) MS-100 (benzyldimethyltetradecyl ammonium chloride) manufactured by Lonza Japan Co., Ltd. ) Was prepared to 35% by weight in DMAc to obtain an antimicrobial solution C2.
ポリマ溶液Ａ２、Ｂ１、Ｃ２を９５重量％、４重量％、１重量％で均一に混合し、紡糸溶液Ｄ４とし、これを実施例１と同様に乾式紡糸して、３３デシテックス、２フィラメント、リン酸ジルコニウムの含有量が４重量％、４級アンモニウム塩系抗菌剤“ＢＡＲＱＵＡＴ”（登録商標）ＭＳ−１００の含有量が１重量％であるポリウレタン糸の２００ｇ巻糸体を得た。 Polymer solutions A2, B1, and C2 were uniformly mixed at 95% by weight, 4% by weight, and 1% by weight to obtain spinning solution D4, which was dry-spun in the same manner as in Example 1 to obtain 33 dtex, 2 filaments, phosphorous 200 g of a polyurethane yarn having a zirconium acid content of 4 wt% and a quaternary ammonium salt antibacterial agent “BARQUAT” (registered trademark) MS-100 content of 1 wt% was obtained.
［実施例５］
ポリマ溶液Ａ２、Ｂ２、Ｃ１を９７．５重量％、１．５重量％、１．０重量％で均一に混合し、紡糸溶液Ｄ５とした。これを実施例１と同様に乾式紡糸し、３３デシテックス、２フィラメント、トリポリリン酸二水素アルミニウムの含有量が１．５重量％であるポリウレタン糸の２００ｇ巻糸体を得た。
[Example 5]
Polymer solutions A2, B2, and C1 were uniformly mixed at 97.5 wt%, 1.5 wt%, and 1.0 wt% to obtain spinning solution D5. This was dry-spun in the same manner as in Example 1 to obtain a 200 g wound body of polyurethane yarn having a content of 33 dtex, 2 filaments, and aluminum dihydrogen tripolyphosphate of 1.5% by weight.
各種評価結果について表２に示す。 Various evaluation results are shown in Table 2.
［実施例６］
４級アンモニウム塩系抗菌剤溶液Ｃ１に代えて、塩化ジデシルジメチルアンモニウムをＤＭＡｃに３５重量％に調製し、抗菌剤溶液Ｃ３とした。
[Example 6]
Instead of the quaternary ammonium salt-based antibacterial agent solution C1, didecyldimethylammonium chloride was prepared in DMAc at 35% by weight to obtain an antibacterial agent solution C3.
ポリマ溶液Ａ２、Ｂ１、Ｃ３を９６．７重量％、３重量％、０．３重量％で均一に混合し、紡糸溶液Ｄ６とし、これを実施例１と同様に乾式紡糸して、３３デシテックス、２フィラメント、リン酸チタンの含有量が３重量％、４級アンモニウム塩系抗菌剤塩化ジデシルジメチルアンモニウムの含有量が０．３重量％であるポリウレタン糸の２００ｇ巻糸体を得た。 The polymer solutions A2, B1, and C3 were uniformly mixed at 96.7% by weight, 3% by weight, and 0.3% by weight to obtain a spinning solution D6, which was dry-spun in the same manner as in Example 1 to obtain 33 dtex. A 200 g wound body of polyurethane yarn having a content of 2 filaments, a titanium phosphate content of 3% by weight and a quaternary ammonium salt antibacterial agent didecyldimethylammonium chloride of 0.3% by weight was obtained.
各種評価結果について表２に示す。 Various evaluation results are shown in Table 2.
［実施例７］
４級アンモニウム塩系抗菌剤溶液Ｃ１に代えて、塩化ベンゼトニウムをＤＭＡｃに３５重量％に調製し、抗菌剤溶液Ｃ４とした。
[Example 7]
Instead of the quaternary ammonium salt-based antibacterial agent solution C1, benzethonium chloride was prepared in DMAc to 35% by weight to obtain an antibacterial agent solution C4.
ポリマ溶液Ａ２、Ｂ１、Ｃ４を９６．８重量％、３重量％、０．２重量％で均一に混合し、紡糸溶液Ｄ７とし、これを実施例１と同様に乾式紡糸して、３３デシテックス、２フィラメント、リン酸チタンの含有量が３重量％、４級アンモニウム塩系抗菌剤塩化ジデシルジメチルアンモニウムの含有量が０．３重量％であるポリウレタン糸の２００ｇ巻糸体を得た。 The polymer solutions A2, B1, and C4 were uniformly mixed at 96.8 wt%, 3 wt%, and 0.2 wt% to obtain a spinning solution D7, which was dry-spun in the same manner as in Example 1 to obtain 33 dtex. A 200 g wound body of polyurethane yarn having a content of 2 filaments, a titanium phosphate content of 3% by weight and a quaternary ammonium salt antibacterial agent didecyldimethylammonium chloride of 0.3% by weight was obtained.
各種評価結果について表２に示す。 Various evaluation results are shown in Table 2.
［実施例８］
ポリマ溶液Ａ２、Ｂ１、Ｃ２を９１．５重量％、８重量％、１．５重量％で均一に混合し、紡糸溶液Ｄ８とした。これを実施例１と同様に乾式紡糸し、３３デシテックス、２フィラメント、リン酸ジルコニウムの含有量が８重量％、４級アンモニウム塩系抗菌剤“ＢＡＲＱＵＡＴ”（登録商標）ＭＳ−１００の含有量が１重量％であるポリウレタン糸の１００ｇ巻糸体を得た。ただし、紡糸中に口金の詰まりと思われる糸切れが発生し、他の実施例に比べて紡糸性は良くなかった。
[Example 8]
Polymer solutions A2, B1, and C2 were uniformly mixed at 91.5 wt%, 8 wt%, and 1.5 wt% to obtain spinning solution D8. This was dry-spun in the same manner as in Example 1, and the content of 33 dtex, 2 filaments, zirconium phosphate was 8% by weight, and the content of the quaternary ammonium salt antibacterial agent “BARQUAT” (registered trademark) MS-100 was A 100 g roll of polyurethane yarn of 1% by weight was obtained. However, the yarn breakage that seemed to be clogged with the die occurred during spinning, and the spinnability was not good as compared with other examples.
各種評価結果について表２に示す。 Various evaluation results are shown in Table 2.
［比較例１］
ポリマ溶液Ａ１を実施例１と同様に乾式紡糸し、３３デシテックス、２フィラメントのポリウレタン糸の２００ｇ巻糸体を得た。 各種評価結果について表２に示す。
[Comparative Example 1]
The polymer solution A1 was dry-spun in the same manner as in Example 1 to obtain 200 g of a 33 dtex, 2-filament polyurethane yarn. Various evaluation results are shown in Table 2.
［比較例２］
ポリマ溶液Ａ２を実施例１と同様に乾式紡糸し、３３デシテックス、２フィラメントのポリウレタン糸の２００ｇ巻糸体を得た。 各種評価結果について表２に示す。
[Comparative Example 2]
The polymer solution A2 was dry-spun in the same manner as in Example 1 to obtain a 200-g wound body of 33 dtex and 2-filament polyurethane yarn. Various evaluation results are shown in Table 2.
［比較例３］
ポリマ溶液Ａ２、Ｂ１を９８重量％、２重量％で均一に混合し、紡糸溶液Ｄ９とした。これを実施例１と同様に乾式紡糸し、３３デシテックス、２フィラメント、リン酸ジルコニウムの含有量が２重量％であるポリウレタン糸の２００ｇ巻糸体を得た。
[Comparative Example 3]
Polymer solutions A2 and B1 were uniformly mixed at 98% by weight and 2% by weight to obtain a spinning solution D9. This was dry-spun in the same manner as in Example 1 to obtain a 200 g wound body of polyurethane yarn having a content of 33 dtex, 2 filaments and zirconium phosphate of 2% by weight.
評価の結果、酢酸ガスに対する消臭性と抗菌性に劣るものであった。各種評価結果について表２に示す。 As a result of evaluation, it was inferior in deodorizing property and antibacterial property against acetic acid gas. Various evaluation results are shown in Table 2.
［比較例４］
ポリマ溶液Ａ２、Ｂ１、Ｃ１を９８．５重量％、０．５重量％、１重量％で均一に混合し、紡糸溶液Ｄ１０とした。これを実施例１と同様に乾式紡糸し、３３デシテックス、２フィラメント、リン酸ジルコニウムの含有量が０．５重量％、４級アンモニウム塩系抗菌剤ネオジャーミＤＦＳの含有量が１重量％であるポリウレタン糸の２００ｇ巻糸体を得た。
[Comparative Example 4]
Polymer solutions A2, B1, and C1 were uniformly mixed at 98.5 wt%, 0.5 wt%, and 1 wt% to obtain spinning solution D10. This was dry-spun in the same manner as in Example 1, and the polyurethane content was 33 decitex, 2-filament, zirconium phosphate content was 0.5% by weight, quaternary ammonium salt antibacterial agent neo-germi DFS content was 1% by weight. A 200 g wound body of yarn was obtained.
評価の結果、金属リン酸塩の含有量が少ないためアンモニアに対する消臭性に劣るものであった。各種評価結果について表２に示す。 As a result of the evaluation, the content of the metal phosphate was small, so that the deodorizing property against ammonia was poor. Various evaluation results are shown in Table 2.
［比較例５］
ポリマ溶液Ａ２、Ｃ２を９９．５重量％、０．５重量％で均一に混合し、紡糸溶液Ｄ１１とした。これを実施例１と同様に乾式紡糸し、３３デシテックス、２フィラメントのポリウレタン糸の２００ｇ巻糸体を得た。
[Comparative Example 5]
Polymer solutions A2 and C2 were uniformly mixed at 99.5 wt% and 0.5 wt% to obtain spinning solution D11. This was dry-spun in the same manner as in Example 1 to obtain a 200 g roll of 33 dtex and 2-filament polyurethane yarn.
評価の結果、金属リン酸塩が含まれていないため消臭性に劣り、洗濯処理後の抗菌性も劣るものだった。各種評価結果について表２に示す。 As a result of the evaluation, the metal phosphate was not contained, so the deodorizing property was inferior and the antibacterial property after the washing treatment was also inferior. Various evaluation results are shown in Table 2.
［比較例６］
リン酸ジルコニウム分散液Ｂ１に代えて、堺化学（株）社製超微粒子酸化亜鉛“ＦＩＮＥＸ”−２５（平均一次粒子径０．０４μｍ）をホモミキサーによりＤＭＡｃに分散し、酸化亜鉛分散液Ｂ４（３５重量％）とした。
[Comparative Example 6]
Instead of zirconium phosphate dispersion B1, ultrafine zinc oxide “FINEX” -25 (average primary particle size 0.04 μm) manufactured by Sakai Chemical Co., Ltd. was dispersed in DMAc with a homomixer, and zinc oxide dispersion B4 ( 35% by weight).
ポリマ溶液Ａ１、Ｂ４、Ｃ１を９６．５重量％、３重量％、０．５重量％で均一に混合し、紡糸溶液Ｄ１２とした。これを実施例１と同様に乾式紡糸し、３３デシテックス、２フィラメント、酸化亜鉛の含有量が３重量％、ネオジャーミＤＦＳの含有量が０．５重量％であるポリウレタン糸の２００ｇ巻糸体を得た。 Polymer solutions A1, B4, and C1 were uniformly mixed at 96.5 wt%, 3 wt%, and 0.5 wt% to obtain spinning solution D12. This was dry-spun in the same manner as in Example 1 to obtain a 200 g roll of polyurethane yarn having 33 decitex, 2 filaments, zinc oxide content of 3% by weight and neogerm DFS content of 0.5% by weight. It was.
評価の結果、アンモニアに対する消臭性が劣る結果であった。各種評価結果について表２に示す。 As a result of the evaluation, the deodorizing property against ammonia was inferior. Various evaluation results are shown in Table 2.
［比較例７］
４級アンモニウム塩溶液に代えて、天然抗菌剤のヒノキチオールをＤＭＡｃに３５重量％に調製し、溶液Ｃ５（３５重量％）とした。
[Comparative Example 7]
Instead of the quaternary ammonium salt solution, hinokitiol, a natural antibacterial agent, was prepared in DMAc at 35% by weight to obtain Solution C5 (35% by weight).
ポリマ溶液Ａ２、Ｂ４、Ｃ５を９５．９重量％、４重量％、０．１重量％で均一に混合し、紡糸溶液Ｄ１３とした。これを実施例１と同様に乾式紡糸し、３３デシテックス、２フィラメント、酸化亜鉛の含有量が４重量％、ヒノキチオールの含有量が０．１重量％であるポリウレタン糸の２００ｇ巻糸体を得た。
評価の結果、アンモニアに対する消臭性が劣り、洗濯１０回後の酢酸に対する消臭性に劣るものであった。各種評価結果について表２に示す。
Polymer solutions A2, B4, and C5 were uniformly mixed at 95.9 wt%, 4 wt%, and 0.1 wt% to obtain spinning solution D13. This was dry-spun in the same manner as in Example 1 to obtain 200 g of a polyurethane yarn having 33 dtex, 2 filaments, zinc oxide content of 4% by weight and hinokitiol content of 0.1% by weight. .
As a result of evaluation, the deodorizing property against ammonia was poor, and the deodorizing property against acetic acid after 10 washings was poor. Various evaluation results are shown in Table 2.
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| JP6677936B2 (en) * | 2014-05-29 | 2020-04-08 | 東レ・オペロンテックス株式会社 | Deodorant fabric |
| KR101889210B1 (en) | 2017-01-05 | 2018-08-17 | 주식회사 효성 | spandex having deodorant and method for preparing the same |
| WO2019220580A1 (en) * | 2018-05-16 | 2019-11-21 | 東亞合成株式会社 | Deodorant for fine particulate fibers |
| JP7341773B2 (en) * | 2019-07-30 | 2023-09-11 | 東レ・オペロンテックス株式会社 | Polyurethane elastic yarn and its manufacturing method |
| CN110565201B (en) * | 2019-10-30 | 2021-05-04 | 华峰化学股份有限公司 | Preparation method of antibacterial and deodorant spandex |
| CN114293281B (en) * | 2022-01-13 | 2023-11-10 | 华峰化学股份有限公司 | Low-temperature-resistant spandex fiber and preparation method thereof |
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