JP5507868B2 - Polyurethane elastic fiber and method for producing the same - Google Patents
Polyurethane elastic fiber and method for producing the same Download PDFInfo
- Publication number
- JP5507868B2 JP5507868B2 JP2009086631A JP2009086631A JP5507868B2 JP 5507868 B2 JP5507868 B2 JP 5507868B2 JP 2009086631 A JP2009086631 A JP 2009086631A JP 2009086631 A JP2009086631 A JP 2009086631A JP 5507868 B2 JP5507868 B2 JP 5507868B2
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane
- elastic fiber
- quaternary ammonium
- sulfonic acid
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 210000004177 elastic tissue Anatomy 0.000 title claims description 87
- 229920002635 polyurethane Polymers 0.000 title claims description 76
- 239000004814 polyurethane Substances 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- -1 sulfonic acid quaternary ammonium salt Chemical class 0.000 claims description 67
- 229920000642 polymer Polymers 0.000 claims description 41
- 238000009987 spinning Methods 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011550 stock solution Substances 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- 239000002480 mineral oil Substances 0.000 claims description 11
- 235000010446 mineral oil Nutrition 0.000 claims description 11
- 229920002545 silicone oil Polymers 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 150000002430 hydrocarbons Chemical group 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 239000000835 fiber Substances 0.000 description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 16
- 235000013351 cheese Nutrition 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 16
- 229910052801 chlorine Inorganic materials 0.000 description 16
- 230000005611 electricity Effects 0.000 description 16
- 230000003068 static effect Effects 0.000 description 16
- 229920003226 polyurethane urea Polymers 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000002216 antistatic agent Substances 0.000 description 10
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000009940 knitting Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000000578 dry spinning Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- SIRKFWZKWMFCMY-UHFFFAOYSA-N C(CCCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.C[N+](CCCCCC)(CCCCCC)C Chemical compound C(CCCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.C[N+](CCCCCC)(CCCCCC)C SIRKFWZKWMFCMY-UHFFFAOYSA-N 0.000 description 1
- NPSIQUDPYRXSHD-JDVCJPALSA-N C(CCCCCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.C[N+](CCCCCCCC\C=C/CCCCCCCC)(CCCCCCCC\C=C/CCCCCCCC)C Chemical compound C(CCCCCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.C[N+](CCCCCCCC\C=C/CCCCCCCC)(CCCCCCCC\C=C/CCCCCCCC)C NPSIQUDPYRXSHD-JDVCJPALSA-N 0.000 description 1
- NNRZZBVSXLKOSY-UHFFFAOYSA-N C(CCCCCCCCCCC)S(=O)(=O)[O-].C(CCCCCCCCCCC)[NH3+] Chemical compound C(CCCCCCCCCCC)S(=O)(=O)[O-].C(CCCCCCCCCCC)[NH3+] NNRZZBVSXLKOSY-UHFFFAOYSA-N 0.000 description 1
- SNWKCKYGWDQFKP-UHFFFAOYSA-M C(CCCCCCCCCCC)S(=O)(=O)[O-].C[N+](CCCCCCCC)(CCCCCCCC)C Chemical compound C(CCCCCCCCCCC)S(=O)(=O)[O-].C[N+](CCCCCCCC)(CCCCCCCC)C SNWKCKYGWDQFKP-UHFFFAOYSA-M 0.000 description 1
- HQZVQZVSIFFFFE-UHFFFAOYSA-M C(CCCCCCCCCCC)S(=O)(=O)[O-].C[N+](CCCCCCCCCC)(CCCCCCCCCC)C Chemical compound C(CCCCCCCCCCC)S(=O)(=O)[O-].C[N+](CCCCCCCCCC)(CCCCCCCCCC)C HQZVQZVSIFFFFE-UHFFFAOYSA-M 0.000 description 1
- VBYGBFDIMDFVHO-UHFFFAOYSA-N C(CCCCCCCCCCC)S(=O)(=O)[O-].C[NH2+]CCCCCCCCCCCC Chemical compound C(CCCCCCCCCCC)S(=O)(=O)[O-].C[NH2+]CCCCCCCCCCCC VBYGBFDIMDFVHO-UHFFFAOYSA-N 0.000 description 1
- QGBXKGSTCUWKBS-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)[O-].C(CCCCCCCCCCC)[NH+](C)C Chemical compound C1(=CC=CC=C1)S(=O)(=O)[O-].C(CCCCCCCCCCC)[NH+](C)C QGBXKGSTCUWKBS-UHFFFAOYSA-N 0.000 description 1
- YDTMGZZFNAKQNE-UHFFFAOYSA-N CCCCCCCCCCCCNCCCCCCCCCCCC.CCCCCCCCCCCCOS(C1=CC=CC=C1)(=O)=O.CCO.CCO Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC.CCCCCCCCCCCCOS(C1=CC=CC=C1)(=O)=O.CCO.CCO YDTMGZZFNAKQNE-UHFFFAOYSA-N 0.000 description 1
- HAXDETGRQWUMNO-UHFFFAOYSA-N CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCC[N+](C)(C)CCCCCCCCCC Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCC[N+](C)(C)CCCCCCCCCC HAXDETGRQWUMNO-UHFFFAOYSA-N 0.000 description 1
- YOZCRYIAGGQKHS-UHFFFAOYSA-N CCCCCCCCCCCC[N+](C)(C)C.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 Chemical compound CCCCCCCCCCCC[N+](C)(C)C.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YOZCRYIAGGQKHS-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- JGFDZZLUDWMUQH-UHFFFAOYSA-N Didecyldimethylammonium Chemical compound CCCCCCCCCC[N+](C)(C)CCCCCCCCCC JGFDZZLUDWMUQH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- RKMJXTWHATWGNX-UHFFFAOYSA-N decyltrimethylammonium ion Chemical compound CCCCCCCCCC[N+](C)(C)C RKMJXTWHATWGNX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 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 1
- QQJDHWMADUVRDL-UHFFFAOYSA-N didodecyl(dimethyl)azanium Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC QQJDHWMADUVRDL-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- BVYKZCWFDFGEDY-UHFFFAOYSA-N dihexyl(dimethyl)azanium Chemical compound CCCCCC[N+](C)(C)CCCCCC BVYKZCWFDFGEDY-UHFFFAOYSA-N 0.000 description 1
- VMCSSRWYFKRLGP-UHFFFAOYSA-M dihexyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCC[N+](C)(C)CCCCCC VMCSSRWYFKRLGP-UHFFFAOYSA-M 0.000 description 1
- MELGLHXCBHKVJG-UHFFFAOYSA-N dimethyl(dioctyl)azanium Chemical compound CCCCCCCC[N+](C)(C)CCCCCCCC MELGLHXCBHKVJG-UHFFFAOYSA-N 0.000 description 1
- RGLFGXMUJWSIQF-WRBBJXAJSA-N dimethyl-bis[(z)-octadec-9-enyl]azanium Chemical compound CCCCCCCC\C=C/CCCCCCCC[N+](C)(C)CCCCCCCC\C=C/CCCCCCCC RGLFGXMUJWSIQF-WRBBJXAJSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- KTUVYMAZYSSBKC-UHFFFAOYSA-N hexyl benzenesulfonate Chemical compound CCCCCCOS(=O)(=O)C1=CC=CC=C1 KTUVYMAZYSSBKC-UHFFFAOYSA-N 0.000 description 1
- XTPRURKTXNFVQT-UHFFFAOYSA-N hexyl(trimethyl)azanium Chemical compound CCCCCC[N+](C)(C)C XTPRURKTXNFVQT-UHFFFAOYSA-N 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
- GVMDZMPQYYHMSV-UHFFFAOYSA-N octyl benzenesulfonate Chemical compound CCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVMDZMPQYYHMSV-UHFFFAOYSA-N 0.000 description 1
- HTKPDYSCAPSXIR-UHFFFAOYSA-N octyltrimethylammonium ion Chemical compound CCCCCCCC[N+](C)(C)C HTKPDYSCAPSXIR-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- RLJSXMVTLMHXJS-UHFFFAOYSA-M sodium;4-decylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 RLJSXMVTLMHXJS-UHFFFAOYSA-M 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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Description
本発明はポリウレタン系弾性繊維の制電性と耐塩素性の向上剤として、特定のスルホン酸4級アンモニウム塩を含有するポリウレタン系弾性繊維およびそのポリウレタン系弾性繊維の製造方法に関する。 The present invention relates to a polyurethane elastic fiber containing a specific sulfonic acid quaternary ammonium salt as an antistatic and chlorine resistance improver of a polyurethane elastic fiber and a method for producing the polyurethane elastic fiber.
ポリウレタン系弾性繊維は、天然繊維や他の化学繊維や合成繊維と交編・交織され、使用されることが多い。その際、巻取りパッケージからの解舒性不良や静電気の発生が多い場合、糸切れが多発することで、整経や編み経てが困難になり、生産性が低下する。ポリウレタン系弾性繊維として用いられるのは、ポリエーテル系ポリウレタン弾性繊維やポリエステル系ポリウレタン弾性繊維であり、近年これらポリウレタン系弾性繊維の後加工工程の高速化および使用繊度の細dtex化が進んできため、後加工工程において静電気によるトラブルが増加する傾向にある。そこで、静電気の発生を抑制するために、特許文献1や特許文献2に記載された弾性繊維用処理剤を繊維に付着させる。これらの処理剤は繊維表面に付着しているため、後加工工程において繊維とガイドとの接触による脱落や、精練などによって脱落するために安定した制電性の維持が困難であった。特に、ガイド上での脱落はスカムの原因となり、糸切れを発生させ生産性を低下させるという問題があった。また、特許文献3に記載されているように種々のスルホン酸塩を繊維に内添する方法もあるが、ポリウレタン系弾性重合体に対する相溶性が十分でない場合があり、高い制電性は付与できないという問題があった。
また、ポリウレタン系弾性繊維は、水泳プールなどの活性塩素濃度0.5〜3ppmの殺菌用塩素水中に繰り返し浸けると、その弾性機能が著しく損なわれ、糸切れを生じる。このため、ポリウレタン系弾性繊維の耐塩素性を向上させる方法として、特許文献4に示すように、金属酸化物等を内添させる方法があるが、紡糸原液に不溶であるため、均一に分散させにくく、作業性や生産性が低下する問題もあった。
Polyurethane elastic fibers are often used after being knitted and woven with natural fibers, other chemical fibers, and synthetic fibers. At that time, when unwinding defects and static electricity are frequently generated from the winding package, the yarn breakage occurs frequently, so that warping and knitting become difficult and productivity is lowered. Polyurethane-based elastic fibers are polyether-based polyurethane elastic fibers and polyester-based polyurethane elastic fibers. In recent years, the speed of post-processing of these polyurethane-based elastic fibers and the finer dtex of the used fineness have progressed. Troubles due to static electricity tend to increase in the post-processing process. Then, in order to suppress generation | occurrence | production of static electricity, the processing agent for elastic fibers described in
Further, when the polyurethane elastic fiber is repeatedly immersed in sterilizing chlorine water having an active chlorine concentration of 0.5 to 3 ppm such as a swimming pool, its elastic function is remarkably impaired and thread breakage occurs. For this reason, as a method for improving the chlorine resistance of polyurethane-based elastic fibers, there is a method in which a metal oxide or the like is internally added as shown in Patent Document 4, but since it is insoluble in the spinning stock solution, it is uniformly dispersed. There is also a problem that workability and productivity are reduced.
本発明は、上記従来技術の有する問題点を解決し、制電性、耐塩素性、生産性に優れたポリウレタン系弾性繊維およびポリウレタン系弾性繊維の製造方法を提供することを目的とする。 The object of the present invention is to solve the above-mentioned problems of the prior art and provide a polyurethane elastic fiber excellent in antistatic property, chlorine resistance and productivity, and a method for producing the polyurethane elastic fiber.
本発明者らは上記課題について鋭意検討した結果、ポリウレタン系弾性繊維の紡糸原液に可溶な制電剤である特定のスルホン酸4級アンモニウム塩をポリウレタン系弾性繊維に内添することで、取扱い性、制電性、耐塩素性、生産性に優れたポリウレタン系弾性繊維を提供できることを見出し、本発明に至った。 As a result of intensive studies on the above-mentioned problems, the present inventors have added a specific sulfonic acid quaternary ammonium salt, which is an antistatic agent soluble in a spinning stock solution of a polyurethane-based elastic fiber, to the polyurethane-based elastic fiber. It has been found that a polyurethane-based elastic fiber having excellent properties, antistatic properties, chlorine resistance, and productivity can be provided, and the present invention has been achieved.
すなわち、本発明はポリウレタン系弾性重合体およびスルホン酸4級アンモニウム塩を含有するポリウレタン系弾性繊維であって、前記スルホン酸4級アンモニウム塩が、下記一般式(1)で示される化合物であり、前記ポリウレタン系弾性重合体に対して0.01〜10重量%含まれる、ポリウレタン系弾性繊維である。
前記R1およびR2は、それぞれ独立して炭素数1〜22の炭化水素基であり、前記R3およびR4は、それぞれ独立して炭素数1〜7の炭化水素基または水酸基を有する炭素数1〜18の炭化水素基であることが好ましい。さらに前記R1およびR2は、それぞれ独立して、炭素数6〜18の炭化水素基であることが好ましい。 R 1 and R 2 are each independently a hydrocarbon group having 1 to 22 carbon atoms, and R 3 and R 4 are each independently a hydrocarbon group having 1 to 7 carbon atoms or a carbon having a hydroxyl group. It is preferable that it is a C1-C18 hydrocarbon group. Further, R 1 and R 2 are preferably each independently a hydrocarbon group having 6 to 18 carbon atoms.
また、本発明のポリウレタン系弾性繊維はベース成分としてシリコーンオイルおよび鉱物油を含有し、鉱物油の重量割合が60重量%以下である弾性繊維用処理剤が、弾性繊維に対して0.1〜15重量%付与されていることが好ましい。 The polyurethane-based elastic fiber of the present invention contains silicone oil and mineral oil as a base component, and the elastic fiber treatment agent having a mineral oil weight ratio of 60% by weight or less is 0.1 to 0.1% of the elastic fiber. It is preferable that 15% by weight is applied.
本発明は、前記ポリウレタン系弾性重合体および前記スルホン酸4級アンモニウム塩を含む紡糸原液を調製し、該紡糸原液を紡糸する、ポリウレタン系弾性繊維の製造方法である。 The present invention is a method for producing a polyurethane elastic fiber, which comprises preparing a spinning stock solution containing the polyurethane elastic polymer and the sulfonic acid quaternary ammonium salt, and spinning the spinning stock solution.
ポリウレタン系弾性繊維の製造方法は、前記ポリウレタン系弾性重合体を含む溶液に前記スルホン酸4級アンモニウム塩を添加して紡糸原液を調製し、該紡糸原液を紡糸することが好ましい。添加される前記スルホン酸4級アンモニウム塩は、その水分量が5重量%以下であり、その不純物である無機塩の含有量が1重量%以下であることが好ましい。 In the method for producing a polyurethane-based elastic fiber, it is preferable to prepare a spinning stock solution by adding the sulfonic acid quaternary ammonium salt to a solution containing the polyurethane-based elastic polymer, and spin the spinning stock solution. The sulfonic acid quaternary ammonium salt to be added preferably has a water content of 5% by weight or less and an inorganic salt content of 1% by weight or less.
本発明のような特定のスルホン酸4級アンモニウム塩は、塩の極性を低下させ、紡糸原液に対して良好な溶解性と相溶性を有する。このようなスルホン酸4級アンモニウム塩をポリウレタン系弾性繊維に内添させることで、制電性、耐塩素性、生産性に優れたポリウレタン系弾性繊維を得ることができる。また、制電性、耐塩素性、生産性に優れた弾性繊維の製造方法を提供することができる。 Certain sulfonic acid quaternary ammonium salts such as the present invention reduce the polarity of the salt and have good solubility and compatibility with the spinning dope. By adding such a sulfonic acid quaternary ammonium salt to a polyurethane elastic fiber, a polyurethane elastic fiber excellent in antistatic property, chlorine resistance and productivity can be obtained. Moreover, the manufacturing method of the elastic fiber excellent in antistatic property, chlorine resistance, and productivity can be provided.
本発明は、ポリウレタン系弾性重合体および特定のスルホン酸4級アンモニウム塩を含有するポリウレタン系弾性繊維およびその製造方法である。本発明をさらに詳細に説明する。 The present invention relates to a polyurethane elastic fiber containing a polyurethane elastic polymer and a specific sulfonic acid quaternary ammonium salt, and a method for producing the same. The present invention will be described in further detail.
(スルホン酸4級アンモニウム塩)
本発明に用いられるスルホン酸4級アンモニウム塩は、上記一般式(1)で示される化合物である。式(1)中、R1、R2、R3、R4は、それぞれ独立して、炭素数1〜22の炭化水素基または水酸基を有する炭素数1〜18の炭化水素基を示す。R1、R2、R3、R4の炭化水素基は、脂肪族炭化水素基、脂環族炭化水素基、芳香族炭化水素基であってもよく、これらの中でも脂肪族炭化水素基が好ましい。脂肪族炭化水素基としては、アルキル基、アルケニル基であってもよく、また直鎖状や分岐を有していてもよい。
R5は、炭素数6〜22の脂肪族炭化水素基または上記一般式(2)で示される置換フェニル基を示す。式(2)中、R6は炭素数6〜22の脂肪族炭化水素基を示す。R5、R6の脂肪族炭化水素基は、アルキル基、アルケニル基であってもよく、また直鎖状や分岐を有していてもよい。
(Sulphonic acid quaternary ammonium salt)
The sulfonic acid quaternary ammonium salt used in the present invention is a compound represented by the above general formula (1). In formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrocarbon group having 1 to 22 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms having a hydroxyl group. The hydrocarbon group of R 1 , R 2 , R 3 , and R 4 may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and among these, an aliphatic hydrocarbon group is preferable. The aliphatic hydrocarbon group may be an alkyl group or an alkenyl group, and may be linear or branched.
R 5 represents an aliphatic hydrocarbon group having 6 to 22 carbon atoms or a substituted phenyl group represented by the general formula (2). In formula (2), R 6 represents an aliphatic hydrocarbon group having 6 to 22 carbon atoms. The aliphatic hydrocarbon group for R 5 and R 6 may be an alkyl group or an alkenyl group, and may be linear or branched.
このように本発明のスルホン酸4級アンモニウム塩は、4級アンモニウムであることとスルホネートに炭素数6〜22の長鎖の脂肪族炭化水素基を導入することで、塩の極性を適度に低下させ、紡糸原液に対する良好な溶解性と相溶性を付与できる。また、式(2)にあるように、スルホネートの炭化水素基を、炭素数6〜22の長鎖の脂肪族炭化水素基を有する置換フェニル基とすることで、より良好な溶解性と相溶性を持つようになる。具体的には、ポリウレタン系弾性繊維の紡糸原液の溶媒として用いられるDMAC、DMFに対して、30〜50重量%程度の溶解性を示すことができる。また、本発明のスルホン酸4級アンモニウム塩の窒素原子が活性塩素を捕捉する効果を有するため、本発明のスルホン酸4級アンモニウム塩をポリウレタン系弾性繊維に添加することで、制電性と耐塩素性を同時に付与できる。 Thus, the sulfonic acid quaternary ammonium salt of the present invention is a quaternary ammonium, and by introducing a long-chain aliphatic hydrocarbon group having 6 to 22 carbon atoms into the sulfonate, the polarity of the salt is appropriately reduced. And good solubility and compatibility with the spinning dope can be imparted. Further, as shown in the formula (2), the hydrocarbon group of the sulfonate is a substituted phenyl group having a long-chain aliphatic hydrocarbon group having 6 to 22 carbon atoms, so that better solubility and compatibility are achieved. To have. Specifically, it can exhibit a solubility of about 30 to 50% by weight with respect to DMAC and DMF used as a solvent for the spinning stock solution of polyurethane-based elastic fibers. In addition, since the nitrogen atom of the sulfonic acid quaternary ammonium salt of the present invention has an effect of capturing active chlorine, the addition of the sulfonic acid quaternary ammonium salt of the present invention to the polyurethane elastic fiber can improve antistatic properties and resistance. Chlorine can be imparted at the same time.
本発明のスルホン酸4級アンモニウム塩において、スルホン酸4級アンモニウム塩を構成する4級アンモニウムに長鎖の炭化水素基を3〜4個導入すると、極性が低下して相溶性が悪化する場合がある。このため、ポリウレタン系弾性重合体表面にブリードアウトし、制電性や耐塩素性の性能が安定して維持できない場合や、これらが発揮されない場合がある。このような理由から、R1およびR2がそれぞれ独立して炭素数1〜22の炭化水素基で、かつR3およびR4がそれぞれ独立して炭素数1〜7の炭化水素基または水酸基を有する炭素数1〜18の炭化水素基であることが好ましい。
R3およびR4は炭素数1〜7の炭化水素基であり、炭化水素基上に水酸基を有しないことがさらに好ましい。R3やR4の炭化水素基上に水酸基が存在すると、スルホン酸4級アンモニウム塩の極性が高くなるため制電性が向上するが、ポリウレタン系弾性繊維からのブリードアウトや水への溶出が起こりやすく、生産性と制電性の維持が困難となる場合がある。R3およびR4は炭素数が1〜3個である炭化水素基であることが特に好ましい。
In the sulfonic acid quaternary ammonium salt of the present invention, when 3 to 4 long-chain hydrocarbon groups are introduced into the quaternary ammonium constituting the sulfonic acid quaternary ammonium salt, the polarity may decrease and the compatibility may deteriorate. is there. For this reason, it may bleed out on the surface of the polyurethane-based elastic polymer, and the antistatic performance and chlorine resistance performance may not be stably maintained or may not be exhibited. For these reasons, R 1 and R 2 are each independently a hydrocarbon group having 1 to 22 carbon atoms, and R 3 and R 4 are each independently a hydrocarbon group or hydroxyl group having 1 to 7 carbon atoms. It is preferably a hydrocarbon group having 1 to 18 carbon atoms.
R 3 and R 4 are each a hydrocarbon group having 1 to 7 carbon atoms, and it is more preferable that no hydroxyl group is present on the hydrocarbon group. When a hydroxyl group is present on the hydrocarbon group of R 3 or R 4 , the polarity of the sulfonic acid quaternary ammonium salt is increased, so that antistatic properties are improved. However, bleeding out from polyurethane-based elastic fibers and elution into water are prevented. It is likely to occur, and it may be difficult to maintain productivity and antistatic performance. R 3 and R 4 are particularly preferably a hydrocarbon group having 1 to 3 carbon atoms.
さらに、スルホン酸4級アンモニウム塩を構成する4級アンモニウムに比較的短鎖の炭化水素基を3〜4個導入すると、極性が高いため親水性が強くなり、ポリウレタン系弾性繊維の紡糸原液に対する溶解性が乏しくなる場合がある。また、繊維ポリマーに対する相溶性も悪くなる場合がある。このような理由から、R1およびR2がそれぞれ独立して炭素数6〜18の炭化水素基で、かつR3およびR4がそれぞれ独立して炭素数1〜7の炭化水素基または水酸基を有する炭素数1〜18の炭化水素基であることが好ましい。R1およびR2は、炭素数が8〜18である炭化水素基がさらに好ましく、炭素数10〜16である炭化水素基が特に好ましい。 Furthermore, when 3 to 4 relatively short-chain hydrocarbon groups are introduced into the quaternary ammonium constituting the sulfonic acid quaternary ammonium salt, the hydrophilicity increases due to the high polarity, and the polyurethane-based elastic fiber dissolves in the spinning dope. May be poor. Moreover, the compatibility with a fiber polymer may also worsen. For these reasons, R 1 and R 2 are each independently a hydrocarbon group having 6 to 18 carbon atoms, and R 3 and R 4 are each independently a hydrocarbon group or hydroxyl group having 1 to 7 carbon atoms. It is preferably a hydrocarbon group having 1 to 18 carbon atoms. R 1 and R 2 are more preferably a hydrocarbon group having 8 to 18 carbon atoms, and particularly preferably a hydrocarbon group having 10 to 16 carbon atoms.
また、上記式(1)のR5が脂肪族炭化水素基の場合、その炭素数は6〜20が好ましく、8〜18がさらに好ましく、10〜16が特に好ましい。R5が上記式(2)で示される置換フェニル基の場合、R6の炭化水素基の炭素数は6〜20が好ましく、8〜18がさらに好ましく、10〜16が特に好ましい。R6の置換位置は特に限定なく、任意の位置でよい。これらの中でも、R5は、上記式(2)で示される置換フェニル基が好ましい。 Further, when R 5 in the formula (1) is an aliphatic hydrocarbon group, the carbon number 6 to 20 by weight, more preferably 8 to 18, particularly preferably 10 to 16. When R 5 is a substituted phenyl group represented by the above formula (2), the hydrocarbon group of R 6 preferably has 6 to 20 carbon atoms, more preferably 8 to 18 carbon atoms, and particularly preferably 10 to 16 carbon atoms. The substitution position of R 6 is not particularly limited, and may be any position. Among these, R 5 is preferably a substituted phenyl group represented by the above formula (2).
本発明に用いられるスルホン酸4級アンモニウム塩は、対応するスルホン酸ナトリウムと4級アンモニウムクロライドを水中で80℃から90℃に保って3時間攪拌し、複製する無機塩を水層に溶解して削減するため生成した有機層を数回イオン交換水で水洗し、140℃で水分量が5重量%以下になるまで乾燥させることで簡便に合成できる。 The sulfonic acid quaternary ammonium salt used in the present invention is prepared by stirring the corresponding sodium sulfonate and quaternary ammonium chloride in water at 80 ° C. to 90 ° C. for 3 hours, and dissolving the replicating inorganic salt in the aqueous layer. In order to reduce, the organic layer produced can be easily synthesized by washing with ion-exchanged water several times and drying at 140 ° C. until the water content is 5% by weight or less.
本発明に用いられるスルホン酸4級アンモニウム塩は、その水分量は5重量%以下が好ましく、1重量%以下がより好ましく、0.3重量%以下がさらに好ましい。水分量が5重量%よりも多くなると、ポリウレタン系弾性繊維の糸強度の低下の原因となる場合がある。また、不純物として含有される無機塩の含有量は1重量%以下が好ましく、0.5重量%以下がより好ましく、0.1重量%以下がさらに好ましい。無機塩の含有量が1重量%よりも多くなると、繊維強度の低下や生産性の低下の原因となる場合がある。
無機塩としては、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム等が挙げられる。
The water content of the sulfonic acid quaternary ammonium salt used in the present invention is preferably 5% by weight or less, more preferably 1% by weight or less, and further preferably 0.3% by weight or less. If the water content exceeds 5% by weight, it may cause a decrease in the yarn strength of the polyurethane elastic fiber. Further, the content of the inorganic salt contained as an impurity is preferably 1% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.1% by weight or less. If the content of the inorganic salt is more than 1% by weight, it may cause a decrease in fiber strength or a decrease in productivity.
Examples of inorganic salts include sodium chloride, potassium chloride, magnesium chloride, calcium chloride and the like.
スルホン酸4級アンモニウム塩を形成する4級アンモニウムカチオンとしては、ジメチルジヘキシルアンモニウムカチオン、ジメチルジオクチルアンモニウムカチオン、ジメチルジデシルアンモニウムカチオン、ジメチルジドデシルアンモニウムカチオン、ジメチルジオレイルアンモニウムカチオン、ジエタノールジドデシルアンモニウムカチオン、ジエタノールジオレイルアンモニウムカチオン、トリメチルヘキシルアンモニウムカチオン、トリメチルオクチルアンモニウムカチオン、トリメチルデシルアンモニウムカチオン、トリメチルドデシルアンモニウムカチオン等が挙げられる。
同様に、スルホン酸4級アンモニウム塩を形成するスルホネートアニオンとしては、ヘキシルスルホネート、オクチルスルホネート、ドデシルスルホネート、ヘキシルベンゼンスルホネート、オクチルベンゼンスルホネート、ドデシルベンゼンスルホネート等が挙げられる。
Examples of the quaternary ammonium cation forming the sulfonic acid quaternary ammonium salt include dimethyldihexyl ammonium cation, dimethyl dioctyl ammonium cation, dimethyl didecyl ammonium cation, dimethyl didodecyl ammonium cation, dimethyl dioleyl ammonium cation, diethanol didodecyl ammonium cation, Examples include diethanoldioleyl ammonium cation, trimethylhexyl ammonium cation, trimethyl octyl ammonium cation, trimethyl decyl ammonium cation, and trimethyl dodecyl ammonium cation.
Similarly, examples of the sulfonate anion that forms a quaternary ammonium salt of sulfonic acid include hexyl sulfonate, octyl sulfonate, dodecyl sulfonate, hexyl benzene sulfonate, octyl benzene sulfonate, and dodecyl benzene sulfonate.
(ポリウレタン系弾性繊維およびその製造方法)
本発明のポリウレタン系弾性繊維はポリウレタン系弾性重合体およびスルホン酸4級アンモニウム塩を含有するものであり、ポリウレタン系弾性重合体を主要な成分とするものである。ポリウレタン系弾性繊維としては、ポリエーテル系ポリウレタン弾性繊維、ポリエステル系ポリウレタン弾性繊維等が挙げられる。
(Polyurethane elastic fiber and method for producing the same)
The polyurethane elastic fiber of the present invention contains a polyurethane elastic polymer and a sulfonic acid quaternary ammonium salt, and has a polyurethane elastic polymer as a main component. Examples of the polyurethane elastic fibers include polyether polyurethane elastic fibers and polyester polyurethane elastic fibers.
ポリウレタン系弾性重合体としては、ハードセグメントにジイソシアナートを用い、ソフトセグメントとしてポリエーテルジオールを用いたポリエーテル系ポリウレタン弾性重合体と、ポリエステルジオールを用いたポリエステル系ポリウレタン弾性重合体がある。
またこれらには、鎖伸長剤として低分子量の多官能性活性水素化合物が使用される。代表的には、有機ジイソシアナートと高分子ジオールとで調整されたイソシアナート末端のプレポリマーに多官能性活性水素原子を有する鎖伸長剤および単官能性活性水素原子を有する末端封鎖剤を1段または多段階に反応せしめて分子内にウレタン基を有するポリウレタンウレア弾性重合体が挙げられる。これを乾式紡糸、湿式紡糸または溶融紡糸してポリウレタンウレア弾性繊維を得ることができる。
Examples of the polyurethane-based elastic polymer include a polyether-based polyurethane elastic polymer using diisocyanate as a hard segment and a polyether diol as a soft segment, and a polyester-based polyurethane elastic polymer using a polyester diol.
These also use low molecular weight polyfunctional active hydrogen compounds as chain extenders. Typically, a chain extender having a polyfunctional active hydrogen atom and an end-capping agent having a monofunctional active hydrogen atom are added to an isocyanate-terminated prepolymer prepared with an organic diisocyanate and a polymer diol. A polyurethane urea elastic polymer having urethane groups in the molecule by reacting in stages or multiple stages can be mentioned. A polyurethane urea elastic fiber can be obtained by dry spinning, wet spinning or melt spinning.
本発明のポリウレタンウレア弾性重合体の製造原料の一つである高分子ジオールとしては、両末端にヒドロキシル基を持つ高分子体である。これらは例えば、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシテトラメチレングリコール、ポリオキシペンタメチレングリコール等を挙げることができる。 The polymer diol that is one of the raw materials for producing the polyurethaneurea elastic polymer of the present invention is a polymer having hydroxyl groups at both ends. These include, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol and the like.
本発明のポリウレタンウレア弾性重合体の製造原料の一つである有機ジイソシアナートとしては、例えば脂肪族、脂環族、芳香族のジイソシアナートの中で、反応条件下で溶解または液状であるものすべてを適用できる。例えば、メチレン−ビス(4−フェニルイソシアナート)、メチレン−ビス(3−メチル−4−フェニルイソシアナート)、2,4−トリレンジイソシアナート、2,6−トリレンジイソシアナート等が例示され、好ましくはメチレン−ビス(4−フェニルイソシアナート)である。 The organic diisocyanate that is one of the raw materials for producing the polyurethaneurea elastic polymer of the present invention is, for example, an aliphatic, alicyclic, or aromatic diisocyanate that is dissolved or liquid under reaction conditions. All things can be applied. Examples include methylene-bis (4-phenyl isocyanate), methylene-bis (3-methyl-4-phenyl isocyanate), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and the like. Methylene-bis (4-phenyl isocyanate) is preferred.
本発明のポリウレタンウレア弾性重合体の製造原料の一つである多官能性活性水素原子を有する鎖伸長剤としては、例えば、ヒドラジン、ポリヒドラジド、ポリオール、エチレンジアミン、プロピレンジアミン、ビス−(4−アミノシクロヘキシル)メタン、m−キシリレンジアミン、p−キシリレンジアミン等のポリアミン、ヒドロキシルアミン、エチレングリコール、1,4−ブタンジオール、1,6−ヘキサンジオール、1,8−オクタンジオール等のポリオール等を用いることができる。 Examples of the chain extender having a polyfunctional active hydrogen atom that is one of the raw materials for producing the polyurethaneurea elastic polymer of the present invention include hydrazine, polyhydrazide, polyol, ethylenediamine, propylenediamine, and bis- (4-amino). (Cyclohexyl) Polyamines such as methane, m-xylylenediamine, p-xylylenediamine, polyols such as hydroxylamine, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, etc. Can be used.
本発明のポリウレタンウレア弾性重合体の製造原料の一つである単官能性活性水素原子を有する末端停止剤としては、例えば、ジエチルアミンのようなジアルキルアミン等が用いられる。これらの鎖伸長剤、末端停止剤は一種または二種以上混合して用いてもよい。上記ポリウレタン重合体組成物には、公知のポリウレタン重合体組成物に使用される特定の化学構造を有する有機または無機の配合剤、例えば、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、ヒンダードアミン系化合物等の紫外線吸収剤;ヒンダードフェノール系化合物等の酸化防止剤;防黴剤;硫酸バリウム、酸化マグネシウム、珪酸マグネシウム、珪酸カルシウム、酸化亜鉛、ハイドロタルサイト等のような無機微粒子;ステアリン酸マグネシウム、ステアリン酸カルシウム、ポリテトラフルオロエチレン、ポリオルガノシロキサン等の粘着防止剤等を適宜配合することもできる。 As the terminal terminator having a monofunctional active hydrogen atom, which is one of the raw materials for producing the polyurethaneurea elastic polymer of the present invention, for example, a dialkylamine such as diethylamine is used. These chain extenders and end terminators may be used alone or in combination. The polyurethane polymer composition includes an organic or inorganic compounding agent having a specific chemical structure used in known polyurethane polymer compositions, for example, ultraviolet rays such as benzophenone compounds, benzotriazole compounds, and hindered amine compounds. Absorbents; Antioxidants such as hindered phenol compounds; Antifungal agents; Inorganic fine particles such as barium sulfate, magnesium oxide, magnesium silicate, calcium silicate, zinc oxide, hydrotalcite; magnesium stearate, calcium stearate, An anti-tacking agent such as polytetrafluoroethylene and polyorganosiloxane can be appropriately blended.
本発明のポリウレタン系弾性繊維の製造方法は、前記ポリウレタン系弾性重合体および前記スルホン酸4級アンモニウム塩を含む紡糸原液を調製し、該紡糸原液を紡糸するものである。紡糸方法としては特に限定はなく、公知の方法を採用できる。本発明のスルホン酸4級アンモニウム塩は疎水性が強いために水洗が容易であり、高温または減圧によって十分に乾燥できる。その結果、ポリウレタン系弾性重合体の原料とともに混合、反応せしめ、紡糸原液を調整することも可能である。しかし、ポリウレタン系弾性重合体の重合が終わる前に本発明のスルホン酸4級アンモニウム塩を添加すると、スルホン酸4級アンモニウム塩の合成中に生成する微量の不純物との反応が起こり、ポリウレタン系弾性繊維の黄変等、糸質低下の原因となる場合がある。よって、ポリウレタン系弾性重合体を含む溶液にスルホン酸4級アンモニウム塩を添加して紡糸原液を調製し、これを紡糸することが好ましい。 The method for producing a polyurethane elastic fiber of the present invention is to prepare a spinning stock solution containing the polyurethane elastic polymer and the sulfonic acid quaternary ammonium salt, and spin the spinning stock solution. The spinning method is not particularly limited, and a known method can be adopted. Since the sulfonic acid quaternary ammonium salt of the present invention is highly hydrophobic, it can be easily washed with water and can be sufficiently dried at high temperature or under reduced pressure. As a result, it is possible to prepare a spinning dope by mixing and reacting together with the raw material of the polyurethane elastic polymer. However, if the sulfonic acid quaternary ammonium salt of the present invention is added before the polymerization of the polyurethane elastic polymer is completed, a reaction with a trace amount of impurities generated during the synthesis of the sulfonic acid quaternary ammonium salt occurs, and the polyurethane elastic It may cause a decrease in yarn quality such as yellowing of the fiber. Therefore, it is preferable to prepare a spinning dope by adding a sulfonic acid quaternary ammonium salt to a solution containing a polyurethane-based elastic polymer, and then spin it.
ポリウレタン系弾性重合体を含む紡糸原液の調整方法としては、例えば、DMAC、DMFなどの溶剤中に、本発明のスルホン酸4級アンモニウム塩を含む各原料を投入、溶解せしめ、適度な温度に加熱し、反応させて紡糸原液を得る方法や、前記高分子ジオールと有機ジイソシアナートを予め混合、適度な温度で反応せしめ、鎖伸長剤のDMAC、DMF溶液を加え、反応させた後に、本発明のスルホン酸4級アンモニウム塩を添加して紡糸原液を得る方法がある。 As a method for preparing a spinning dope containing a polyurethane-based elastic polymer, for example, each raw material containing the sulfonic acid quaternary ammonium salt of the present invention is put in a solvent such as DMAC or DMF, dissolved, and heated to an appropriate temperature. Then, a method for obtaining a spinning dope by reacting, or mixing the polymer diol and the organic diisocyanate in advance, reacting them at an appropriate temperature, adding a DMAC or DMF solution of a chain extender and reacting them, then the present invention There is a method of adding a sulfonic acid quaternary ammonium salt to obtain a spinning dope.
紡糸原液を調製する際に、本発明のスルホン酸4級アンモニウム塩をそのまま添加することも可能であるが、紡糸原液に用いられるDMACまたはDMF溶媒を用いてスルホン酸4級アンモニウム塩を30〜50重量%含有する溶液とし、これを添加することでより均一に混合でき、取扱い性もよい。 In preparing the spinning dope, it is possible to add the sulfonic acid quaternary ammonium salt of the present invention as it is, but using a DMAC or DMF solvent used in the spinning dope, 30 to 50 sulfonic acid quaternary ammonium salt is added. A solution containing wt% can be mixed more uniformly by adding this, and the handleability is also good.
紡糸原液を調製する際に使用されるスルホン酸4級アンモニウム塩は、上述しているようにその水分量が5重量%以下であり、その不純物である無機塩の含有量が1重量%以下であることが好ましい。
ポリウレタン系弾性重合体に対する(ポリウレタン系弾性重合体を100重量%としたとき)スルホン酸4級アンモニウム塩の重量割合は、0.01〜10重量%であり、好ましくは0.5〜3重量%であり、さらに好ましくは1〜3重量%である。0.01重量%よりも少ない場合、制電性の効果がなく、10重量%より多くなると繊維表面への析出や繊維強度の低下を招くため、生産性、糸質が著しく悪化する。
As described above, the sulfonic acid quaternary ammonium salt used in preparing the spinning dope has a water content of 5% by weight or less, and the content of the inorganic salt as an impurity is 1% by weight or less. Preferably there is.
The weight ratio of the sulfonic acid quaternary ammonium salt to the polyurethane elastic polymer (when the polyurethane elastic polymer is 100% by weight) is 0.01 to 10% by weight, preferably 0.5 to 3% by weight. More preferably, it is 1 to 3% by weight. When the amount is less than 0.01% by weight, there is no antistatic effect, and when the amount exceeds 10% by weight, precipitation on the fiber surface and a decrease in fiber strength are caused, so that productivity and yarn quality are remarkably deteriorated.
(弾性繊維用処理剤)
本発明のポリウレタン系弾性繊維は、弾性繊維用処理剤を付与することができる。弾性繊維用処理剤としては、ベース成分としてシリコーンオイルおよび鉱物油を必須に含有し、処理剤全体に対する鉱物油の重量割合が60重量%以下となることが好ましい。処理剤全体に占める鉱物油の重量割合は、10〜50重量%が好ましく、10〜30重量%がさらに好ましい。鉱物油の割合が60重量%よりも大きくなると、ポリウレタン系弾性繊維中のスルホン酸4級アンモニウム塩がブリードアウトし易くなる。
(Treatment agent for elastic fibers)
The polyurethane elastic fiber of the present invention can be provided with an elastic fiber treating agent. The elastic fiber treatment agent preferably contains silicone oil and mineral oil as base components, and the weight ratio of mineral oil to the treatment agent as a whole is preferably 60% by weight or less. The weight ratio of the mineral oil in the entire treatment agent is preferably 10 to 50% by weight, and more preferably 10 to 30% by weight. When the proportion of the mineral oil is larger than 60% by weight, the sulfonic acid quaternary ammonium salt in the polyurethane elastic fiber is likely to bleed out.
シリコーンオイルとしては特に限定はないが、たとえば、ポリジメチルシロキサン、ポ
リアルキルシロキサン、ポリアルキルフェニルシロキサン(いずれのシリコーンオイルも
25℃における粘度:2〜100mm2/s)等を挙げることができ、1種または2種以
上を併用してもよい。これらのシリコーンオイルのうちでも、処理剤のオイリング時に扱
いやすく、粘度が高すぎると糸がローラーに取られて切れてしまう等の理由から、弾性繊
維用処理剤の30℃における粘度が、好ましくは3〜100mm2/s、さらに好ましく
は5〜50mm2/sに調整することができるようなシリコーンオイルを選択することが
好ましい。
The silicone oil is not particularly limited, and examples thereof include polydimethylsiloxane, polyalkylsiloxane, and polyalkylphenylsiloxane (both silicone oils have a viscosity at 25 ° C .: 2 to 100 mm 2 / s). You may use a seed | species or 2 or more types together. Among these silicone oils, the viscosity at 30 ° C. of the elastic fiber treatment agent is preferable because it is easy to handle during the oiling of the treatment agent, and the viscosity is too high. It is preferable to select a silicone oil that can be adjusted to 3 to 100 mm 2 / s, more preferably 5 to 50 mm 2 / s.
鉱物油としては特に限定はないが、たとえば、30℃における粘度が30〜150秒、
好ましくは60〜100秒のスピンドル油や流動パラフィン等を挙げることができ、1種
または2種以上を併用してもよい。鉱物油の粘度が30秒よりも低いと、得られる弾性繊
維の品質が低下することがある。一方、鉱物油の粘度が150秒超であると、弾性繊維用
処理剤全体の粘度が高くなり、得られる弾性繊維がローラーに取られ、糸が切れてしまう
ことがある。
Although there is no limitation in particular as mineral oil, For example, the viscosity in 30 degreeC is 30 to 150 second,
Preferred examples include spindle oil and liquid paraffin for 60 to 100 seconds, and one kind or two or more kinds may be used in combination. When the viscosity of the mineral oil is lower than 30 seconds, the quality of the obtained elastic fiber may be deteriorated. On the other hand, if the viscosity of the mineral oil is more than 150 seconds, the viscosity of the entire elastic fiber treatment agent increases, and the resulting elastic fiber may be taken by the roller and the yarn may be broken.
弾性繊維用処理剤は、平滑剤、解舒性向上剤、つなぎ剤、制電剤、酸化防止剤、紫外線吸収剤等の通常弾性繊維の処理剤に用いられる成分をさらに含有することができる。 The processing agent for elastic fibers can further contain components usually used for the processing agent for elastic fibers, such as a smoothing agent, an unraveling improver, a binder, an antistatic agent, an antioxidant, and an ultraviolet absorber.
弾性繊維用処理剤は、30℃における粘度が2〜100mm2/sの範囲にあることが好ましく、5〜15mm2/sの範囲がより好ましい。粘度が2mm2/s未満では、油剤の揮発が問題となる事があり、50mm2/sより大きいと弾性繊維への表面への濡れ性が悪くなる事がある。 The elastic fiber treatment agent preferably has a viscosity at 30 ° C. of 2 to 100 mm 2 / s, and more preferably 5 to 15 mm 2 / s. If the viscosity is less than 2 mm 2 / s, volatilization of the oil agent may be a problem, and if it is greater than 50 mm 2 / s, the wettability of the elastic fiber to the surface may be deteriorated.
弾性繊維用処理剤を製造する方法については、特に限定はなく、公知の方法を適用することができる。弾性繊維用処理剤は、構成する上記の各成分を任意の順番で添加混合することによって製造される。また、弾性繊維用処理剤を付与する方法については、特に限定はなく、公知の方法を適用することができる。 There is no limitation in particular about the method of manufacturing the processing agent for elastic fibers, A well-known method is applicable. The processing agent for elastic fibers is produced by adding and mixing the above-described constituent components in an arbitrary order. Moreover, there is no limitation in particular about the method of providing the processing agent for elastic fibers, A well-known method is applicable.
本発明のポリウレタン系弾性繊維は、上記弾性繊維用処理剤が弾性繊維に対して0.1〜15重量%(好ましくは1〜10重量%)付与されている弾性繊維である。0.1重量%より少ないと本発明の効果が充分でなく、15重量%を越えると不経済である。 The polyurethane-based elastic fiber of the present invention is an elastic fiber in which the above-mentioned elastic fiber treating agent is applied to the elastic fiber in an amount of 0.1 to 15% by weight (preferably 1 to 10% by weight). If it is less than 0.1% by weight, the effect of the present invention is not sufficient, and if it exceeds 15% by weight, it is uneconomical.
本発明のポリウレタン系弾性繊維は、その糸上静電気が−1KV〜+1KVであり、好ましくは−0.7KV〜+0.7KV、さらに好ましくは−0.5KV〜+0.5KVである。糸上静電気が−1KVより小さいまたは1KVより大きいと、ほこり等を糸に引き付け、糸品位や生産性を低下させることがある。 The polyurethane elastic fiber of the present invention has a static electricity on the yarn of -1 KV to +1 KV, preferably -0.7 KV to +0.7 KV, more preferably -0.5 KV to +0.5 KV. When the static electricity on the yarn is smaller than -1 KV or larger than 1 KV, dust or the like may be attracted to the yarn, and the yarn quality and productivity may be lowered.
本発明のポリウレタン系弾性繊維の用途として、CSY、シングルカバリング、PLY、エアーカバリング等のカバリング糸等の加工糸や、丸編み、トリコット等により、布帛として使用することができる。また、これらの加工糸、布帛を使用してストッキング、靴下、下着、水着等の伸縮性が必要とされる製品や、ジーンズ、スーツ等のアウターウェア等に快適性のために伸縮性を付与させる目的でも使用される。さらに最近では、紙おむつにも適用される。 As a use of the polyurethane elastic fiber of the present invention, it can be used as a fabric by processing yarn such as covering yarn such as CSY, single covering, PLY and air covering, circular knitting, tricot and the like. In addition, using these processed yarns and fabrics, products that require elasticity such as stockings, socks, underwear and swimwear, and outerwear such as jeans and suits are given elasticity for comfort. Also used for purposes. More recently, it has been applied to disposable diapers.
以下の実施例および比較例で本発明を詳細に説明するが、本発明はこれらに限定されるものではない。なお、実施例6は参考例6とする。各実施例および比較例における評価項目と評価方法は以下の通りである。 The present invention is described in detail in the following examples and comparative examples, but the present invention is not limited thereto. Example 6 is referred to as Reference Example 6. Evaluation items and evaluation methods in the examples and comparative examples are as follows.
〔スルホン酸4級アンモニウム塩溶液の調製〕
デシルベンゼンスルホン酸ナトリウム(60重量%水溶液)とジメチルジヘキシルアンモニウムクロライド(75重量%イソプロパノール溶液)をモル比率1:1で混合し、系中の水が、生成するスルホン酸4級アンモニウム塩と同重量となるようにイオン交換水を加えた。この混合溶液を90℃で1時間攪拌したあと、攪拌を停止して1時間静置し、有機層と水層とを分離させた。水層を捨て、生成するスルホン酸4級アンモニウム塩と同重量のイオン交換水を加え、90℃で15分攪拌し、1時間静置した後、水層を捨てた。さらにもう一回、同様にイオン交換水で有機層を洗浄し複製する塩化ナトリウムを0.1重量%とした。さらに140℃で3時間攪拌し、水分量が0.3重量%以下になるまで乾燥した。100℃まで冷却したあと、スルホン酸4級アンモニウム塩が30重量%となるようにDMACを加え溶液とし、室温まで冷却した(実施例1のスルホン酸4級アンモニウム塩溶液)。他の実施例に用いたスルホン酸4級アンモニウム塩についても、対応するスルホン酸ナトリウムとアンモニウムクロライドを変更する以外は同様に調製した。
[Preparation of sulfonic acid quaternary ammonium salt solution]
Sodium decylbenzenesulfonate (60% by weight aqueous solution) and dimethyldihexylammonium chloride (75% by weight isopropanol solution) were mixed at a molar ratio of 1: 1, and the water in the system was the same weight as the sulfonic acid quaternary ammonium salt produced. Ion exchange water was added so that After stirring this mixed solution at 90 ° C. for 1 hour, stirring was stopped and the mixture was allowed to stand for 1 hour to separate the organic layer and the aqueous layer. The aqueous layer was discarded, ion-exchanged water having the same weight as the sulfonic acid quaternary ammonium salt produced was added, stirred at 90 ° C. for 15 minutes, allowed to stand for 1 hour, and then the aqueous layer was discarded. Further, the organic layer was washed with ion-exchanged water in the same manner once more, and the amount of sodium chloride replicated was adjusted to 0.1% by weight. Furthermore, it stirred at 140 degreeC for 3 hours, and dried until the moisture content became 0.3 weight% or less. After cooling to 100 ° C., DMAC was added so that the sulfonic acid quaternary ammonium salt would be 30% by weight, and the solution was cooled to room temperature (the sulfonic acid quaternary ammonium salt solution of Example 1). The sulfonic acid quaternary ammonium salts used in other examples were prepared in the same manner except that the corresponding sodium sulfonate and ammonium chloride were changed.
〔紡糸原液の調製〕
数平均分子量1800のポリオキシテトラメチレングリコールとメチレン−ビス(4−フェニルイソシアナート)をモル比率1:2で反応させ、次いでプロピレンジアミンのDMAC溶液を用いて鎖延長し、ポリマー濃度27%のDMAC溶液を得た。30℃での粘度は1700mPaSであった。この溶液に、ポリマー(ポリウレタン系弾性重合体)に対して、スルホン酸4級アンモニウム塩が目的の添加量となるように、調製したスルホン酸4級アンモニウム塩溶液を添加して混合し、紡糸原液を調製した。
[Preparation of spinning dope]
A polyoxytetramethylene glycol having a number average molecular weight of 1800 and methylene-bis (4-phenylisocyanate) are reacted at a molar ratio of 1: 2, and then chain-extended using a propylenediamine in DMAC solution to form a DMAC having a polymer concentration of 27%. A solution was obtained. The viscosity at 30 ° C. was 1700 mPaS. To this solution, the prepared sulfonic acid quaternary ammonium salt solution is added to and mixed with the polymer (polyurethane-based elastic polymer) so that the sulfonic acid quaternary ammonium salt has a target addition amount. Was prepared.
〔ポリウレタンウレア弾性繊維の調製〕
上記の紡糸原液を230℃の窒素気流中に吐出して乾式紡糸した。毎分500mの速度でボビンに巻き取り44dtexモノフィラメントチーズ(巻き量400g)を得た。
[Preparation of polyurethane urea elastic fiber]
The above spinning solution was discharged into a nitrogen stream at 230 ° C. for dry spinning. A bobbin was wound at a speed of 500 m / min to obtain 44 dtex monofilament cheese (wound amount 400 g).
〔ポリウレタンウレア弾性繊維用処理剤〕
上記のポリウレタンウレア弾性繊維を乾式紡糸する際、ポリジメチルシロキサン(粘度10センチストークス)と流動パラフィン50秒を重量比7:3で混合した油剤をオイリングローラーで弾性繊維に対して5重量%となるように付着させた。
[Treatment agent for polyurethane urea elastic fiber]
When dry-spinning the above polyurethane urea elastic fiber, an oil agent obtained by mixing polydimethylsiloxane (viscosity 10 centistokes) and liquid paraffin 50 seconds at a weight ratio of 7: 3 is 5% by weight with respect to the elastic fiber by an oiling roller. It was made to adhere.
ポリウレタンウレア弾性繊維の評価方法
〔編成張力、静電気発生量〕
図2において、チーズ(3)から縦取りした弾性糸(4)をコンペンセーター(5)を経てローラー(6)、編み針(7)を介して、Uゲージ(8)に付したローラー(9)を経て速度計(10)、巻き取りローラー(11)に連結する。速度計(10)での走行速度が定速(例えば、10m/分、100m/分)になるように巻き取りローラーの回転速度を調整して、巻き取りローラーに巻き取り、そのときの編成張力をUゲージ(8)で測定し、繊維/編み針間の摩擦(g)を計測する。走行糸条より1cmのところで春日式電位差測定装置(12)で静電気発生量(kV)を測定する。
Polyurethane urea elastic fiber evaluation method (knitting tension, static electricity generation amount)
In FIG. 2, the roller (9) attached to the U gauge (8) with the elastic yarn (4) vertically taken from the cheese (3) through the compensator (5), the roller (6), and the knitting needle (7). And connected to a speedometer (10) and a take-up roller (11). The rotational speed of the take-up roller is adjusted so that the traveling speed of the speedometer (10) becomes a constant speed (for example, 10 m / min, 100 m / min), and the knitting tension at that time is taken up by the take-up roller. Is measured with a U gauge (8), and the friction (g) between the fibers / knitting needles is measured. The amount of static electricity generated (kV) is measured with a Kasuga-type potentiometer (12) at a distance of 1 cm from the running yarn.
〔繊維間摩擦係数(F/Fμs)〕
図3において、処理剤が付与された弾性繊維のモノフィラメントを50〜60cm程取り、一方の端に荷重T1(13)を吊り、ローラー(14)を介して、Uゲージ(15)にもう一方の端を掛けて定速(例えば、3cm/分)で引っ張り、そのときの2次張力T2をUゲージ(15)で測定し、下記式(1)により、繊維間摩擦係数を求める。
摩擦係数(F/Fμs=1/θ・ln(T2/T1) (1)
(式1において、θ=2π、ln=自然対数、T1は22dtex当り1g)
[Friction coefficient between fibers (F / Fμs)]
In FIG. 3, a monofilament of elastic fiber to which a treatment agent has been applied is taken about 50 to 60 cm, a load T1 (13) is suspended at one end, and the other is attached to the U gauge (15) via a roller (14). Pull the end and pull at a constant speed (for example, 3 cm / min), measure the secondary tension T2 at that time with the U gauge (15), and obtain the inter-fiber friction coefficient by the following equation (1).
Friction coefficient (F / Fμs = 1 / θ · ln (T2 / T1) (1)
(In
〔解舒速度比〕
図4において、解舒速度比測定機の解舒側に処理剤を付与した繊維のチーズ(16)をセットし、巻き取り側に紙管(17)をセットする。巻き取り速度を一定速度にセットした後、ローラー(18)および(19)を同時に起動させる。この状態では糸(20)に張力はほとんどかからないため、糸はチーズ上で膠着して離れないので、解舒点(21)は図4に示す状態にある。解舒速度を変えることによって、チーズからの糸(20)の解舒点(21)が変わるので、この点がチーズとローラーとの接点(22)と一致するように解舒速度を設定する。解舒速度比は下記式(2)によって求める。この値が小さいほど、解舒性が良いことを示す。
解舒速度比(%)=((巻取速度−解舒速度)/解舒速度)×100 (2)
[Unwinding speed ratio]
In FIG. 4, the fiber cheese (16) to which the treatment agent is applied is set on the unwinding side of the unwinding speed ratio measuring machine, and the paper tube (17) is set on the winding side. After setting the winding speed to a constant speed, the rollers (18) and (19) are activated simultaneously. In this state, there is almost no tension on the yarn (20), so the yarn is stuck on the cheese and does not leave, so the unwinding point (21) is in the state shown in FIG. By changing the unwinding speed, the unwinding point (21) of the yarn (20) from the cheese changes, so the unwinding speed is set so that this point coincides with the contact point (22) between the cheese and the roller. The unraveling speed ratio is obtained by the following equation (2). The smaller this value is, the better the unpacking property is.
Unwinding speed ratio (%) = ((winding speed−unwinding speed) / unwinding speed) × 100 (2)
〔ローラー静電気、糸上静電気〕
図1において、解舒速度比測定機の解舒側に熱処理したチーズ(1)をセットし、50m/分の周速で回転させ、巻き取り側を100m/分とし、チーズ上2cmのところにおいて、春日式電位差測定装置(2)で、回転を始めて1時間後のローラー静電気(チーズ上静電気)を測定する。ローラー静電気を測定している時の走行糸上2mmでの発生静電気(糸上静電気)を測定する。
[Roller static electricity, yarn static electricity]
In FIG. 1, the heat-treated cheese (1) is set on the unwinding side of the unwinding speed ratio measuring machine, rotated at a peripheral speed of 50 m / min, the winding side is set to 100 m / min, and the cheese is 2 cm above the cheese. Using a Kasuga-type potentiometer (2), the roller static electricity (static electricity on cheese) after 1 hour from the start of rotation is measured. Measure the static electricity generated on the running thread (static electricity on the thread) when measuring the static electricity on the roller.
〔耐塩素性の作用効果の評価方法〕
図5において、チーズより繊維を1.0gとりn−ヘキサン50mlで洗浄・乾燥後、有効塩素濃度100ppmの次亜塩素酸ナトリウム水溶液100gに浸漬し、50℃で100時間処理した。この繊維1本、20cmをUゲージ(8)に掛け、切れるまで20cm/minで引張り、破断点荷重を測定した。なお、処理前の繊維の破断点加重(強度)は51gであった。
[Method for evaluating the effect of chlorine resistance]
In FIG. 5, 1.0 g of fiber was taken from cheese, washed and dried with 50 ml of n-hexane, immersed in 100 g of an aqueous sodium hypochlorite solution having an effective chlorine concentration of 100 ppm, and treated at 50 ° C. for 100 hours. One fiber, 20 cm, was applied to a U gauge (8), pulled at 20 cm / min until it was cut, and the load at break was measured. In addition, the breaking point load (strength) of the fiber before a process was 51g.
なお、これら評価に用いたチーズは35℃、50%RHの雰囲気中で48時間処理を行ったものである。 The cheese used for these evaluations was processed for 48 hours in an atmosphere of 35 ° C. and 50% RH.
(水分量、無機塩含有量)
スルホン酸4級アンモニウム塩および比較例の制電剤の水分量と無機塩の含有量は、それぞれカールフィッシャー法とイオンクロマトグラフによって測定した。また、実施例のスルホン酸4級アンモニウム塩はDMAC溶液とする前に測定を行って確認した。
(Water content, inorganic salt content)
The water content and inorganic salt content of the sulfonic acid quaternary ammonium salt and the antistatic agent of the comparative example were measured by the Karl Fischer method and the ion chromatograph, respectively. In addition, the sulfonic acid quaternary ammonium salt of the example was confirmed by measurement before making the DMAC solution.
〔実施例1〜7および比較例1〜7〕
以下に各実施例で添加したスルホン酸4級アンモニウムおよび比較例で添加した制電剤を示す。実施例1〜7のスルホン酸4級アンモニウムについては、前述のように調製した。比較例1の制電剤については、過剰のイソプロパノールに溶解し、無機塩を析出させた後ろ過し乾燥させたものを用いた。比較例2〜5の制電剤については、過剰のイソプロパノール中で対応するスルホン酸ナトリウムとアンモニウムクロライドを反応させ、無機塩をろ過した後、乾燥させたものを用いた。比較例6については、特に精製等が必要でなかったため、そのまま用いた。
[Examples 1-7 and Comparative Examples 1-7]
The quaternary ammonium sulfonate added in each Example and the antistatic agent added in Comparative Examples are shown below. The quaternary ammonium sulfonates of Examples 1-7 were prepared as described above. About the antistatic agent of the comparative example 1, what was melt | dissolved in excess isopropanol, precipitated the inorganic salt, and then filtered and dried was used. About the antistatic agent of Comparative Examples 2-5, the corresponding sodium sulfonate and ammonium chloride were made to react in excess isopropanol, the inorganic salt was filtered, and the dried thing was used. Comparative Example 6 was used as it was because no purification or the like was required.
実施例1〜7については、前述のように、スルホン酸4級アンモニウム塩溶液、紡糸原液を調製し、ポリウレタンウレア弾性繊維を得た。また、比較例1〜6については、スルホン酸4級アンモニウム塩溶液を添加する代わりに、各比較例の制電剤を添加して紡糸原液を調製する以外は、実施例1と同様にして、ポリウレタンウレア弾性繊維を得た。比較例7については、制電剤を含まない紡糸原液を調製する以外は実施例1と同様にして、ポリウレタンウレア弾性繊維を得た。得られたポリウレタンウレア弾性繊維を上記方法により評価した。その評価結果および添加したスルホン酸4級アンモニウム・制電剤の水分量と無機塩含有量を表1、2に示す。
なお、実施例、比較例ともに、ポリマーに対して3重量%となるよう、スルホン酸4級アンモニウムまたは制電剤を添加して紡糸原液を調製した。
実施例1:ジメチルジヘキシルアンモニウムデシルベンゼンスルホネート
実施例2:ジメチルジオクチルアンモニウムドデシルスルホネート
実施例3:ジメチルジドデシルアンモニウムドデシルベンゼンスルホネート
実施例4:ジメチルジドデシルアンモニウムドデシルスルホネート
実施例5:ジメチルジオレイルアンモニウムドデシルベンゼンスルホネート
実施例6:ジエタノールジドデシルアンモニウムドデシルベンゼンスルホネート
実施例7:トリメチルドデシルアンモニウムドデシルベンゼンスルホネート
比較例1:ドデシルベンゼンスルホン酸ナトリウム
比較例2:ドデシルアンモニウムドデシルスルホネート
比較例3:メチルドデシルアンモニウムドデシルスルホネート
比較例4:ジメチルドデシルアンモニウムベンゼンスルホネート
比較例5:トリオクチルメチルアンモニウムトルエンスルホネート
比較例6:酸化亜鉛
比較例7:無添加
About Examples 1-7, as mentioned above, the sulfonic acid quaternary ammonium salt solution and the spinning dope were prepared, and the polyurethane urea elastic fiber was obtained. For Comparative Examples 1 to 6, instead of adding the sulfonic acid quaternary ammonium salt solution, except for adding the antistatic agent of each Comparative Example to prepare the spinning dope, the same as in Example 1, A polyurethaneurea elastic fiber was obtained. For Comparative Example 7, a polyurethaneurea elastic fiber was obtained in the same manner as in Example 1 except that a spinning stock solution containing no antistatic agent was prepared. The obtained polyurethane urea elastic fiber was evaluated by the above method. Tables 1 and 2 show the evaluation results and the water content and inorganic salt content of the added quaternary ammonium sulfonate / antistatic agent.
In both Examples and Comparative Examples, a spinning stock solution was prepared by adding quaternary ammonium sulfonate or antistatic agent so as to be 3% by weight based on the polymer.
Example 1: Dimethyldihexylammonium decylbenzenesulfonate Example 2: Dimethyldioctylammonium dodecyl sulfonate Example 3: Dimethyldidecylammonium dodecylbenzene sulfonate Example 4: Dimethyldidecylammonium dodecyl sulfonate Example 5: Dimethyldioleylammonium dodecylbenzene Sulfonate Example 6: Diethanol didodecyl ammonium dodecyl benzene sulfonate Example 7: Trimethyl dodecyl ammonium dodecyl benzene sulfonate Comparative example 1: Sodium dodecyl benzene sulfonate Comparative example 2: Dodecyl ammonium dodecyl sulfonate Comparative example 3: Methyl dodecyl ammonium dodecyl sulfonate Comparative example 4: Dimethyldodecyl ammonium benzene Sulfonate Comparative Example 5: Trioctylmethylammonium toluene sulfonate Comparative Example 6: Zinc oxide Comparative Example 7: No addition
〔実施例8〜12〕
実施例3で使用したスルホン酸4級アンモニウム塩において、ポリマーに対して0.1〜5重量%の範囲で添加量を検討した。なお、試料糸は紡糸原液に添加するスルホン酸4級アンモニウム塩溶液の量を調節したのみで、実施例3と同様に作成した。評価結果を表3に示す。
[Examples 8 to 12]
In the sulfonic acid quaternary ammonium salt used in Example 3, the addition amount was examined in the range of 0.1 to 5% by weight with respect to the polymer. The sample yarn was prepared in the same manner as in Example 3 only by adjusting the amount of the sulfonic acid quaternary ammonium salt solution added to the spinning dope. The evaluation results are shown in Table 3.
表1、2に示すように、比較例1〜5のスルホン酸塩は、繊維のポリマーと相溶性が悪くなり、実施例のスルホン酸4級アンモニウム塩よりも制電性が悪化している。比較例6の無機系添加剤では、制電性には殆ど効果がない。また、表3に示すように、添加量は1〜3重量%が最適である。実施例のスルホン酸4級アンモニウム塩を添加することで、ポリウレタン系弾性繊維に制電性と耐塩素性を付与できることがわかる。 As shown in Tables 1 and 2, the sulfonates of Comparative Examples 1 to 5 have poor compatibility with the fiber polymer, and the antistatic properties are worse than those of the sulfonic acid quaternary ammonium salts of Examples. The inorganic additive of Comparative Example 6 has little effect on antistatic properties. As shown in Table 3, the addition amount is optimally 1 to 3% by weight. It can be seen that antistatic properties and chlorine resistance can be imparted to the polyurethane elastic fiber by adding the sulfonic acid quaternary ammonium salt of the example.
本発明により、制電性、生産性、耐塩素性等が改善されたポリウレタン系弾性繊維を提供することができる。 According to the present invention, it is possible to provide a polyurethane-based elastic fiber having improved antistatic properties, productivity, chlorine resistance and the like.
1 弾性繊維のチーズ
2 春日式電位差測定装置
3 弾性繊維のチーズ
4 弾性糸
5 コンペンセーター
6 ローラー
7 編み針
8 Uゲージ
9 ローラー
10 速度計
11 巻き取りローラー
12 春日式電位差測定装置
13 荷重
14 ローラー
15 Uゲージ
16 チーズ
17 巻き取り用紙管
18 ローラー
19 ローラー
20 走行糸条
21 解舒点
22 チーズとローラーの接点
DESCRIPTION OF
Claims (7)
前記スルホン酸4級アンモニウム塩が、下記一般式(1)で示される化合物であり、前記ポリウレタン系弾性重合体に対して0.01〜10重量%含まれる、ポリウレタン系弾性繊維。
A polyurethane-based elastic fiber, wherein the sulfonic acid quaternary ammonium salt is a compound represented by the following general formula (1) and is contained in an amount of 0.01 to 10% by weight based on the polyurethane-based elastic polymer.
前記ポリウレタン系弾性重合体および前記スルホン酸4級アンモニウム塩を含む紡糸原液を調製し、該紡糸原液を紡糸する、ポリウレタン系弾性繊維の製造方法。 It is a manufacturing method of the polyurethane-type elastic fiber in any one of Claims 1-4, Comprising:
A method for producing a polyurethane elastic fiber, comprising preparing a spinning stock solution containing the polyurethane elastic polymer and the sulfonic acid quaternary ammonium salt, and spinning the spinning stock solution.
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |