EP2484821A2 - Spandex fiber with excellent chlorine resistance, and preparation method thereof - Google Patents
Spandex fiber with excellent chlorine resistance, and preparation method thereof Download PDFInfo
- Publication number
- EP2484821A2 EP2484821A2 EP10820828A EP10820828A EP2484821A2 EP 2484821 A2 EP2484821 A2 EP 2484821A2 EP 10820828 A EP10820828 A EP 10820828A EP 10820828 A EP10820828 A EP 10820828A EP 2484821 A2 EP2484821 A2 EP 2484821A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- spandex fiber
- polyurethane
- tertiary
- butyl
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002334 Spandex Polymers 0.000 title claims abstract description 74
- 239000004759 spandex Substances 0.000 title claims abstract description 74
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000460 chlorine Substances 0.000 title claims abstract description 63
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 63
- 239000000835 fiber Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title 1
- -1 hydrotalcite compound Chemical class 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 26
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 26
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 23
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- CXUJOBCFZQGUGO-UHFFFAOYSA-F calcium trimagnesium tetracarbonate Chemical compound [Mg++].[Mg++].[Mg++].[Ca++].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O CXUJOBCFZQGUGO-UHFFFAOYSA-F 0.000 claims abstract description 9
- 229910000515 huntite Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 7
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004814 polyurethane Substances 0.000 claims description 49
- 229920002635 polyurethane Polymers 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 37
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 32
- 239000000194 fatty acid Substances 0.000 claims description 32
- 229930195729 fatty acid Natural products 0.000 claims description 32
- 239000011777 magnesium Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 229920000877 Melamine resin Polymers 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229910020038 Mg6Al2 Inorganic materials 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- JHYLOZKQMTWGPP-UHFFFAOYSA-N 2,9-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]decanedioic acid Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC(CCCCCCC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(O)=O)C(O)=O)=C1 JHYLOZKQMTWGPP-UHFFFAOYSA-N 0.000 claims description 2
- MQMPGAZMYYLSGW-UHFFFAOYSA-N 3-tert-butyl-1-[2-(3-tert-butyl-1,4-dihydroxy-6,6-dimethylheptyl)hydrazinyl]-6,6-dimethylheptane-1,4-diol Chemical compound CC(C)(C)CC(O)C(C(C)(C)C)CC(O)NNC(O)CC(C(C)(C)C)C(O)CC(C)(C)C MQMPGAZMYYLSGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 14
- 230000000996 additive effect Effects 0.000 abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 21
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 14
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 235000019359 magnesium stearate Nutrition 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 235000021314 Palmitic acid Nutrition 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 150000007974 melamines Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 5
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 239000004970 Chain extender Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical class NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical class CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 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
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 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
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-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
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- MGFGCLYIHWYZLF-UHFFFAOYSA-N 1-(isocyanatomethyl)-4-(5-isocyanatopentyl)benzene Chemical compound O=C=NCCCCCC1=CC=C(CN=C=O)C=C1 MGFGCLYIHWYZLF-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- XHFOXACKHBOLCX-UHFFFAOYSA-N 2-n-[10-[(4,6-diamino-1,3,5-triazin-2-yl)amino]decyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCCCCCCCCCCNC=2N=C(N)N=C(N)N=2)=N1 XHFOXACKHBOLCX-UHFFFAOYSA-N 0.000 description 1
- YWZIIYJZQKWCIE-UHFFFAOYSA-N 2-n-[3-[(4,6-diamino-1,3,5-triazin-2-yl)amino]propyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCCCNC=2N=C(N)N=C(N)N=2)=N1 YWZIIYJZQKWCIE-UHFFFAOYSA-N 0.000 description 1
- BRCJAKSIYWHLPW-UHFFFAOYSA-N 2-n-[4-[(4,6-diamino-1,3,5-triazin-2-yl)amino]butyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCCCCNC=2N=C(N)N=C(N)N=2)=N1 BRCJAKSIYWHLPW-UHFFFAOYSA-N 0.000 description 1
- XMUGVXZKCPQZAB-UHFFFAOYSA-N 2-n-[4-[(4,6-diamino-1,3,5-triazin-2-yl)amino]phenyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2C=CC(NC=3N=C(N)N=C(N)N=3)=CC=2)=N1 XMUGVXZKCPQZAB-UHFFFAOYSA-N 0.000 description 1
- UHRBOLIZWMDRRD-UHFFFAOYSA-N 2-n-[6-[(4,6-diamino-1,3,5-triazin-2-yl)amino]hexyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCCCCCCNC=2N=C(N)N=C(N)N=2)=N1 UHRBOLIZWMDRRD-UHFFFAOYSA-N 0.000 description 1
- KYCZUBOPFDXYAU-UHFFFAOYSA-N 2-n-[[(4,6-diamino-1,3,5-triazin-2-yl)amino]methyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCNC=2N=C(N)N=C(N)N=2)=N1 KYCZUBOPFDXYAU-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- HENCHDCLZDQGIQ-UHFFFAOYSA-N 3-[3,5-bis(2-carboxyethyl)-2,4,6-trioxo-1,3,5-triazinan-1-yl]propanoic acid Chemical compound OC(=O)CCN1C(=O)N(CCC(O)=O)C(=O)N(CCC(O)=O)C1=O HENCHDCLZDQGIQ-UHFFFAOYSA-N 0.000 description 1
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-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
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- MLJVEOBSFPHRPV-UHFFFAOYSA-N C=C.C=C.C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 Chemical compound C=C.C=C.C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 MLJVEOBSFPHRPV-UHFFFAOYSA-N 0.000 description 1
- FYXDCPKEDZBMHV-UHFFFAOYSA-N C=C.C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 Chemical compound C=C.C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 FYXDCPKEDZBMHV-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- HSMNQINEKMPTIC-UHFFFAOYSA-N N-(4-aminobenzoyl)glycine Chemical compound NC1=CC=C(C(=O)NCC(O)=O)C=C1 HSMNQINEKMPTIC-UHFFFAOYSA-N 0.000 description 1
- NCMVAAYMJYKKRO-UHFFFAOYSA-N N1=C(N)N=C(N)N=C1N.N1=C(N)N=C(N)N=C1N.C1(=CC=C(C=C1)C)C Chemical compound N1=C(N)N=C(N)N=C1N.N1=C(N)N=C(N)N=C1N.C1(=CC=C(C=C1)C)C NCMVAAYMJYKKRO-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229960004567 aminohippuric acid Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OSNSGMPCJPCTJZ-UHFFFAOYSA-N ethene 1,3,5-triazine-2,4,6-triamine Chemical compound C=C.C=C.C=C.C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 OSNSGMPCJPCTJZ-UHFFFAOYSA-N 0.000 description 1
- VOBXLYOWBUPHIK-UHFFFAOYSA-N ethene 1,3,5-triazine-2,4,6-triamine Chemical compound C=C.C=C.C=C.C=C.C=C.C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 VOBXLYOWBUPHIK-UHFFFAOYSA-N 0.000 description 1
- WLPKFQRBARNCNR-UHFFFAOYSA-N ethene 1,3,5-triazine-2,4,6-triamine Chemical compound C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 WLPKFQRBARNCNR-UHFFFAOYSA-N 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- 239000000314 lubricant Substances 0.000 description 1
- 150000004988 m-phenylenediamines Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000006259 organic additive 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
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- CZQYVJUCYIRDFR-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O CZQYVJUCYIRDFR-UHFFFAOYSA-N 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Definitions
- the present invention relates to a spandex fiber having enhanced chlorine resistance and a production method thereof, and more particularly to a spandex fiber containing a symmetrically di-hindered hydroxyphenyl-based additive and an inorganic chlorine-resistant agent, which improve the chlorine resistance of the spandex fiber while maintaining the inherent physical properties of the polyurethane polymer of the spandex fiber.
- Spandex a typical polyurethane elastic fiber, has high rubber-like elasticity and excellent physical properties such as tensile stress and resilience, and thus is frequently used for underwear, socks, sports and leisure wear, and the like.
- the physical properties of the main component of spandex which is polyurethane show significant deterioration when it is bleached with chlorine, and the physical properties such as tenacity of swimwear made of spandex and polyamide deteriorate when they are used in swimming pools having an active chlorine content of 0.5-3.5 ppm or higher.
- Chlorine-resistant agents used in spandex include zinc oxide disclosed in US Patent No. 4,340,527 , a mixture of huntite and hydromagnesite disclosed in US Patent No. 5,626,960 , calcium carbonate and barium carbonate disclosed in Korean Patent Publication No. 92-03250 , a MgO/ZnO solid solution disclosed in Japanese Unexamined Patent Publication No. Hei 6-81215 , magnesium oxide or magnesium hydroxide or hydrotalcite disclosed in Japanese Unexamined Patent Publication No.
- Sho 59-133248 and a hydrotalcite treated with a higher fatty acid and a silane coupling agent, disclosed in Japanese Unexamined Patent Publication No. Hei 3-292364 .
- phenolic compounds are also used as additives to improve the chlorine resistance of spandex fibers.
- Japanese Unexamined Patent Publication No. Sho 50-004387 discloses a phenolic additive which is used as a stabilizer for spandex
- US Patent No. 6,846,866 discloses the technology of using a mixture of an inorganic additive and an organic additive to improve the resistance to chlorine and the resistance to discoloration caused by combustion fumes.
- the present invention has been made in order to satisfy the above technical requirement, and it is an object of the present invention to provide a spandex fiber which has improved chlorine resistance while maintaining the inherent physical properties of the polyurethane polymer of the spandex fiber.
- Another object of the present invention is to provide a method for producing a spandex fiber, which can improve the chloride resistance of the spandex fiber while maintaining the inherent physical properties of the polyurethane polymer of the spandex fiber.
- One aspect of the present invention for achieving the above objects is directed to a spandex fiber having excellent chlorine resistance, which contains, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent.
- Another aspect of the present invention for achieving the above objects is directed to a method for producing a spandex fiber, comprising the steps of:
- the spandex fiber according to the present invention has excellent discoloration resistance and chlorine resistance while maintaining the inherent physical properties of polyurethane, such as whiteness, holding power, tearing strength, bursting strength and elasticity. Thus, it can be effectively used in underwear such as shapewear, socks, and sportswear such as swimwear and gymnastic wear.
- a spandex fiber according to one embodiment of the present invention contains, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent.
- This spandex fiber has improved discoloration resistance and chlorine resistance while maintaining the inherent physical properties of the polyurethane polymer, and thus can be applied to various wear, such as underwear, sportswear, and casual wear.
- the spandex fiber of the present invention is a fiber produced from a fiber-forming substance which is a long chain synthetic polymer comprised of at least 85% of segmented polyurethane.
- a polymer which is spun into the spandex fiber is a copolymer comprising a urethane bond.
- the polyurethane polymer which is used for the production of the spandex fiber is prepared by reacting an organic diisocyanate with a polymeric diol to prepare a polyurethane precursor, dissolving the polyurethane precursor in an organic solvent, and then reacting the polyurethane precursor with a diamine and a monoamine.
- organic diisocyanate examples include diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, methylene-bis(4-phenylisocyanate), 2,4-tolylene diisocyanate, methylene-bis(4-cyclohexylisocyanate), isophorone diisocyanate, tetramethylene-p-xylylene diisocyanate, and mixtures thereof.
- examples of the polymeric diol that is used in the present invention include polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and the like.
- the diamine is used as a chain extender, and examples thereof include ethylenediamine, propylenediamine, hydrazine, 1,4-cyclohexanediamine, hydrogenated m-phenylenediamine (HPMD), 2-methylpentamethylenediamine (MPMD), and the like.
- the chain extender is one or more of ethylenediamine, 1,3-propylenediamine, and 1,4-cyclohexanediamine, optionally mixed with HPMD, MPMD and/or 1,2-propylenediamine.
- the monoamine is used as a chain terminator, and examples thereof include diethylamine, monoethanolamine, dimethylamine, and the like.
- the symmetrically di-hindered hydroxyphenyl-based compound that is used in the present invention may be one or more selected from the group consisting of tetrakis [methylene-2-(3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate]methane, tris(3,5-di-tertiary-butyl-4-hydroxy-5-methylphenyl) propionate, 3,3',3",5,5',5"-hexa-tetra-butyl-a,a',a"-(mesitylene-2,4,6-trile)tri-p-cresol, hexamethylenbis[3-(3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate], 1,2-bis(3,5-di-tertiary-butyl-4-hydroxyhydroxyamyl)hydrazine, N,N'-hexamethylenbis(3,5-di-tertiary-butyl-4-
- the symmetrically di-hindered hydroxyphenyl-based compound is preferably added in an amount of 0.1-5 wt% based on the polyurethane solid content. If the amount of the symmetrically di-hindered hydroxyphenyl-based compound that is added is less than 0.1 wt%, it will not significantly contribute to improving the chlorine resistance of the spandex fiber, and once more than 5 wt% is added, any further increase will not lead to an improvement in the effect thereof.
- the inorganic chlorine-resistant agent that is used in the present invention may be a hydrotalcite represented by the following formula 1, a huntite represented by the following formula 2, a hydromagnesite represented by the following formula 3, zinc oxide, magnesium oxide, or the like.
- Inorganic chlorine-resistant agents such as hydrotalcite, a physical mixture of huntite and hydromagnesite, basic magnesium carbonate, zinc oxide, and magnesium oxide, have the property of capturing halogen atoms, and thus are very effective at neutralizing chlorine.
- M 2+ is Mg 2+ , Ca 2+ or Zn 2+
- a n- is an anion having a valence of n
- x and y are positive numbers of 2 or greater
- Z is a positive number of 3 or smaller
- k is 0 or a positive number of 3 or smaller
- m is 0 or a positive number
- a n- is OH - , F - , Cl - , B r- , NO 3- , SO 4 2- , CH 3 COO - , CO 3 2- , HPO 4 2- , an oxalate ion, a salicylate ion, or a silicate ion.
- M 2+ is Mg 2+ or Ca 2+
- a n- is CO 3 2-
- x is from 1 to 5
- z is from 0 to 2
- m is from 0 to 5.
- Huntite and hydromagnesite are minerals which are present in the form of mixtures and are difficult to separate into pure huntite or hydromagnesite.
- Non-limiting examples of the hydrotalcite compound represented by formula 1 include Mg 4.5 Al 2 (OH) 13 CO 3 ⁇ 3.5H 2 O, Mg 6 Al 2 (OH) 16 CO 3 ⁇ 5H 2 O, Mg 8 Al 2 (OH) 20 CO 3 ⁇ 6H 2 O, Mg 4 Al 2 (OH) 12 CO 3 ⁇ 3H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3 , Mg 6 Al 2 (OH) 16 CO 3, Mg 8 Al 2 (OH) 20 CO 3 , Mg 4 Al 2 (OH) 20 CO 3 , Mg 4.5 Al 2 (OH) 13 (CO 3 ) 0.6 O 0.4, Mg 6 Al 2 (OH) 16 (CO 3 ) 0.7 O 0.3 , Mg 4.5 Al 2 (OH) 12.2 (CO 3 ) 0.8 O 0.6 , Mg 4 Al 2 (OH) 12 (CO 3 ) 0.6 O 0.4 , and any mixtures thereof.
- Hydrotalcite has the property of absorbing water, and thus when it is added to a polyurethane polymer in an uncoated state, it will cause gelation and coagulation, thereby causing yarn breakage and the like in a spinning process.
- hydrotalcite may be used after it has been coated. Even when uncoated hydrotalcite is used, sand grinding or milling of the uncoated hydrotalcite can provide the same spinning properties as those obtained when coated hydrotalcite is used.
- Examples of the coating agent which may be used in the present invention include, but are not limited to, aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, phosphoric acid esters, styrene/maleic acid anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents, polyorganosiloxanes, polyorganohydrogensiloxanes and melamine-based compounds.
- fatty acids, fatty acid salts and/or melamine-based compounds are preferred.
- Fatty acids and fatty acid salts exhibit excellent coating effects compared to other coating agents.
- the coating process for hydrotalcite may be carried out by adding a coating agent to a solvent such as water, alcohol, ether or dioxane in an amount of 0.1 to 10 wt% based on the weight of hydrotalcite, adding uncoated hydrotalcite thereto and stirring the resulting solution at an elevated temperature of 60 to 180 °C (if necessary, using a high-pressure reactor) for about 20 minutes to 2 hours, followed by filtering and drying.
- a coating process may be performed by heat-melting a coating agent without using a solvent and mixing the melted coating agent with hydrotalcite at high speed.
- the coating process should be performed in water at a temperature of 160 °C or higher under pressure, because the melamine-based compound has a high melting point.
- the fatty acid which may be used as the coating agent for hydrotalcite in the present invention is preferably one or more selected from mono- or poly-hydroxy fatty acids having a linear or branched hydrocarbon chain containing 3 to 40 carbon atoms.
- Specific examples of the fatty acid include lauric acid, caproic acid, palmitic acid and stearic acid.
- the fatty acid salt which may be used in the present invention contains either a metal selected from metals of Groups I to III of the Periodic Table or zinc.
- the fatty acid of the fatty acid salt may be saturated or unsaturated, may contain 6 to 30 carbon atoms and may be monofunctional or bifunctional.
- Examples of the fatty acid salt include lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate and aluminum stearate, more preferably magnesium stearate.
- the melamine-based compound which may be used as a coating agent in the present invention may be one or a mixture of two or more selected from melamine compounds, phosphor-containing melamine compounds and melamine cyanurate compounds, which may be substituted with an organic compound having a carboxyl group.
- the melamine compound may be selected from methylene dimelamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, decamethylene dimelamine, dodecamethylene dimelamine, 1,3-cyclohexylene dimelamine, p -phenylene dimelamine, p -xylene dimelamine, diethylene trimelamine, triethylene tetramelamine, tetraethylene pentamelamine, hexaethylene heptamelamine, melamine formaldehyde and the like.
- the phosphor-containing melamine compounds comprise a phosphoric acid or phosphate coupled to the above-described melamine compounds, and specific examples thereof include dimelamine pyrophosphate, melamine primary phosphate, melamine secondary phosphate, melamine polyphosphate, and a melamine salt of bis-(pentaerythritol phosphate) phosphoric acid, etc.
- the melamine cyanurate compounds are melamine cyanurates substituted with at least one substituent of selected from methyl, phenyl, carboxymethyl, 2-carboxyethyl, cyanomethyl, 2-cyanoethyl and the like.
- the above melamine-based compounds preferably contain an organic compound having a carboxyl group.
- the organic compound having a carboxyl group include aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aromatic monocarboxylic acids, aromatic dicarboxylic acids, aromatic tetracarboxylic acids, cycloaliphatic monocarboxylic acids, and cycloaliphatic dicarboxylic acids.
- the aliphatic monocarboxylic acids include caprylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid and behenic acid;
- the aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebasic acid, 1,9-nonanedicarboylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid and 1,14-tetradecanedicarboxylic acid;
- the aromatic monocarboxylic acids include benzoic acid,
- the hydromagnesite of formula 3 may be obtained from minerals or by synthesis.
- a coating agent which may be used for coating of hydromagnesite in the present invention include, but are not limited to, aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, phosphoric acid esters, styrene/maleic acid anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents, polyorganosiloxanes, polyorganohydrogensiloxanes and melamine-based compounds.
- fatty acids, fatty acid salts and/or melamine-based compounds are preferred.
- Fatty acids and fatty acid salts exhibit excellent coating effects compared to other coating agents.
- the coating process for hydromagnesite may be carried out by adding a coating agent to a solvent such as water, alcohol, ether or dioxane in an amount of 0.1 to 10 wt% based on the weight of hydrotalcite, adding an uncoated hydromagnesite thereto and stirring the resulting solution at an elevated temperature of 50 to 170 °C (if necessary, using a high-pressure reactor) for about 20 minutes to 2 hours, followed by filtering and drying.
- the coating process may be performed by heat-melting a coating agent without using a solvent and mixing the melted coating agent with hydromagnesite at high speed.
- the coating process should be performed in water at a temperature of 160 °C or higher under pressure, because the melamine-based compound has a high melting point.
- the fatty acid which may be used as a coating agent for hydromagnesite in the present invention is preferably one or more selected from mono- or poly-hydroxy fatty acids having a linear or branched hydrocarbon chain containing 3 to 40 carbon atoms.
- Specific examples of the fatty acid include lauric acid, caproic acid, palmitic acid and stearic acid.
- the fatty acid salt which may be used in the present invention contains either a metal selected from metals of Groups I to III of the Periodic Table or zinc.
- the fatty acid of the fatty acid salt may be saturated or unsaturated, may contain 6 to 30 carbon atoms and may be monofunctional or bifunctional.
- Examples of the fatty acid salt include lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate and aluminum stearate, more preferably magnesium stearate.
- the chlorine-resistant agent which is used in the present invention is preferably added in an amount of 0.1-10 wt% based on the polyurethane solid content. If the amount added of the chlorine-resistant agent is less than 0.1 wt%, the chloride resistance of the spandex fiber will be insufficient, and if the amount is more than 10 wt%, the strength, elongation and modulus of the spandex fiber will deteriorate due to the excessive content of inorganic compounds.
- a stabilizer may be added to the polyurethane polymer in order to prevent the discoloration and deterioration in physical properties of the spandex which result from either heat treatment during spandex processing or UV light, smog and the like.
- Specific examples of the stabilizer include hindered phenolic compounds, benzofuranone-based compounds, semi-carbazide-based compounds, benzotriazol-based compounds, hindered amine-based compounds, polymeric tertiary amine stabilizers (e.g., a tertiary nitrogen atom-containing polyurethane, polydialkyl aminoalkyl methacrylate, etc.), and the like.
- the spandex fiber of the present invention may further include, in addition to the above-described compounds, inorganic additives such as titanium dioxide, magnesium stearate, etc.
- the titanium dioxide may be used in an amount of 0.1-5 wt% based on the weight of the spandex fiber, depending on the whiteness of the spandex fiber.
- the magnesium stearate is used to enhance the unwinding property of the spandex fiber and is added in an amount of 0.1 to 2 wt% based on the weight of the spandex fiber.
- the polyurethane spinning solution may contain other various additives for specific purposes, unless these additives interfere with the effects of the present invention.
- additives include stabilizers, UV light absorbers, light resistant agents, antioxidants, anti-tack agents, lubricants such as mineral oil and silicone oils, antistatic agents, and the like.
- examples of the additives include hindered phenolic stabilizers such as 2,6-di-t-butyl-4-methyl-phenol as a light stabilizer, antioxidants, phosphorus-containing chemicals, nitrogen oxide traps, light stabilizers, hindered amine stabilizers, metal salts such as magnesium stearate and barium sulfate, bactericides containing silver, zinc, or compounds thereof, deodorants, anti-static agents, and the like.
- Another aspect of the present invention is directed to a method for producing a spandex fiber having excellent chlorine resistance.
- an organic diisocyanate is reacted with a diol to prepare a polyurethane precursor, after which the polyurethane precursor is dissolved in an organic solvent and then reacted with a diamine and a monoamine, thereby preparing a polyurethane solution.
- 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent are added to the polyurethane solution, and the resulting mixture is spun to form a spandex yarn which is then wound.
- the polyurethane solution may be melt-spun, dry-spun or wet-spun into spandex fibers.
- the symmetrically di-hindered hydroxyphenyl-based compound and the inorganic chlorine-resistant agent may be added to the polyurethane polymer at any convenient point of time.
- the inorganic chlorine-resistant agent may be added to the polyurethane solution together with other additives and be mixed with the polyurethane polymer during a sand-grinding or milling process.
- the inorganic chlorine-resistant agent may also be mixed with the polyurethane polymer in a solvent during the sand-grinding or milling process in the absence of other additives.
- the symmetrically di-hindered hydroxyphenyl-based compound may be added during the sand-grinding or milling process after it has been separately dissolved in a solvent.
- a coated inorganic chlorine-resistant agent may also be added.
- the process of sand-grinding or milling the inorganic chlorine-resistant agent can be performed by milling either a mixture of the inorganic chlorine-resistant agent, a solvent and a small amount of the polyurethane polymer or a slurry mixture of the inorganic chlorine-resistant agent, a solvent, a small amount of the polyurethane polymer, and other additives, using a conventional bead mill.
- the small amount of the polyurethane polymer serves to increase the dispersibility of the inorganic chlorine-resistant agent.
- the solvent used may be one or more selected from among dimethylacetamide, dimethylformamide and dimethylsulfoxide.
- the polyurethane solution was mixed with, based on the solid content of the polyurethane solution, 1 wt% of poly(N,N-diethyl-2-aminoethyl methacrylate) as an acid dye enhancer, 0.1 wt% of titanium oxide as a light resistant agent, 0.26 wt% of magnesium stearate as an unwinding property enhancer, and 4 wt% of the chlorine-resistant agent hydrotalcite (Mg 4 Al 2 (OH) 12 CO 3 ⁇ 3H 2 O) coated with, based on the weight of the hydrotalcite, 2 wt% of stearic acid and 1 wt% of melamine phosphate.
- the chlorine-resistant agent hydrotalcite Mg 4 Al 2 (OH) 12 CO 3 ⁇ 3H 2 O
- the spinning solution was defoamed, after it was dry-spun at a spinning temperature of 260 °C and wound at a speed of 900 m/min, thereby producing a 4-filament 40-denier spandex yarn.
- the chlorine resistance of the spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- the strength retention rate in chlorinated water was evaluated in the following manner.
- the spandex yarn was stretched at a stretching ratio of 50%, treated with water (pH 4.5; 99 to 100 °C) for 2 hours, and dried and cooled at room temperature.
- the spandex yarn was dipped in 45 l of chlorinated water (pH 7.0-7.5) containing 3.5 ppm of active chlorine at room temperature for 120 hours, and the strength retention rate thereof was calculated using the following equation.
- the strength of the spandex yarn was measured using MEI by applying 32 kgf cell to a 20 cm-long sample at a cross head speed of 1000 mm/min.
- Strength retention rate % S / S o ⁇ 100 wherein So is strength before treatment, and S is strength after treatment.
- a spandex yarn was produced in the same manner, except that 3,3',3",5,5',5"-hexa-tetra-butyl-a,a',a"-(mesitylene-2,4,6-trile)tri-p-cresol was used as the symmetrically di-hindered hydroxyphenyl-based compound.
- the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- a spandex yarn was produced in the same manner, except that tetrakis[methylene-2-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionate]methane was used as the symmetrically di-hindered hydroxyphenyl-based compound and that 4 wt% of an uncoated hydrotalcite (Mg 4 Al 2 (OH) 12 CO 3 ⁇ 3H 2 O) was added as the chlorine-resistant agent.
- the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- a spandex yarn was produced in the same manner, except that a mixture of huntite and hydromagnesite was used as the inorganic chlorine-resistant agent.
- the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- a spandex yarn was produced in the same manner, except that hydromagnesite was used as the inorganic chlorine-resistant agent.
- the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- a spandex yarn was produced in the same manner, except that 2,4-di-tertiary-butylphenyl-4'-hydroxy-3',5'-di-tertiarybutyl benzoate was used as the inorganic chlorine-resistant agent.
- the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- a spandex yarn was produced in the same manner, except that an unsymmetrically di-hindered hydroxyphenyl-based compound was used instead of the symmetrically di-hindered hydroxyphenyl-based compound.
- the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- a spandex yarn was produced in the same manner, except that the inorganic chlorine-resistant agent was used alone without using the symmetrically di-hindered hydroxyphenyl-based compound.
- the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- Table 1 Examples Comparative Examples 1 2 3 4 5 6 1 2 Strength retention rate (%) 91.1 90.3 89.8 87.4 90.7 80.61 59.7 63.8
- the inventive spandex fibers comprising both the symmetrically di-hindered hydroxyphenyl-based compound and the inorganic chlorine-resistant agent showed significantly high strength retention rates in chlorinated water compared to the conventional spandex fiber comprising either the symmetrically di-hindered hydroxyphenyl-based compound alone or the inorganic chlorine-resistant agent alone.
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Abstract
Description
- The present invention relates to a spandex fiber having enhanced chlorine resistance and a production method thereof, and more particularly to a spandex fiber containing a symmetrically di-hindered hydroxyphenyl-based additive and an inorganic chlorine-resistant agent, which improve the chlorine resistance of the spandex fiber while maintaining the inherent physical properties of the polyurethane polymer of the spandex fiber.
- Spandex, a typical polyurethane elastic fiber, has high rubber-like elasticity and excellent physical properties such as tensile stress and resilience, and thus is frequently used for underwear, socks, sports and leisure wear, and the like. However, the physical properties of the main component of spandex which is polyurethane show significant deterioration when it is bleached with chlorine, and the physical properties such as tenacity of swimwear made of spandex and polyamide deteriorate when they are used in swimming pools having an active chlorine content of 0.5-3.5 ppm or higher.
- Efforts have been made impart spandex fibers with resistance against the deterioration caused by chlorine. Chlorine-resistant agents used in spandex include zinc oxide disclosed in
US Patent No. 4,340,527 , a mixture of huntite and hydromagnesite disclosed inUS Patent No. 5,626,960 , calcium carbonate and barium carbonate disclosed in Korean Patent Publication No.92-03250 Hei 6-81215 Sho 59-133248 Hei 3-292364 Sho 50-004387 US Patent No. 6,846,866 discloses the technology of using a mixture of an inorganic additive and an organic additive to improve the resistance to chlorine and the resistance to discoloration caused by combustion fumes. - However, there has not yet been an additive capable of dramatically improving the chlorine resistance of spandex fibers. Thus, it is required to improve the chlorine resistance of spandex fibers.
- Accordingly, the present invention has been made in order to satisfy the above technical requirement, and it is an object of the present invention to provide a spandex fiber which has improved chlorine resistance while maintaining the inherent physical properties of the polyurethane polymer of the spandex fiber.
- Another object of the present invention is to provide a method for producing a spandex fiber, which can improve the chloride resistance of the spandex fiber while maintaining the inherent physical properties of the polyurethane polymer of the spandex fiber.
- One aspect of the present invention for achieving the above objects is directed to a spandex fiber having excellent chlorine resistance, which contains, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent.
- Another aspect of the present invention for achieving the above objects is directed to a method for producing a spandex fiber, comprising the steps of:
- reacting an organic diisocyanate with a diol to prepare a polyurethane precursor, dissolving the polyurethane precursor in an organic solvent, and then reacting the polyurethane precursor with a diamine and a monoamine, thereby preparing a polyurethane solution; and
- adding, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent, to the polyurethane solution, followed by spinning.
- The spandex fiber according to the present invention has excellent discoloration resistance and chlorine resistance while maintaining the inherent physical properties of polyurethane, such as whiteness, holding power, tearing strength, bursting strength and elasticity. Thus, it can be effectively used in underwear such as shapewear, socks, and sportswear such as swimwear and gymnastic wear.
- Hereinafter, the present invention will be described in detail.
- A spandex fiber according to one embodiment of the present invention contains, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent. This spandex fiber has improved discoloration resistance and chlorine resistance while maintaining the inherent physical properties of the polyurethane polymer, and thus can be applied to various wear, such as underwear, sportswear, and casual wear.
- The spandex fiber of the present invention is a fiber produced from a fiber-forming substance which is a long chain synthetic polymer comprised of at least 85% of segmented polyurethane. In other words, a polymer which is spun into the spandex fiber is a copolymer comprising a urethane bond. The polyurethane polymer which is used for the production of the spandex fiber is prepared by reacting an organic diisocyanate with a polymeric diol to prepare a polyurethane precursor, dissolving the polyurethane precursor in an organic solvent, and then reacting the polyurethane precursor with a diamine and a monoamine.
- Examples of the organic diisocyanate include diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, methylene-bis(4-phenylisocyanate), 2,4-tolylene diisocyanate, methylene-bis(4-cyclohexylisocyanate), isophorone diisocyanate, tetramethylene-p-xylylene diisocyanate, and mixtures thereof.
- In addition, examples of the polymeric diol that is used in the present invention include polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and the like. The diamine is used as a chain extender, and examples thereof include ethylenediamine, propylenediamine, hydrazine, 1,4-cyclohexanediamine, hydrogenated m-phenylenediamine (HPMD), 2-methylpentamethylenediamine (MPMD), and the like. More preferably, the chain extender is one or more of ethylenediamine, 1,3-propylenediamine, and 1,4-cyclohexanediamine, optionally mixed with HPMD, MPMD and/or 1,2-propylenediamine. Meanwhile, the monoamine is used as a chain terminator, and examples thereof include diethylamine, monoethanolamine, dimethylamine, and the like.
- The symmetrically di-hindered hydroxyphenyl-based compound that is used in the present invention may be one or more selected from the group consisting of tetrakis [methylene-2-(3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate]methane, tris(3,5-di-tertiary-butyl-4-hydroxy-5-methylphenyl) propionate, 3,3',3",5,5',5"-hexa-tetra-butyl-a,a',a"-(mesitylene-2,4,6-trile)tri-p-cresol, hexamethylenbis[3-(3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate], 1,2-bis(3,5-di-tertiary-butyl-4-hydroxyhydroxyamyl)hydrazine, N,N'-hexamethylenbis(3,5-di-tertiary-butyl-4-hydroxy-hydrocinnamide), and 2,4-di-tertiary-butylphenyl-4'-hydroxy-3',5'-di-tertiary-butyl benzoate.
- In the present invention, the symmetrically di-hindered hydroxyphenyl-based compound is preferably added in an amount of 0.1-5 wt% based on the polyurethane solid content. If the amount of the symmetrically di-hindered hydroxyphenyl-based compound that is added is less than 0.1 wt%, it will not significantly contribute to improving the chlorine resistance of the spandex fiber, and once more than 5 wt% is added, any further increase will not lead to an improvement in the effect thereof.
- The inorganic chlorine-resistant agent that is used in the present invention may be a hydrotalcite represented by the following formula 1, a huntite represented by the following formula 2, a hydromagnesite represented by the following formula 3, zinc oxide, magnesium oxide, or the like. Inorganic chlorine-resistant agents, such as hydrotalcite, a physical mixture of huntite and hydromagnesite, basic magnesium carbonate, zinc oxide, and magnesium oxide, have the property of capturing halogen atoms, and thus are very effective at neutralizing chlorine.
wherein M2+ is Mg2+, Ca2+ or Zn2+, An- is an anion having a valence of n, x and y are positive numbers of 2 or greater, Z is a positive number of 3 or smaller, k is 0 or a positive number of 3 or smaller, m is 0 or a positive number, and An- is OH-, F-, Cl-, Br-, NO3-, SO4 2-, CH3COO-, CO3 2-, HPO4 2-, an oxalate ion, a salicylate ion, or a silicate ion.
wherein M2+ is Mg2+ or Ca2+, An- is CO3 2-, x is from 1 to 5, z is from 0 to 2, and m is from 0 to 5. - Huntite and hydromagnesite are minerals which are present in the form of mixtures and are difficult to separate into pure huntite or hydromagnesite.
- Non-limiting examples of the hydrotalcite compound represented by formula 1 include Mg4.5Al2(OH)13CO3·3.5H2O, Mg6Al2(OH)16CO3·5H2O, Mg8Al2(OH)20CO3·6H2O, Mg4Al2(OH)12CO3·3H2O, Mg4.5Al2(OH)13CO3, Mg6Al2(OH)16CO3, Mg8Al2(OH)20CO3, Mg4Al2(OH)20CO3, Mg4.5Al2(OH)13(CO3)0.6O0.4, Mg6Al2(OH)16(CO3)0.7O0.3, Mg4.5Al2(OH)12.2(CO3)0.8O0.6, Mg4Al2(OH)12(CO3)0.6O0.4, and any mixtures thereof.
- Hydrotalcite has the property of absorbing water, and thus when it is added to a polyurethane polymer in an uncoated state, it will cause gelation and coagulation, thereby causing yarn breakage and the like in a spinning process. In order to prevent an increase in discharge pressure and yarn breakage during a spinning process by preventing water absorption into hydrotalcite and improving the dispersibility of hydrotalcite, hydrotalcite may be used after it has been coated. Even when uncoated hydrotalcite is used, sand grinding or milling of the uncoated hydrotalcite can provide the same spinning properties as those obtained when coated hydrotalcite is used.
- Examples of the coating agent which may be used in the present invention include, but are not limited to, aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, phosphoric acid esters, styrene/maleic acid anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents, polyorganosiloxanes, polyorganohydrogensiloxanes and melamine-based compounds. Among these, fatty acids, fatty acid salts and/or melamine-based compounds are preferred. Fatty acids and fatty acid salts exhibit excellent coating effects compared to other coating agents.
- The coating process for hydrotalcite may be carried out by adding a coating agent to a solvent such as water, alcohol, ether or dioxane in an amount of 0.1 to 10 wt% based on the weight of hydrotalcite, adding uncoated hydrotalcite thereto and stirring the resulting solution at an elevated temperature of 60 to 180 °C (if necessary, using a high-pressure reactor) for about 20 minutes to 2 hours, followed by filtering and drying. Alternatively, the coating process may be performed by heat-melting a coating agent without using a solvent and mixing the melted coating agent with hydrotalcite at high speed.
- When hydrotalcite is coated with the melamine-based compound, the coating process should be performed in water at a temperature of 160 °C or higher under pressure, because the melamine-based compound has a high melting point.
- The fatty acid which may be used as the coating agent for hydrotalcite in the present invention is preferably one or more selected from mono- or poly-hydroxy fatty acids having a linear or branched hydrocarbon chain containing 3 to 40 carbon atoms. Specific examples of the fatty acid include lauric acid, caproic acid, palmitic acid and stearic acid.
- The fatty acid salt which may be used in the present invention contains either a metal selected from metals of Groups I to III of the Periodic Table or zinc. The fatty acid of the fatty acid salt may be saturated or unsaturated, may contain 6 to 30 carbon atoms and may be monofunctional or bifunctional. Examples of the fatty acid salt include lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate and aluminum stearate, more preferably magnesium stearate.
- The melamine-based compound which may be used as a coating agent in the present invention may be one or a mixture of two or more selected from melamine compounds, phosphor-containing melamine compounds and melamine cyanurate compounds, which may be substituted with an organic compound having a carboxyl group.
- Specifically, the melamine compound may be selected from methylene dimelamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, decamethylene dimelamine, dodecamethylene dimelamine, 1,3-cyclohexylene dimelamine, p-phenylene dimelamine, p-xylene dimelamine, diethylene trimelamine, triethylene tetramelamine, tetraethylene pentamelamine, hexaethylene heptamelamine, melamine formaldehyde and the like.
- The phosphor-containing melamine compounds comprise a phosphoric acid or phosphate coupled to the above-described melamine compounds, and specific examples thereof include dimelamine pyrophosphate, melamine primary phosphate, melamine secondary phosphate, melamine polyphosphate, and a melamine salt of bis-(pentaerythritol phosphate) phosphoric acid, etc.
- The melamine cyanurate compounds are melamine cyanurates substituted with at least one substituent of selected from methyl, phenyl, carboxymethyl, 2-carboxyethyl, cyanomethyl, 2-cyanoethyl and the like.
- The above melamine-based compounds preferably contain an organic compound having a carboxyl group. Examples of the organic compound having a carboxyl group include aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aromatic monocarboxylic acids, aromatic dicarboxylic acids, aromatic tetracarboxylic acids, cycloaliphatic monocarboxylic acids, and cycloaliphatic dicarboxylic acids. For example, the aliphatic monocarboxylic acids include caprylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid and behenic acid; the aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebasic acid, 1,9-nonanedicarboylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid and 1,14-tetradecanedicarboxylic acid; the aromatic monocarboxylic acids include benzoic acid, phenylacetic acid, α-naphthoic acid, β-naphthoic acid, cynnamic acid, p-amino hippuric acid and 4-(2-thiazoylsulfamyl)-phthalaninoic acid); the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid and phthalic acid; the aromatic tricarboxylic acids include trimellitic acid, 1,3,5-benzenetricarboxylic acid and tris(2-carboxyethyl) isocyanurate; the aromatic tetracarboxylic acids include pyromellitic acid and biphenyltetracarboxylic acid; the cycloaliphatic monocarboxylic acids include cyclohexane carboxylic acid; and the cycloaliphatic dicarboxylic acids include 1,2-cyclohexane dicarboxylic acid.
- The hydromagnesite of formula 3 may be obtained from minerals or by synthesis. Examples of a coating agent which may be used for coating of hydromagnesite in the present invention include, but are not limited to, aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, phosphoric acid esters, styrene/maleic acid anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents, polyorganosiloxanes, polyorganohydrogensiloxanes and melamine-based compounds. Among these, fatty acids, fatty acid salts and/or melamine-based compounds are preferred. Fatty acids and fatty acid salts exhibit excellent coating effects compared to other coating agents. The coating process for hydromagnesite may be carried out by adding a coating agent to a solvent such as water, alcohol, ether or dioxane in an amount of 0.1 to 10 wt% based on the weight of hydrotalcite, adding an uncoated hydromagnesite thereto and stirring the resulting solution at an elevated temperature of 50 to 170 °C (if necessary, using a high-pressure reactor) for about 20 minutes to 2 hours, followed by filtering and drying. Alternatively, the coating process may be performed by heat-melting a coating agent without using a solvent and mixing the melted coating agent with hydromagnesite at high speed.
- When hydromagnesite is coated with the melamine-based compound, the coating process should be performed in water at a temperature of 160 °C or higher under pressure, because the melamine-based compound has a high melting point.
- The fatty acid which may be used as a coating agent for hydromagnesite in the present invention is preferably one or more selected from mono- or poly-hydroxy fatty acids having a linear or branched hydrocarbon chain containing 3 to 40 carbon atoms. Specific examples of the fatty acid include lauric acid, caproic acid, palmitic acid and stearic acid.
- The fatty acid salt which may be used in the present invention contains either a metal selected from metals of Groups I to III of the Periodic Table or zinc. The fatty acid of the fatty acid salt may be saturated or unsaturated, may contain 6 to 30 carbon atoms and may be monofunctional or bifunctional. Examples of the fatty acid salt include lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate and aluminum stearate, more preferably magnesium stearate.
- The chlorine-resistant agent which is used in the present invention is preferably added in an amount of 0.1-10 wt% based on the polyurethane solid content. If the amount added of the chlorine-resistant agent is less than 0.1 wt%, the chloride resistance of the spandex fiber will be insufficient, and if the amount is more than 10 wt%, the strength, elongation and modulus of the spandex fiber will deteriorate due to the excessive content of inorganic compounds.
- A stabilizer may be added to the polyurethane polymer in order to prevent the discoloration and deterioration in physical properties of the spandex which result from either heat treatment during spandex processing or UV light, smog and the like. Specific examples of the stabilizer include hindered phenolic compounds, benzofuranone-based compounds, semi-carbazide-based compounds, benzotriazol-based compounds, hindered amine-based compounds, polymeric tertiary amine stabilizers (e.g., a tertiary nitrogen atom-containing polyurethane, polydialkyl aminoalkyl methacrylate, etc.), and the like.
- The spandex fiber of the present invention may further include, in addition to the above-described compounds, inorganic additives such as titanium dioxide, magnesium stearate, etc. The titanium dioxide may be used in an amount of 0.1-5 wt% based on the weight of the spandex fiber, depending on the whiteness of the spandex fiber. The magnesium stearate is used to enhance the unwinding property of the spandex fiber and is added in an amount of 0.1 to 2 wt% based on the weight of the spandex fiber.
- The polyurethane spinning solution may contain other various additives for specific purposes, unless these additives interfere with the effects of the present invention. These additives include stabilizers, UV light absorbers, light resistant agents, antioxidants, anti-tack agents, lubricants such as mineral oil and silicone oils, antistatic agents, and the like. Examples of the additives include hindered phenolic stabilizers such as 2,6-di-t-butyl-4-methyl-phenol as a light stabilizer, antioxidants, phosphorus-containing chemicals, nitrogen oxide traps, light stabilizers, hindered amine stabilizers, metal salts such as magnesium stearate and barium sulfate, bactericides containing silver, zinc, or compounds thereof, deodorants, anti-static agents, and the like.
- Another aspect of the present invention is directed to a method for producing a spandex fiber having excellent chlorine resistance. In the inventive method for producing the spandex fiber, an organic diisocyanate is reacted with a diol to prepare a polyurethane precursor, after which the polyurethane precursor is dissolved in an organic solvent and then reacted with a diamine and a monoamine, thereby preparing a polyurethane solution. Then, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent are added to the polyurethane solution, and the resulting mixture is spun to form a spandex yarn which is then wound. The polyurethane solution may be melt-spun, dry-spun or wet-spun into spandex fibers.
- In the production of the spandex fiber according to the present invention, the symmetrically di-hindered hydroxyphenyl-based compound and the inorganic chlorine-resistant agent may be added to the polyurethane polymer at any convenient point of time. For example, the inorganic chlorine-resistant agent may be added to the polyurethane solution together with other additives and be mixed with the polyurethane polymer during a sand-grinding or milling process. Alternatively, the inorganic chlorine-resistant agent may also be mixed with the polyurethane polymer in a solvent during the sand-grinding or milling process in the absence of other additives. In addition, the symmetrically di-hindered hydroxyphenyl-based compound may be added during the sand-grinding or milling process after it has been separately dissolved in a solvent. In order to improve the dispersibility of the inorganic chlorine-resistant agent, a coated inorganic chlorine-resistant agent may also be added.
- The process of sand-grinding or milling the inorganic chlorine-resistant agent can be performed by milling either a mixture of the inorganic chlorine-resistant agent, a solvent and a small amount of the polyurethane polymer or a slurry mixture of the inorganic chlorine-resistant agent, a solvent, a small amount of the polyurethane polymer, and other additives, using a conventional bead mill. Herein, the small amount of the polyurethane polymer serves to increase the dispersibility of the inorganic chlorine-resistant agent. The solvent used may be one or more selected from among dimethylacetamide, dimethylformamide and dimethylsulfoxide.
- Hereinafter, the present invention will be described in further detail with reference to examples. These examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention. All parts, percentages, etc., are by weight unless otherwise specified.
- 518 g of diphenylmethane-4,4'-diisocyanate and 2,328 g of polytetramethylene ether glycol (molecular weight: 1,800) were reacted with stirring at 90 °C under a nitrogen atmosphere for 95 minutes to prepare a polyurethane prepolymer having isocyanate groups at both ends. After cooling the prepolymer to room temperature, 4,269 g of dimethylacetamide was added thereto to obtain a polyurethane prepolymer solution.
- Subsequently, 43 g of ethylenediamine and 9.1 g of diethylamine were dissolved in 1,889 g of dimethylacetamide. The resultant solution was added to the prepolymer solution at 9 °C or below to obtain a polyurethane solution. The polyurethane solution was mixed with, based on the solid content of the polyurethane solution, 1 wt% of poly(N,N-diethyl-2-aminoethyl methacrylate) as an acid dye enhancer, 0.1 wt% of titanium oxide as a light resistant agent, 0.26 wt% of magnesium stearate as an unwinding property enhancer, and 4 wt% of the chlorine-resistant agent hydrotalcite (Mg4Al2(OH)12CO3·3H2O) coated with, based on the weight of the hydrotalcite, 2 wt% of stearic acid and 1 wt% of melamine phosphate. In addition, 1.5 wt% of tetrakis[methylene-2-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionate]methane as a symmetrically di-hindered hydroxyphenyl-based compound was added to and mixed with the resulting slurry, thereby obtaining a spinning solution.
- The spinning solution was defoamed, after it was dry-spun at a spinning temperature of 260 °C and wound at a speed of 900 m/min, thereby producing a 4-filament 40-denier spandex yarn.
- The chlorine resistance of the spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below. In order to evaluate the chlorine resistance of the obtained spandex yarn, the strength retention rate in chlorinated water was evaluated in the following manner. The spandex yarn was stretched at a stretching ratio of 50%, treated with water (pH 4.5; 99 to 100 °C) for 2 hours, and dried and cooled at room temperature. Then, the spandex yarn was dipped in 45 ℓ of chlorinated water (pH 7.0-7.5) containing 3.5 ppm of active chlorine at room temperature for 120 hours, and the strength retention rate thereof was calculated using the following equation. The strength of the spandex yarn was measured using MEI by applying 32 kgf cell to a 20 cm-long sample at a cross head speed of 1000 mm/min.
wherein So is strength before treatment, and S is strength after treatment. - A spandex yarn was produced in the same manner, except that 3,3',3",5,5',5"-hexa-tetra-butyl-a,a',a"-(mesitylene-2,4,6-trile)tri-p-cresol was used as the symmetrically di-hindered hydroxyphenyl-based compound. The chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- A spandex yarn was produced in the same manner, except that tetrakis[methylene-2-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionate]methane was used as the symmetrically di-hindered hydroxyphenyl-based compound and that 4 wt% of an uncoated hydrotalcite (Mg4Al2(OH)12CO3·3H2O) was added as the chlorine-resistant agent. The chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- A spandex yarn was produced in the same manner, except that a mixture of huntite and hydromagnesite was used as the inorganic chlorine-resistant agent. The chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- A spandex yarn was produced in the same manner, except that hydromagnesite was used as the inorganic chlorine-resistant agent. The chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- A spandex yarn was produced in the same manner, except that 2,4-di-tertiary-butylphenyl-4'-hydroxy-3',5'-di-tertiarybutyl benzoate was used as the inorganic chlorine-resistant agent. The chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- A spandex yarn was produced in the same manner, except that an unsymmetrically di-hindered hydroxyphenyl-based compound was used instead of the symmetrically di-hindered hydroxyphenyl-based compound. The chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
- A spandex yarn was produced in the same manner, except that the inorganic chlorine-resistant agent was used alone without using the symmetrically di-hindered hydroxyphenyl-based compound. The chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
[Table] Examples Comparative Examples 1 2 3 4 5 6 1 2 Strength retention rate (%) 91.1 90.3 89.8 87.4 90.7 80.61 59.7 63.8 - As can be seen from the results in Table 1 above, the inventive spandex fibers comprising both the symmetrically di-hindered hydroxyphenyl-based compound and the inorganic chlorine-resistant agent showed significantly high strength retention rates in chlorinated water compared to the conventional spandex fiber comprising either the symmetrically di-hindered hydroxyphenyl-based compound alone or the inorganic chlorine-resistant agent alone.
- Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (8)
- A spandex fiber having excellent chlorine resistance, which contains, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent.
- The spandex fiber of claim 1, wherein the symmetrically di-hindered hydroxyphenyl-based compound is one or more selected from the group consisting of tetrakis [methylene-2-(3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate]methane, tris(3,5-di-tertiary-butyl-4-hydroxy-5-methylphenyl) propionate, 3,3',3",5,5',5"-hexa-tetra-butyl-a,a',a"-(mesitylene-2,4,6-trile)tri-p-cresol, hexamethylenbis[3-(3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate], 1,2-bis(3,5-di-tertiary-butyl-4-hydroxyhydroxyamyl)hydrazine, N,N'-hexamethylenbis(3,5-di-tertiary-butyl-4-hydroxy-hydrocinnamide), and 2,4-di-tertiary-butylphenyl-4'-hydroxy-3',5'-di-tertiary-butyl benzoate.
- The spandex fiber of claim 1, wherein the inorganic chlorine-resistant agent is one or more selected from the group consisting of a hydrotalcite compound, a mixture of huntite and hydromagnesite, hydromagnesite, zinc oxide, and magnesium oxide.
- The spandex fiber of claim 3, wherein the hydrotalcite compound is one or more selected from the group consisting of Mg4.5Al2(OH)13CO3·3.5H2O, Mg6Al2(OH)16CO3·5H2O, Mg8Al2(OH)20CO3·6H2O, Mg4Al2(OH)12CO3·3H2O, Mg4.5Al2(OH)13CO3, Mg6Al2(OH)16CO3, Mg8Al2(OH)20CO3, Mg4Al2(OH)20CO3, Mg4.5Al2(OH)13(CO3)0.6O0.4, Mg6Al2(OH)16(CO3)0.7O0.3, Mg4.5Al2(OH)12.2(CO3)0.8O0.6, and Mg4Al2(OH)12(CO3)0.6O0.4.
- The spandex fiber of claim 3, wherein the hydromagnesite is one or more selected from the group consisting of Mg4(CO3)4·Mg(OH)2·4H2O, Mg3(CO3)3·Mg(OH)23H2O, Mg4(CO3)4·Mg(OH)2, Mg3(CO3)3·Mg(OH)2, and MgCO3.
- The spandex fiber of claim 1, wherein the inorganic chlorine-resistant agent is coated with at least one coating agent selected from the group consisting of aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, phosphoric acid esters, styrene/maleic acid anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents, polyorganosiloxanes, polyorganohydrogensiloxanes and melamine-based compounds.
- A method for producing a spandex fiber, comprising the steps of:reacting an organic diisocyanate with a diol to prepare a polyurethane precursor, dissolving the polyurethane precursor in an organic solvent, and then reacting the polyurethane precursor with a diamine and a monoamine, thereby preparing a polyurethane solution; andadding, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent, to the polyurethane solution, followed by spinning.
- The method of claim 1, wherein the inorganic chlorine-resistant agent is one or more selected from the group consisting of a hydrotalcite compound, a mixture of huntite and hydromagnesite, hydromagnesite, zinc oxide, and magnesium oxide.
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KR1020090092992A KR101130510B1 (en) | 2009-09-30 | 2009-09-30 | Anti-chlorine Spandex Fiber and Preparation Method thereof |
PCT/KR2010/006634 WO2011040755A2 (en) | 2009-09-30 | 2010-09-29 | Spandex fiber with excellent chlorine resistance, and preparation method thereof |
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EP2484821A2 true EP2484821A2 (en) | 2012-08-08 |
EP2484821A4 EP2484821A4 (en) | 2013-07-24 |
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KR (1) | KR101130510B1 (en) |
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KR101157328B1 (en) * | 2009-12-31 | 2012-06-15 | 주식회사 효성 | Anti-chlorine and anti-discoloration Spandex Fiber and Preparation Method thereof |
JP5688601B2 (en) * | 2011-06-23 | 2015-03-25 | 東レ・オペロンテックス株式会社 | Polyurethane yarn and fabric and swimsuit using the same |
CN103380995A (en) * | 2013-07-30 | 2013-11-06 | 常熟市新达纬编厂 | Super-chlorine-resistant swimwear fabric |
CN103422250A (en) * | 2013-07-30 | 2013-12-04 | 常熟市新达纬编厂 | Preparing process of super chlorine-resistant bathing suit fabric |
KR101684792B1 (en) * | 2015-07-10 | 2016-12-21 | 주식회사 효성 | Spandex fiber having improved chlorine resistance |
KR101885843B1 (en) | 2016-09-12 | 2018-08-06 | 주식회사 단석산업 | Hydromagnecite particles and a method of producing the same |
CN107059159A (en) * | 2017-05-19 | 2017-08-18 | 江苏华昌织物有限公司 | A kind of preparation method of anti-aging shading screen cloth |
CN114892294B (en) * | 2022-05-09 | 2023-08-29 | 西南大学 | Multifunctional polyurethane fiber and preparation method and application thereof |
KR20240008108A (en) * | 2022-07-11 | 2024-01-18 | (주)석경에이티 | The manufacturing method of synthetic huntite and polyurethane yarn using the same |
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WO2006052318A1 (en) * | 2004-11-03 | 2006-05-18 | Invista Technologies S.A R.L. | Dyeable spandex |
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JPS59133248A (en) | 1983-01-20 | 1984-07-31 | Asahi Chem Ind Co Ltd | Polyurethane composition |
JP2887402B2 (en) | 1990-04-10 | 1999-04-26 | 旭化成工業株式会社 | Polyurethane composition |
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JP3228351B2 (en) | 1992-09-02 | 2001-11-12 | 東洋紡績株式会社 | Polyurethane elastic fiber |
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CN1089821C (en) * | 1997-02-13 | 2002-08-28 | 旭化成株式会社 | Elastic polyurethane fiber and process for producing same |
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KR100397704B1 (en) * | 2001-03-30 | 2003-09-17 | 주식회사 효성 | Stabilized spandex |
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KR100780602B1 (en) * | 2006-09-04 | 2007-11-30 | 태광산업주식회사 | Chlorine resistant polyurethaneurea composition |
KR20090015242A (en) * | 2007-08-08 | 2009-02-12 | 주식회사 효성 | Chlorine-resistant spandex fiber |
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- 2009-09-30 KR KR1020090092992A patent/KR101130510B1/en active IP Right Grant
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- 2010-09-29 WO PCT/KR2010/006634 patent/WO2011040755A2/en active Application Filing
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WO2002098970A1 (en) * | 2001-06-05 | 2002-12-12 | E. I. Du Pont De Nemours And Company | Spandex containing a mixture of phenolic compounds |
WO2006052318A1 (en) * | 2004-11-03 | 2006-05-18 | Invista Technologies S.A R.L. | Dyeable spandex |
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KR101130510B1 (en) | 2012-03-28 |
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WO2011040755A2 (en) | 2011-04-07 |
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CN102666947A (en) | 2012-09-12 |
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