JP6425410B2 - Polyurethane elastic fiber and method for producing the same - Google Patents
Polyurethane elastic fiber and method for producing the same Download PDFInfo
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- JP6425410B2 JP6425410B2 JP2014089283A JP2014089283A JP6425410B2 JP 6425410 B2 JP6425410 B2 JP 6425410B2 JP 2014089283 A JP2014089283 A JP 2014089283A JP 2014089283 A JP2014089283 A JP 2014089283A JP 6425410 B2 JP6425410 B2 JP 6425410B2
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- 229920002635 polyurethane Polymers 0.000 title claims description 88
- 239000004814 polyurethane Substances 0.000 title claims description 88
- 210000004177 elastic tissue Anatomy 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 70
- 239000002184 metal Substances 0.000 claims description 70
- 238000009987 spinning Methods 0.000 claims description 68
- 150000003839 salts Chemical class 0.000 claims description 59
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 50
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 26
- 229940114069 12-hydroxystearate Drugs 0.000 claims description 21
- 150000001408 amides Chemical class 0.000 claims description 19
- 239000011550 stock solution Substances 0.000 claims description 18
- 238000004804 winding Methods 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 15
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000000578 dry spinning Methods 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- -1 hydrotalcite compound Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229920006306 polyurethane fiber Polymers 0.000 claims description 2
- 239000004744 fabric Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 239000006185 dispersion Substances 0.000 description 18
- 238000009940 knitting Methods 0.000 description 18
- 239000000835 fiber Substances 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
- 239000000194 fatty acid Substances 0.000 description 13
- 229930195729 fatty acid Natural products 0.000 description 13
- 150000004665 fatty acids Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 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 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VIALJPAGUCTUBQ-UHFFFAOYSA-L magnesium;12-hydroxyoctadecanoate Chemical compound [Mg+2].CCCCCCC(O)CCCCCCCCCCC([O-])=O.CCCCCCC(O)CCCCCCCCCCC([O-])=O VIALJPAGUCTUBQ-UHFFFAOYSA-L 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008041 oiling agent Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241001589086 Bellapiscis medius Species 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000010296 bead milling Methods 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [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
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000515 huntite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
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- 239000002905 metal composite material Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 210000003205 muscle Anatomy 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Description
本発明は、１２−ヒドロキシステアリン酸金属塩及び無機固形物を用いることにより、紡糸時の安定生産性、フィラメントの合着性、紙管からの解除性、対金属摩擦性等を改良したポリウレタン弾性繊維及びその製造方法に関するものである。更に詳しくは、ポリウレタン弾性繊維の細糸の高速紡糸安定性や繊維表面の摩擦特性が改善され、整経、製織、製編み工程での対金属摩擦が良好で、糸切れや摩擦応力変動も少なく、その結果、商品価値の良好な生地表面品位が得ることができるポリウレタン弾性繊維およびその製造方法に関する。 The present invention is a polyurethane elasticity improved in stable production during spinning, filament cohesion, release from a paper tube, friction with metal, etc. by using 12-hydroxystearate metal salt and inorganic solid. The present invention relates to a fiber and a method of manufacturing the same. More specifically, the high-speed spinning stability of fine fibers of polyurethane elastic fiber and the friction characteristics of the fiber surface are improved, the metal-to-metal friction in the warping, weaving, and knitting processes is good, and yarn breakage and friction stress fluctuation are small. The present invention relates to a polyurethane elastic fiber capable of obtaining a good fabric surface quality as a result, and a method for producing the same.
４，４’−ジフェニルメタンジイソシアネート、ポリヒドロキシ重合体および多官能活性水素含有化合物から得られるポリウレタン弾性繊維は、高度のゴム弾性を有し、引張応力、回復性等の機械的性質に優れ、さらに熱的挙動についても優れた性質を有するために、紙おむつ、ファンデーション、レッグ、スポーツウェア、医療用繊維資材等の商品に広汎に使用されている。
近年、生地の薄手化要求と生産コスト低減要求のために、単糸が５〜２０デシテックスの細糸を１０００ｍ/分以上の高速で安定的に紡糸をするポリウレタン弾性繊維の技術開発が進められている。
Polyurethane elastic fibers obtained from 4,4'-diphenylmethane diisocyanate, polyhydroxy polymers and polyfunctional active hydrogen-containing compounds have a high degree of rubber elasticity, excellent mechanical properties such as tensile stress, recoverability, and heat It is widely used in products such as disposable diapers, foundations, legs, sportswear, medical textile materials and the like because it also has excellent properties with regard to its behavioral behavior.
In recent years, technological development of polyurethane elastic fiber that stably spins thin yarn of 5 to 20 dtex per single yarn at a high speed of 1000 m / min or more is advanced for the demand for thinning of fabric and the demand for reduction of production cost There is.
ポリウレタン弾性繊維は、優れた弾性特性を有してはいるが、耐光性、染色性、耐塩素性、摩擦特性等の性能が充分でなく、その改善のために、酸化チタン、ハイドロタルサイト類、ハンタイト類等の多くの無機固形物が用いられている。しかし、これらの無機固形物は、ポリウレタン重合体やアミド系溶剤に対する親和性が乏しく、原液配管中や紡口口金内部で粒子同士が凝集しやすく、フィルターや紡口孔を閉塞し、フィルター詰まりや、糸キレを起こしやすく、高速での長期の安定生産が困難であった。そこで、無機固形物の表面を高級脂肪酸でのコーティングする方法（下記特許文献１参照）や、比表面積（ＢＥＴ値）を改善することが提案されている（下記特許文献２参照）。しかし、１０００ｍ／分以上の細糸の高速紡糸の安定生産には未だ十分でなかった。
Polyurethane elastic fibers, although having excellent elastic properties, do not have sufficient properties such as light resistance, dyeability, chlorine resistance, and friction properties, and titanium oxide and hydrotalcites for their improvement Many inorganic solids such as huntite are used. However, these inorganic solids have poor affinity to polyurethane polymers and amide solvents, particles tend to aggregate in the stock solution piping and inside the spinneret, clog the filters and pores, and clog the filters.糸, 起 こ し 糸 、 生産 生産 生産 生産 生産 生産 た や す く, 、 や す く 、 や す く や す く や す く や す く や す く 起 こ し キ キ や す く や す く や す く や す く キ キ や す く や す く キ や す く 起 こ し キ, easy to cause yarn squeeze, long-term stable production at high speed was difficult. Therefore, a method of coating the surface of the inorganic solid with a higher fatty acid (see
更にまた、ポリウレタン弾性繊維自体が、粘着性があり、かつ、柔軟なゴム糸状の性質を有するので、巻きとられた糸の紙管内層部からの解除不良や、更には、整経機の筬や編成編み機の編み針との金属摩擦性も悪く、摩擦変動幅も大きい為、加工特性が劣り、出来上がった生地は、表面品位が不均一になりやすく、商品価値が低下する問題があった。 Furthermore, since the polyurethane elastic fiber itself is sticky and has a soft rubber thread-like property, the release failure of the wound yarn from the inner layer portion of the paper, and further, the wrinkles of the warper. Also, the metal friction with the knitting needles of the knitting machine is poor, and the fluctuation range of the friction is large, so the processing characteristics are inferior, and the finished fabric tends to be uneven in surface quality, and there is a problem that the commercial value decreases.
これに関して、金属石鹸とシリコーン及び変性シリコーンの配合剤をポリウレタン重合体溶液に、紡糸前に添加する試みも提案されている（下記特許文献３および４参照）。しかし、この場合も前述した無機固形物と同様に、金属石鹸もシリコーンもポリウレタン重合体やそのアミド系溶剤に対する親和性が乏しい為に、ポリマー原液中で経時的に凝集や分離が起こりやすく、それにより紡糸時の糸キレや、添加した金属石鹸やシリコーンが紡糸塔内で繊維表面にブリードし、合着性が低下したり、繊維表面のシリコーンにより糸と糸が滑りやすく、紙管糸巻の形状が型崩れし、商品価値を低下させる問題があった。
In this regard, it has also been proposed to add a combination of metal soap and silicone and modified silicone to the polyurethane polymer solution prior to spinning (see
また別の方法として、ポリウレタン弾性糸の摩擦性改善に関して、糸表面に不純物を限定したステアリン酸金属塩とシリコーン分散媒体とを一体化して紡糸後に、巻き取り工程で繊維の油剤処理剤として付着させる事も提案されている（下記特許文献５参照）。しかしながら、この場合、シリコーンに分散したステアリン酸金属塩であっても、ポリウレタン重合体との親和性が乏しい為、繊維表面で偏在化したり、スカムを発生したりして、安定した摩擦性能が充分でないポリウレタン弾性繊維となる問題があった。 As another method, in order to improve the frictional property of the polyurethane elastic yarn, the metal salt of stearic acid and the silicone dispersion medium having impurities limited on the yarn surface are integrated and spun and then attached as an oiling agent for fibers in the winding process. The thing is also proposed (refer the following patent document 5). However, in this case, even if it is a metal salt of stearic acid dispersed in silicone, its affinity to the polyurethane polymer is poor, so localized distribution on the fiber surface and scum are generated, and a stable friction performance is sufficient. There is a problem of not becoming polyurethane elastic fiber.
すなわち、無機固形物やステアリン酸金属塩は、ポリウレタン弾性繊維の製造に多用されている機能剤ではあるが、いずれも、ポリウレタン重合体やそのアミド系溶剤に対する親和性に乏しく、さらに、近年、細糸の１０００ｍ／分以上の高速生産に対応するために、無機固形物の微粒子化したものが用いられるため、その微粒子は、原液配管中や紡口口金内部で再凝集しやすく、フィルター詰まりや糸キレを頻発する原因となり、細糸の高速安定生産には十分対応できていなかった。 That is, although inorganic solids and metal salts of stearic acid are functional agents frequently used for producing polyurethane elastic fibers, all have poor affinity to polyurethane polymers and their amide solvents, and in recent years, they are fine. Since fine particles of inorganic solid are used to cope with high-speed production of 1000 m / min or more of yarn, the fine particles are easily reaggregated in the stock solution piping or inside the spinneret, and filter clogging and yarn are caused. It has been a cause of frequent squeezing and has not been able to cope with high-speed stable production of fine yarn.
本発明の課題は、無機固形物を含むポリウレタン重合体を用いて弾性繊維の細糸を高速紡糸するにあたって、無機固形物の凝集を抑制し、長期に渡って高速紡糸での安定な紡糸ができ、かつ、加工特性に優れ、生地品位が良好なポリウレタン弾性繊維を提供することである。 It is an object of the present invention to suppress aggregation of inorganic solids and achieve stable spinning in high-speed spinning over a long period of time in spinning fine threads of elastic fibers using polyurethane polymers containing inorganic solids. Also, it is to provide a polyurethane elastic fiber which is excellent in processing characteristics and good in fabric quality.
本発明者らは、無機固形物を含むポリウレタン弾性繊維の細糸を高速紡糸するにあたって、長期に安定生産を可能にし、フィラメント間の合着性が良好で、得られたポリウレタン弾性繊維表面が優れた対金属摩擦特性を有し、その結果、出来上がった生地の品位に優れた商品価値の高いポリウレタン弾性繊維を得る目的で、鋭意検討を行い、本発明に至った。 The present inventors have made stable production possible for long-term stable spinning of fine filaments of polyurethane elastic fibers containing inorganic solids at a high speed, the adhesion between filaments is good, and the surface of the obtained polyurethane elastic fibers is excellent. In order to obtain polyurethane elastic fibers of high commercial value having excellent metal-to-metal friction characteristics and as a result, excellent quality of finished fabrics, the present inventors have made extensive studies.
すなわち、ポリウレタン重合体、無機固形物、アミド系溶剤のいずれに対しても親和性の良好な１２−ヒドロキシステアリン酸金属塩を無機固形物と併用した場合、驚くべきことに、紡糸原液中の各々の物質の詰まりの問題が解決でき、その結果、細糸の高速紡糸の生産を長期に安定できることが分かった。更に、得られたポリウレタン弾性繊維は、優れた対金属摩擦特性を有すると共に、単糸フィラメント同士の合着が良好なため、マルチフィラメントの糸割れに起因する加工時の糸キレも減少し、出来上がった生地の品位は、各々単独で用いる場合に比較して、格段に向上し商品価値を極めて高める事が出来た。 That is, when a metal salt of 12-hydroxystearate having good affinity to any of polyurethane polymer, inorganic solid and amide solvent is used in combination with inorganic solid, it is surprising that each in the spinning stock solution It has been found that the problem of material clogging can be solved, and as a result, the production of high speed spinning of fine yarn can be stabilized for a long time. Furthermore, the obtained polyurethane elastic fiber has excellent metal-to-metal friction characteristics and good bonding between single yarn filaments, thereby reducing yarn shrinkage during processing due to multifilament yarn breakage, resulting in a finished product. The quality of the dough can be significantly improved and the commercial value can be extremely enhanced as compared to the case where each is used alone.
更に詳しくは、１２−ヒドロキシステアリン酸金属塩及び無機固形物を併用した場合、無機固形物の微粒子がアミド系溶媒中で再凝集して、フィルターや紡口ノズルでつまりの原因となる大きな粒子となることを抑制できることが分かった。このことにより、工程中のフィルター詰まりと紡口ノズル中の詰まりを改善でき、高速紡糸時の糸切れ抑制効果と同時に、ポリウレタン弾性繊維の対金属摩擦性も向上することが分かった。その結果、得られたポリウレタン弾性繊維を用いて生地を製造した場合、生地の表面品位は均一であり、商品価値の高い生地が得られ本発明に到達した。
すなわち本発明は、以下のとおりである。
More specifically, when a metal salt of 12-hydroxystearate and an inorganic solid are used in combination, fine particles of the inorganic solid reaggregate in an amide solvent to cause large particles that cause clogging in a filter or a spinning nozzle. Was found to be able to suppress It has been found that this makes it possible to improve filter clogging in the process and clogging in the spinning nozzle, and at the same time the yarn breakage suppressing effect at the time of high speed spinning also improves the metal abrasion resistance of polyurethane elastic fiber. As a result, when a fabric was manufactured using the obtained polyurethane elastic fiber, the surface quality of the fabric was uniform, and a high commercial value fabric was obtained, reaching the present invention.
That is, the present invention is as follows.
（１）ポリウレタン重合体１００重量部に対して、平均粒子径が１μｍより大きく２０μｍ以下である１２−ヒドロキシステアリン酸金属塩０．００１〜５重量部、並びに平均粒径が０．１〜２０μｍの酸化チタン、ハイドロタルサイト類化合物、及び二酸化ケイ素と酸化亜鉛の複合塩からなる群から選ばれる化合物である無機固形物０．００１〜１０重量部有することを特徴とするポリウレタン弾性繊維。
（２）前記１２−ヒドロキシステアリン酸金属塩を構成する金属がマグネシウム、カルシウム、アルミニウム、及び亜鉛からなる群から選ばれる、前記（１）に記載のポリウレタン弾性繊維。
（３）前記１２−ヒドロキシステアリン酸金属塩及び無機固形物の合計量が、ポリウレタン重合体１００重量部に対して０．００２〜１０重量部である、前記（１）又は（２）に記載のポリウレタン弾性繊維。
（４）単糸デシテックスが５〜２０である、請求項１〜３のいずれかに記載のポリウレタン弾性繊維。
（５）ポリウレタン重合体、平均粒径が０．１〜２０μｍの酸化チタン、ハイドロタルサイト類化合物、及び二酸化ケイ素と酸化亜鉛の複合塩からなる群から選ばれる化合物である無機固形物、並びに平均粒子径が１μｍより大きく２０μｍ以下である１２−ヒドロキシステアリン酸金属塩をアミド系溶剤に溶解及び混合して紡糸原液を作製する工程、得られた紡糸原液を乾式紡糸法で紡糸する工程、並びに得られた糸を巻き取る工程からなる、前記（１）〜（４）のいずれかに記載のポリウレタン弾性繊維の製造方法。
（６）ポリウレタン重合体、平均粒径が０．１〜２０μｍの酸化チタン、ハイドロタルサイト類化合物、及び二酸化ケイ素と酸化亜鉛の複合塩からなる群から選ばれる化合物である無機固形物、並びに平均粒子径が１μｍより大きく２０μｍ以下である１２−ヒドロキシステアリン酸金属塩をアミド系溶剤に溶解及び混合して紡糸原液を作製する工程、得られた紡糸原液を乾式紡糸法で紡糸する工程、１２−ヒドロキシステアリン酸金属塩が含有された油剤を得られた糸に付着する工程、並びに付着後の糸を巻き取る工程からなる、前記（１）〜（４）のいずれかに記載のポリウレタン弾性繊維の製造方法。
(1) 0.001 to 5 parts by weight of 12-hydroxystearic acid metal salt having an average particle diameter of more than 1 μm and not more than 20 μm and 100 to 20 parts of polyurethane polymer with an average particle diameter of 0.1 to 20 μm An elastic polyurethane fiber comprising 0.001 to 10 parts by weight of an inorganic solid, which is a compound selected from the group consisting of titanium oxide, a hydrotalcite compound and a complex salt of silicon dioxide and zinc oxide .
(2) the metal constituting the 12-hydroxystearic acid metal salt is magnesium, calcium, selected aluminum, and from the group consisting of zinc, polyurethane elastic fibers according to (1).
(3) the total amount of said 12-hydroxystearic acid metal salt and inorganic solids, is 0.002 to 10 parts by weight based on the polyurethane polymer 100 parts by weight, according to (1) or (2) Polyurethane elastic fiber.
(4) The polyurethane elastic fiber according to any one of
(5) Inorganic solid which is a compound selected from the group consisting of polyurethane polymers, titanium oxide having an average particle diameter of 0.1 to 20 μm, hydrotalcites compounds, and complex salts of silicon dioxide and zinc oxide, and averages step having a particle diameter to prepare a spinning solution dissolved and mixed and the larger than 20μm amide solvent of 12-hydroxystearic acid metal salt is below 1 [mu] m, the step of spinning a spinning solution obtained by the dry spinning method, and obtained was composed of a step of winding the yarn, the (1) to (4) noise Re method for producing polyurethane elastic fiber according to any.
(6) polyurethane polymer, titanium oxide having an average particle diameter of 0.1 to 20 μm, inorganic compound which is a compound selected from the group consisting of hydrotalcites compounds and complex salts of silicon dioxide and zinc oxide, and average A step of dissolving and mixing a metal salt of 12-hydroxystearate having a particle size of more than 1 μm and not more than 20 μm in an amide solvent to prepare a spinning stock solution, a step of spinning the obtained spinning stock solution by dry spinning, depositing a yarn obtained hydroxystearic acid metal salt is contained oil, and the yarn comprises the step of winding the subsequent deposition, the (1) to (4) noise Re polyurethane elastic according to either How to make fiber.
本発明の１２−ヒドロキシステアリン酸金属塩及び無機固形物を有するポリウレタン弾性繊維は、工程中や紡口ノズルでの再凝集が抑制されている為、細糸を高速紡糸するに際して、長期に安定な紡糸ができ、かつ、得られた該ポリウレタン弾性繊維は、生地作成工程での、紙管内層部からの糸の解除もスムーズで、対金属摩擦特性も優れ、更にフィラメント割れによる糸キレも少ないため、出来上がった生地は品位良好で商品価値が高い。 The polyurethane elastic fiber having the metal salt of 12-hydroxystearate and the inorganic solid of the present invention has long-term stability in high-speed spinning of fine yarn because reaggregation in the process and at the spinning nozzle is suppressed. The polyurethane elastic fiber which can be spun and obtained has smooth release of the yarn from the inner layer of the paper in the step of forming the fabric, is excellent in friction characteristics against metal, and is less in yarn shrinkage due to filament cracking. The finished fabric is of good quality and has high commercial value.
本発明について、以下詳細に説明する。
本発明のポリウレタン弾性繊維は、ポリウレタン重合体１００重量部に対して、１２−ヒドロキシステアリン酸金属塩０．００１〜５重量部及び無機固形物０．００１〜１０重量部有することを特徴とする。
The present invention will be described in detail below.
The polyurethane elastic fiber of the present invention is characterized by having 0.001 to 5 parts by weight of metal 12-hydroxystearate and 0.001 to 10 parts by weight of inorganic solid with respect to 100 parts by weight of the polyurethane polymer.
本発明で用いる１２−ヒドロキシステアリン金属塩の効果は、その化学構造中に１つの水酸基を有する為、ステアリル基の親油性と水酸基の親水性とを併せ持つところに由来すると考える。すなわち、１２−ヒドロキシステアリル金属塩は、従来から多用されているステアリン酸金属塩に比較して、ポリウレタン重合体及びアミド系溶剤のいずれに対しても親和性が向上し、さらに、親水性のある無機固形物に対しても親和性を有する。よって、本発明に用いる１２−ヒドロキシステアリン酸金属塩は、ポリウレタン、アミド系溶剤、無機固形物のいずれに対しても、親和性を有し、自らもその系内において安定であり、且つ、ポリウレタン重合体のアミド系溶液中での無機固形物の凝集を抑制する分散剤的役割の特性を有すると考える。 The effect of the 12-hydroxystearin metal salt used in the present invention is considered to be derived from having both the lipophilicity of the stearyl group and the hydrophilicity of the hydroxyl group, since it has one hydroxyl group in its chemical structure. That is, 12-hydroxystearyl metal salt has improved affinity to both polyurethane polymer and amide solvents and is more hydrophilic than stearic acid metal salt which has been widely used conventionally. It also has an affinity to inorganic solids. Therefore, the metal salt of 12-hydroxystearate used in the present invention has an affinity to any of polyurethane, amide solvents and inorganic solid substances, and is itself stable in the system, and polyurethane It is considered to have the property of a dispersing agent role to suppress the aggregation of inorganic solids in an amide solution of a polymer.
１２−ヒドロキシステアリン酸金属塩を構成する金属は、マグネシウム、カルシウム、アルミニウムおよび亜鉛からなる群から選ばれることが好ましい。さらに好ましくは、マグネシウムおよびカルシウムである。１２−ヒドロキシステアリン金属塩の配合量は、ポリウレタン重合体１００重量部に対して、０．００１〜５重量部であり、０．００１重量部未満では効果が充分に発揮できない。５重量部を超えても、効果が飽和し経済的でない。さらに好ましくは、０．００５〜３重量部である。 The metal constituting the 12-hydroxystearate metal salt is preferably selected from the group consisting of magnesium, calcium, aluminum and zinc. More preferably, they are magnesium and calcium. The compounding amount of the 12-hydroxy stearin metal salt is 0.001 to 5 parts by weight with respect to 100 parts by weight of the polyurethane polymer, and if less than 0.001 part by weight, the effect can not be sufficiently exhibited. Even if it exceeds 5 parts by weight, the effect is saturated and it is not economical. More preferably, it is 0.005 to 3 parts by weight.
本発明で用いる無機固形物は、酸化チタン、酸化亜鉛、酸化亜鉛とシリカの金属複合塩、酸化亜鉛とシリカとアルミナの複合塩、酸化マグネシウムとシリカとアルミナの複合塩、酸化マグネシウムと酸化亜鉛とシリカとアルミナの複合塩、ハイドロタルサイト類化合物、フンタイト類化合物、ＭｇＯとＺｎＯの固溶体、二酸化ケイ素と酸化亜鉛の複合塩、多孔質性合成シリカ、カーボンブラック、着色剤顔料の群から選ばれた化合物が好ましい。これらの無機固形物の内で、Ｔｉ，Ｓｉ、Ｍｇ、Ａｌ、Ｚｎ等の元素を１つ又は２つ以上含む無機固形物がさらに好ましく、特に好ましくは、酸化チタン、酸化亜鉛、ハイドロタルサイト類、フンタイト類、酸化亜鉛とシリカの金属複合塩、酸化亜鉛とシリカとアルミナの複合塩である。 The inorganic solid used in the present invention includes titanium oxide, zinc oxide, metal composite salt of zinc oxide and silica, composite salt of zinc oxide, silica and alumina, composite salt of magnesium oxide, silica and alumina, magnesium oxide and zinc oxide, Composite salts of silica and alumina, hydrotalcite compounds, huntite compounds, solid solutions of MgO and ZnO, composite salts of silicon dioxide and zinc oxide, porous synthetic silica, carbon black, selected from the group of colorant pigments Compounds are preferred. Among these inorganic solids, inorganic solids containing one or more elements such as Ti, Si, Mg, Al, Zn, etc. are more preferable, and particularly preferably titanium oxide, zinc oxide, hydrotalcites , Huntites, metal complex salts of zinc oxide and silica, complex salts of zinc oxide, silica and alumina.
無機固形物の量はポリウレタン重合体１００重量部に対して０．００１〜１０重量部である。０．００１重量部未満であると効果が充分でなく、１０重量部を超えると弾性回復性が低下する。好ましい無機固形物の量は、０．０１〜８重量部である。
また、無機固形物の平均粒径の好ましい範囲は０．１〜２０μｍであり、０．１μｍ未満であると再凝集を起こしやすく、２０μｍより大きければ、フィルターや紡口ノズルでの詰りによって高速紡糸時に糸キレを起こしやすい。
The amount of inorganic solid is 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyurethane polymer. When the amount is less than 0.001 part by weight, the effect is not sufficient. When the amount is more than 10 parts by weight, the elastic recovery is reduced. The preferred amount of inorganic solids is 0.01 to 8 parts by weight.
In addition, the preferable range of the average particle diameter of the inorganic solid is 0.1 to 20 μm, reaggregation is easily caused if it is less than 0.1 μm, and if it is more than 20 μm, high-speed spinning is caused by clogging in a filter or spinning nozzle. Sometimes it is easy to cause yarn squeezing.
１２−ヒドロキシステアリン酸金属塩と無機固形物は、紡糸前のポリマー原液中に適当な段階で個別又は同時に加えることができる。１２−ヒドロキシステアリン酸金属塩と無機固形物とを一体として分散混合し、又は、各々別々に溶剤中で分散した後に混合し、紡糸前のポリマー原液中に適当な段階で同時に加えてもよい。ここで分散又は微粒子化するために湿式粉砕に用いる粉砕機としては、縦型ビーズミル、横型ビーズミル、サンドグラインダー、コロイドミル、ボールミル等の各種の湿式粉砕機を使用できる。又、１２−ヒドロキシステアリン酸金属塩は、アミド系溶剤との親和性が良好であるため、ホモミキサーやラインミキサー等を用いて微分散することも可能である。分散の際に使用できる温度は、１０〜１１０℃である。１２−ヒドロキシステアリン酸金属塩を、約９０℃で、アミド系溶剤に均一溶解した状態でホモミキサーやラインミキサーで高速撹拌分散してもよい。こうして得られた分散液は、スタティックミキサー等用いて、紡糸原液ポリマー中に均一に添加し、混合することができる。 The 12-hydroxystearate metal salt and the inorganic solid can be added separately or simultaneously at an appropriate stage to the polymer stock solution before spinning. The 12-hydroxystearate metal salt and the inorganic solid may be dispersed and mixed together, or may be separately dispersed in a solvent and then mixed, and simultaneously added to the polymer stock solution before spinning at an appropriate stage. Here, as a grinder used for wet grinding in order to disperse or micronize, various wet grinders such as a vertical bead mill, a horizontal bead mill, a sand grinder, a colloid mill, a ball mill and the like can be used. Further, since the metal salt of 12-hydroxystearic acid has a good affinity to an amide solvent, it can be finely dispersed using a homomixer, a line mixer or the like. The temperature which can be used at the time of dispersion | distribution is 10-110 degreeC. The metal salt of 12-hydroxystearic acid may be dispersed at high speed with a homomixer or line mixer in a state of being uniformly dissolved in an amide solvent at about 90 ° C. The dispersion obtained in this manner can be uniformly added to and mixed with the spinning stock solution polymer using a static mixer or the like.
本発明の１２−ヒドロキシステアリン酸金属塩の好ましい粒径は、アミド系溶剤中、例えばジメチルアセトアミド中での測定で、平均粒子径が１μｍより大きく２０μｍ以下が好ましい。
平均粒径が１μｍ以下の微粒子は、再凝集し易く、アミド系溶剤中で大きな粒子に成長する為、フィルターや紡口で詰まりを起こしやすい。２０μｍより大きな粒子の物は、細糸の高速紡糸を行う際に、工程でのフィルター詰まりや糸キレを起こしやすい。好ましい平均粒子径は１．５μｍ以上１０μｍ以下である。
The preferable particle size of the metal salt of 12-hydroxystearate of the present invention is preferably not less than 1 μm and not more than 20 μm in average particle size as measured in an amide solvent, for example, dimethylacetamide.
Fine particles having an average particle size of 1 μm or less tend to reaggregate and grow into large particles in an amide solvent, so that they are easily clogged with a filter or a spinneret. Particles larger than 20 μm tend to cause clogging of the filter in the process and yarn squeezing during high speed spinning of fine yarns. The preferred average particle size is 1.5 μm to 10 μm.
又、１２−ヒドロキシステアリン酸を無機固形物と一体化して混合、粉砕した場合、１２−ヒドロキシステアリン酸金属塩が無機固形物の表面上に一部分がコートされる場合もあるが、その場合でも本発明に述べる優れた効果を発揮する。又、１２−ヒドロキシステアリン酸金属塩は、前記の様に紡糸前のポリマー原液に混合して用いてもよいし、又は、紡糸筒内のノズルから出た糸が、紙管に巻きとる前に用いられるシリコーン油剤中の成分の一つとして用いて、繊維表面に付着させてもよい。この場合でも、１２−ヒドロキシステアリン酸金属塩の場合は、ポリウレタン重合体との親和性が良好であるため繊維表面に均一に分散存在する。その為、摩擦性は良好で、摩擦応力変動の小さい効果が発揮される。本発明において、ポリウレタン弾性繊維が１２−ヒドロキシステアリン酸金属塩を有するとは、１２−ヒドロキシステアリン酸金属塩が、ポリウレタン重合体に紡糸前に添加されたのち、紡糸され、ポリウレタン弾性繊維の内部及び内部から繊維表面に移行して存在するもの、または油剤の一成分として紡糸後に紙管に巻きとられる前に付着されて存在するものも含むことを意味する。前述の効果を発現させるために、ポリウレタン弾性繊維が有する１２−ヒドロキシステアリン酸の少なくとも一部が、紡糸前のポリウレタン重合体溶液に添加されたものであることが好ましい。 In addition, when 12-hydroxystearic acid is mixed with inorganic solids, mixed and pulverized, the 12-hydroxystearate metal salt may be partially coated on the surface of the inorganic solids, but even in such a case, It exerts the excellent effects described in the invention. Also, the metal salt of 12-hydroxystearic acid may be used by being mixed with the undiluted polymer solution as described above, or the yarn from the nozzle in the spinning cylinder may be wound before it is wound into a paper tube. It may be used as one of the components in the silicone oil used and be attached to the fiber surface. Even in this case, in the case of the metal salt of 12-hydroxystearic acid, since it has a good affinity to the polyurethane polymer, it is uniformly dispersed on the fiber surface. Therefore, the frictional property is good and the effect of small fluctuation of the frictional stress is exhibited. In the present invention, that the polyurethane elastic fiber has a metal salt of 12-hydroxystearate means that the metal salt of 12-hydroxystearate is added to the polyurethane polymer prior to spinning, and then spun to form the inside of the polyurethane elastic fiber and It is meant to include those which are transferred from the inside to the fiber surface, or those which are adhered as a component of an oil before being wound on a paper tube after spinning. In order to exert the above-mentioned effect, it is preferable that at least a portion of 12-hydroxystearic acid possessed by the polyurethane elastic fiber is added to the polyurethane polymer solution before spinning.
１２−ヒドロキシステアリン酸金属塩と無機固形物との合計含有量は、ポリウレタン重合体１００重量部に対して０．００２〜１０重量部が好ましい。０．００２重量部未満であれば、期待する効果が充分に発揮できない。１０重量部より多ければ、紡糸中に糸キレや生地作成中にガイドや編み針にスカムを発生しやすい。 The total content of the 12-hydroxystearate metal salt and the inorganic solid is preferably 0.002 to 10 parts by weight with respect to 100 parts by weight of the polyurethane polymer. If it is less than 0.002 parts by weight, the expected effect can not be sufficiently exhibited. If the amount is more than 10 parts by weight, scum may be easily generated in the guide and the knitting needle during yarn spinning and fabric preparation during spinning.
本発明において、ポリウレタン重合体とは、両末端にヒドロキシル基を有し、分子量が６００〜４０００である、実質的に線上の重合体、例えばホモまたは共重合体からなるポリエステルジオール、ポリエーテルジオール、ポリエステルアミドジオール、ポリ炭酸エステルジオール、ポリアクリルジオール、ポチオエステルジオール、ポリチオエーテルジオール、ポリ炭化水素ジオールまたはこれらの混合物またはこれらの共重合物と、有機ジイソシアネートと、多官能性活性水素原子を有する鎖延長剤、例えばポリオール、ポリアミン、ヒドロキシルアミン、ヒドラジン、ポリヒドラジド、ポリセミカルバジド、水、またはこれらの混合物等とを主成分とする重合体である。更に詳細には、特開２０１２−２０７３３２号公報の段落［００４３］〜［００４９］に記載されている。本発明で用いる１２−ヒドロキシステアリン酸金属塩及び無機固形物は、通常はポリウレタンプレポリマーと鎖伸長剤を反応せしめたポリウレタン重合体溶液中に添加される。 In the present invention, the polyurethane polymer means a substantially linear polymer having a hydroxyl group at both ends and having a molecular weight of 600 to 4000, for example, a polyester diol consisting of a homo or copolymer, a polyether diol, Polyester amide diol, polycarbonate ester diol, polyacrylic diol, polythioester diol, polythioether diol, polyhydrocarbon diol or a mixture thereof or a copolymer thereof, an organic diisocyanate, and a chain having a multifunctional active hydrogen atom It is a polymer based on an extender such as a polyol, a polyamine, a hydroxylamine, a hydrazine, a polyhydrazide, a polysemicarbazide, water, or a mixture thereof. Further details are described in paragraphs [0043] to [0049] of JP 2012-207332A. The metal 12-hydroxystearate and the inorganic solid used in the present invention are usually added to a polyurethane polymer solution in which a polyurethane prepolymer and a chain extender are reacted.
本発明のポリウレタン弾性繊維は、従来から知られている溶融紡糸法、湿式紡糸法、乾式紡糸法で製造できる。これらの紡糸法の中で、ジメチルアセトアミド、ジメチルフォルアミドといったアミド系溶媒に溶解せしめたポリウレタン紡糸原液を、細糸であっても高速紡糸で長期に安定に製造できるので乾式紡糸が好ましい。乾式紡糸におけるポリウレタン紡糸原液の好ましいポリマー固形分濃度は２０〜５０重量％であり、濃度が２０重量％未満であると高速紡糸時に紡塔内で脱溶媒が不完全となる恐れがあり、５０重量％を超える濃度であると、ポリウレタン紡糸原液が不安定で粘度上昇やゲル化現象を引き起こしやすく、紡糸時糸キレの原因となる場合がある。より好ましい濃度は３０〜４０重量％である。
本発明のポリウレタン弾性繊維の好ましい単糸デシテックスは５〜２０デシテックスで、更に好ましい単糸デシテックスは８〜１５デシテックスである。単糸デシテックスが５デシテックス未満の細い糸の場合、紡糸時に紡塔内で溶剤乾燥用の高温気流と糸との摩擦抵抗に抗しきれずに、糸切れが起こり、安定な高速生産が困難になる。また、単糸デシテックスが２０デシテックスより大きい繊維の場合、繊維中からの溶剤の乾燥が遅くなるため、紡糸速度を大きく低下させる必要があり、生産コストが上昇する。
The polyurethane elastic fiber of the present invention can be produced by a conventionally known melt spinning method, wet spinning method or dry spinning method. Among these spinning methods, dry spinning is preferable because a polyurethane spinning stock solution dissolved in an amide solvent such as dimethylacetamide and dimethylformamide can be stably produced for a long time even by fine spinning at high speed. The preferred polymer solids concentration of the polyurethane spinning solution in dry spinning is 20 to 50% by weight, and if the concentration is less than 20% by weight, there is a risk that the desolvation may be incomplete in the spinner during high speed spinning, If the concentration is more than 10%, the polyurethane spinning solution is unstable and easily causes a viscosity increase and a gelation phenomenon, which may cause yarn breakage during spinning. A more preferred concentration is 30 to 40% by weight.
A preferred single yarn decitex of the polyurethane elastic fiber of the present invention is 5 to 20 dtex, and a further preferred single yarn decitex is 8 to 15 dtex. In the case of thin yarn with single yarn decitex less than 5 dtex, the yarn can not be resisted by the high temperature air stream for solvent drying and yarn friction resistance in spinning when spinning, and yarn breakage occurs, making stable high-speed production difficult . In addition, in the case of a fiber having a single yarn decitex of more than 20 dtex, the drying of the solvent from the inside of the fiber is delayed, so the spinning speed needs to be greatly reduced, and the production cost is increased.
これらの単糸が紡糸筒内で、溶剤が除去される段階でマルチフィラメントの場合、複数本合着された弾性繊維になる。１２−ヒドロキシステアリン酸金属塩を用いた本発明のポリウレタン弾性繊維の合着性は従来用いられているステアリン酸マグネシシウムの場合と比較して、均一でかつ良好である。
これは、従来用いられているステアリン酸マグネシウムの場合は、アミド系溶剤やポリウレタン重合体との親和性が乏しい為に、紡糸筒内で溶剤が乾燥し始めると同時に繊維の単糸表面に移行しやすい為、そのことにより単糸表面同士の合着に必要な接着性が阻害され単糸間の合着性が低下すると推測する。一方、本発明で用いられる１２−ヒドロキシステアリン酸金属塩は、アミド系溶剤やポリウレタン重合体との親和性が比較的良好であるために、紡糸塔内での単糸表面への移行が比較的遅い為、紡糸塔内中での単糸同士の合着が良好になると考えられる。
In the case of a multifilament, these single yarns become elastic fibers combined in a multiple filament at the stage where the solvent is removed in the spinning cylinder. The bonding property of the polyurethane elastic fiber of the present invention using a 12-hydroxystearic acid metal salt is uniform and good as compared with the case of conventionally used magnesium stearate.
This is because, in the case of conventionally used magnesium stearate, the solvent starts to dry in the spinning cylinder and simultaneously migrates to the surface of the single yarn of the fiber because of the poor affinity with the amide solvent and the polyurethane polymer. Since it is easy, it is estimated that the adhesiveness required for the adhesion of single yarn surfaces is inhibited by that, and the adhesion between single yarns falls. On the other hand, the metal 12-hydroxystearate used in the present invention has a relatively good affinity to the amide solvent and the polyurethane polymer, so that the migration to the surface of the single yarn in the spinning tower is relatively high. Since it is slow, it is considered that the coalescence of single yarns in the spinning tower is improved.
本発明のポリウレタン弾性繊維は、総フィラメント数が１〜１００フィラメントからなるモノ及びマルチフィラメントのポリウレタン弾性繊維であり、特に好ましい総フィラメント数は１〜５０フィラメントである。マルチフィラメントの場合、紡糸工程で回転リング又は回転空気流を用いて数本のマルチフィラメントが仮撚りされ、合着されているために見かけ上、一本の弾性繊維として紙管に巻き取られる。本発明のポリウレタン弾性繊維は紙管に巻きとられた糸巻形状も良好である。
合着性が低いと、生地の加工工程でガイドや編み針の摩擦によって単糸が剥離し単糸バラケが起こり、糸キレの原因になり、生地の表面上に傷欠点を生じさせ品位の低下につながる。
The polyurethane elastic fiber of the present invention is a mono- and multifilament polyurethane elastic fiber consisting of 1 to 100 filaments in total, and a particularly preferable total filament number is 1 to 50 filaments. In the case of multifilaments, several multifilaments are temporarily twisted in a spinning process using a rotating ring or a rotating air flow, and because they are bonded, they are apparently wound on a paper tube as a single elastic fiber. The polyurethane elastic fiber of the present invention is also good in a wound shape wound around a paper tube.
If the cohesion is low, the single yarn may peel off due to the friction of the guide or knitting needle in the fabric processing process, causing single yarn loose, which may cause yarn squeezing, causing a flaw defect on the surface of the fabric and lowering the quality. Connect.
本発明のポリウレタン弾性繊維には、通常用いられる他の化合物、例えば紫外線吸収剤、酸化防止剤、光安定剤、耐ガス安定剤、着色剤、艶消し剤、充填剤等と併用してもよい。更に、前述のように１２−ヒドロキシステアリン酸金属塩は、紡糸後に紡糸筒から出た糸を紙管に巻きとる前に油剤中の１つの成分としてとして、繊維表面に付着させてもよい。
本発明のポリウレタン弾性繊維から得られる生地の品位は均一で商品価値も高い。
The polyurethane elastic fiber of the present invention may be used in combination with other commonly used compounds such as UV absorbers, antioxidants, light stabilizers, gas stabilizers, colorants, matting agents, fillers and the like. . Furthermore, as described above, the metal salt of 12-hydroxystearate may be attached to the fiber surface as one component in the oil prior to winding the yarn from the spinning tube after spinning into a paper tube.
The quality of the fabric obtained from the polyurethane elastic fiber of the present invention is uniform and has high commercial value.
以下、実施例および比較例によって本発明を詳細に説明する。しかし、本発明はこれら実施例のみに限定されるものではない。実施例で述べられている各種の測定法は、以下に述べる方法を用いて行った。
（１）＜脂肪酸金属塩又は無機固形物の平均粒子径測定法＞
あらかじめジメチルアセトアミド溶剤中でスラリー状に均一分散した脂肪酸金属塩類や無機固形物の固形分濃度が１５％の溶液を、ジメチルアセトアミド溶媒中でベックマン・コールター社製ＬＳ１３―３２０型粒度分布測定装置にて測定し、体積統計値基準での測定値から平均粒子径を求めた。
Hereinafter, the present invention will be described in detail by way of examples and comparative examples. However, the present invention is not limited to these examples. The various measurement methods described in the examples were performed using the methods described below.
(1) <Method of measuring average particle size of fatty acid metal salt or inorganic solid>
A solution of fatty acid metal salts and inorganic solids 15% solid concentration dispersed uniformly in the form of slurry in dimethylacetamide solvent in advance is mixed with a solution of 15% solid particle concentration in dimethylacetamide solvent using a LS13-320 particle size distribution analyzer manufactured by Beckman Coulter It measured and calculated | required the average particle diameter from the measured value on the basis of a volume statistics value.
（２）＜強伸度物性の測定法＞
２２デシテックス／２フィラメントの弾性繊維を、引張試験機オリエンテック（株）製ＵＴＭ−ＩＩＩ−１００型を用いて測定した。引張試験機にサンプルを掴み間隔５０ｍｍでセットし、引張速度５００ｍｍ／ｍｉｎ、温度２０℃、湿度６５ｗｔ％の条件下で測定した。
(2) <Method of measuring physical properties of strength and elongation>
The elastic fiber of 22 dtex / 2 filaments was measured using a tensile tester ORIENTEC Co., Ltd. UTM-III-100 type. The sample was set in a tensile tester at a grip interval of 50 mm, and measured under conditions of a tensile speed of 500 mm / min, a temperature of 20 ° C., and a humidity of 65 wt%.
（３）＜紡糸安定性及び吐出圧上昇率の評価法＞
２２デシテックス／２フィラメント紡糸時の２４時間の紡糸中に起こった糸切れ回数で評価した。また濾材として４００メッシュの金網フィルターを用いた時の、２４時間後の吐出圧の上昇（ｋｇｆ／ｃｍ２）を吐出圧上昇率として求めた。
(3) <Method for evaluating spinning stability and discharge pressure increase rate>
The number of yarn breaks which occurred during 24 hours of spinning at 22 dtex / 2 filament spinning was evaluated. In addition, when a 400 mesh wire mesh filter was used as a filter medium, an increase in discharge pressure (kgf / cm 2 ) after 24 hours was determined as a discharge pressure increase rate.
（４）＜紙管上への糸の巻姿評価法＞
毎分１０２０ｍ／分の速度で、２２デシテックス／２フィラメント（単糸繊度１１デシテックス）のポリウレタン弾性繊維５００ｇを紙管に巻き取った。この紙管に巻きとられた糸の巻姿の状態を、以下の評価基準に従って５人の目視判定で総合評価した。
○：紙管上の糸の巻姿が整っていて美しい。
△：紙管上の糸の巻姿がやや崩れ始めている。
×：紙管上の糸の巻姿が大いに崩れて美しくない。
(4) <Method for evaluating winding form of yarn on paper tube>
500 g of polyurethane elastic fiber of 22 dtex / 2 filaments (single yarn fineness 11 dtex) was wound on a paper tube at a speed of 1020 m / min. The state of the winding form of the yarn wound around the paper tube was comprehensively evaluated by visual judgment of five persons in accordance with the following evaluation criteria.
○: The winding form of the yarn on the paper tube is in order and beautiful.
Δ: The winding shape of the yarn on the paper tube is starting to break up a little.
X: The winding form of the yarn on the paper tube is broken so much that it is not beautiful.
（５）＜ポリウレタン弾性繊維の紙管からの解除性の評価法＞
４４デシテックス／４フィラメントポリウレタン弾性繊維を４５℃、６５％ＲＨの雰囲気にて３０日間放置後、紙管を梨地ローラー上に置き、ローラーを回転させながら、ローラー表面速度４０ｍ／分で、弾性繊維を送り出す。送り出された弾性繊維を５０ｃｍ離れた所に設置された同じ径の梨地ローラー上に巻き取る。巻き取るローラー上の表面速度を８０ｍ／分から徐々に低下させて、送り出すローラー上の紙管に弾性繊維が紙管にからみついて逆巻きし、弾性繊維が切断されて送り出されなくなった時点の速度Ｓｍ／分を測定する。Ｓｍ／分の値が小さいほど紙管から弾性糸の糸離れが良いことを示し、これを解除性が良好と判断する。
しかし、逆にあまりに糸離れが良すぎると、紙管に巻かれたポリウレタン弾性繊維を運搬する時に、紙管に巻かれた弾性繊維の外層が糸落ちし易く、取り扱い上の問題となるので、適正な範囲が存在する。本測定において、好ましい紙管外層の弾性繊維のＳ（以下ＳＯと表す）は、ＳＯ＝４５〜５５ｍ／分、紙管内層の弾性繊維のＳ（以下、ＳＩと表す）は、ＳＩ＝５０〜６５ｍ／分である。ＳＩおよびＳＯがこの範囲に入っているか否かで判断する。ＳＩ、ＳＯのいずれかの値がこの範囲をはずれ、値が小さいと運搬時や整経工程で、糸落ちし易く、逆に値が大きいと紙管への逆巻きや糸切れが頻発する場合があり、問題となる。
(5) <Method of evaluating release of polyurethane elastic fiber from paper tube>
After leaving the paper tube at 45 ° C. and 65% RH for 30 days, place the paper tube on a textured roller and rotate the roller at a roller surface speed of 40 m / min. Send out. The fed elastic fiber is wound on a satin roller of the same diameter installed at a distance of 50 cm. The surface velocity on the take-up roller is gradually reduced by 80 m / min, elastic fiber is caught in the paper tube and reverse-wound in the paper tube on the delivery roller, and the speed Sm / s when elastic fiber is cut and not sent out Measure the minutes. The smaller the value of Sm / min, the better the separation of the elastic yarn from the paper tube, and it is judged that the releasability is good.
However, if the yarn separation is too good, on the other hand, the outer layer of the elastic fiber wound on the paper tube tends to fall off when transporting the polyurethane elastic fiber wound on the paper tube, which causes a handling problem, There is a proper range. In this measurement, S (hereinafter referred to as SO) of elastic fibers of preferable outer layer of paper tube is SO = 45 to 55 m / min, S (hereinafter referred to as SI) of elastic fibers of inner layer of paper is SI = 50 to 50 It is 65 m / min. It is judged whether SI and SO fall within this range. If any of SI and SO is out of this range, if the value is small, it is easy to drop the yarn during transportation or warping process, and conversely, if the value is large, reverse winding to the paper tube or yarn breakage often occur. Yes, it becomes a problem.
（６）＜ポリウレタン弾性繊維の合着性の評価法＞
引張試験機オリエンテック（株）製ＵＴＭ−ＩＩＩ−１００型を用いた。引張試験機にサンプルを掴み間隔５０ｍｍでセットし、温度２０℃、湿度６５ｗｔ％の条件下で以下の方法で測定した。２２デシテックス／２フィラメントの単糸を２つに分ける。引き裂いた各一本のフィラメントを、上下のチャックに別々に股を引き裂くようにセットした後に、強伸度測定と同じ方法で応力測定を開始する。
単糸を引き裂くように測定すると強く合着している部分は応力が高く、合着が弱い部分は低い値を示す。そのため測定が進行するにつれて値が上下に変動する。変動幅が小さく、かつ、平均値応力が大きい値を示すサンプル弾性糸が、フィラメントの合着性が強く良好であると判断できる。
図２に測定結果の一例を示す。図２に示したように、測定チャートより応力の平均値と変動幅を求める。測定スタート時をベースラインとして平均値応力（ａ）が大きく、変動幅（ｂ）が小さければ、ポリウレタン弾性繊維は、フィラメントの合着性が強く良好であると判断できる。図２において、（１）は合着性が良好な例であり、（２）は合着性が不良な例である。
(6) <Method of evaluating bonding of polyurethane elastic fiber>
A tensile tester, Orientec Co., Ltd. UTM-III-100 was used. The sample was set in a tensile tester at a grip interval of 50 mm, and measurement was performed under the conditions of a temperature of 20 ° C. and a humidity of 65 wt% according to the following method. Divide a single yarn of 22 dtex / 2 filaments into two. After setting each torn filament to tear the crotch separately on the upper and lower chucks, the stress measurement is started in the same manner as the strength and elongation measurement.
When measurement is made so as to tear a single yarn, the portion where the bonding is strong shows high stress, and the portion where the bonding is weak shows a low value. Therefore, the value fluctuates up and down as the measurement progresses. It can be judged that the sample elastic yarn having a small fluctuation range and a large average stress value has a strong cohesiveness of the filaments and is good.
An example of a measurement result is shown in FIG. As shown in FIG. 2, the average value and fluctuation range of stress are determined from the measurement chart. If the average value stress (a) is large and the fluctuation range (b) is small with the measurement start as a baseline, it can be judged that the polyurethane elastic fiber has a strong cohesiveness of the filaments and is good. In FIG. 2, (1) is an example in which the cohesion is good, and (2) is an example in which the cohesion is poor.
（７）＜金属摩擦性の評価法＞
４４デシテックス／４フィラメントの弾性繊維を、２５℃、６５％ＲＨの雰囲気で３０日間放置後、図１の装置を用いて評価した。図１において、１は試験糸、２は送り出しローラー、３はテンションメーター、４は編み針、５は巻き取り部、６は巻き取りローラー、７は試験糸走行糸状であり、８は編み針にかかる糸状がなす角度で２９°である。試験糸を、送り速度１００ｍ／分、巻き取り速度２００ｍ／分の延伸倍率２倍で走行させ、編み針通過前後の試験糸の糸条の走行応力とその応力変動を測定した。図３は測定結果の一例であり、Ｔ１、Ｔ２は、それぞれ、編み針通過後の走行応力の中心値（ｇ）、編み針通過前の走行応力の中心値（ｇ）である。摩擦係数μｄは下記式（１）で与えられる。
μｄ＝Ｌｎ（Ｔ１／Ｔ２）／２．６３７６・・・式（１）
摩擦係数μｄは、値が小さい程、摩擦が小さく良好である。
(7) <Evaluation method of metal friction property>
The elastic fiber of 44 dtex / 4 filament was evaluated using the apparatus of FIG. 1 after being left for 30 days in an atmosphere of 25 ° C. and 65% RH. In FIG. 1, 1 is a test yarn, 2 is a delivery roller, 3 is a tension meter, 4 is a knitting needle, 5 is a winding portion, 6 is a winding roller, 7 is a test yarn running thread, and 8 is a thread applied to the knitting needle Is 29 ° at the angle that The test yarn was run at a feed rate of 100 m / min and a take-up speed of 200 m / min and a draw ratio of 2 times, and the running stress of the yarn of the test thread before and after passing through the knitting needles and its stress variation were measured. FIG. 3 shows an example of the measurement result, and T1 and T2 are the center value (g) of the running stress after passing the knitting needle and the center value (g) of the running stress before passing the knitting needle, respectively. The coefficient of friction μd is given by the following equation (1).
μd = Ln (T1 / T2) /2.6376 Formula (1)
The smaller the friction coefficient μd, the smaller the friction and the better.
（８）＜生地作成の整経及び編成方法＞
４４デシテックス／４フィラメントの弾性繊維５８８本をリバー社製の弾性糸用整経機に取り付け、弾性繊維送り出し速度１５０ｍ／分、ビーム巻き取り速度３００ｍ／分にて整経し、１ビームあたり弾性繊維重量で１４．７ｋｇを１６ビーム整経した。このように整経したポリウレタン弾性繊維をバックの試験糸とし、ナイロン６６加工糸４４デシテックス／３４フィラメントをフロントとしドラフト率８０％で整経し、下記条件のハーフ生地編成条件で編成した。
＜編成条件＞
編機：３６ゲージ／インチ カールマイヤー社製 トリコット編機
組織：フロント １０／２３、バック １２／１０
ランナー長：フロント１２０ｃｍ／４８０コース
バック７７．６ｃｍ／４８０コース
機上コース：１００コース／インチ
この編成工程で１５ｋｇ／１反の条件で２０反編んだ。
(8) <Warning and knitting methods of fabric preparation>
Attach 588 elastic fibers of 44 dtex / 4 filament to the elastic yarn warper manufactured by River Co., and carry out elastic fiber feeding speed 150 m / min, beam winding speed 300 m / min, elastic fiber per beam 16 beams of 14.7 kg by weight were warped. The polyurethane elastic fibers thus warped were used as test yarns for the back, nylon 66 processed yarns 44 dtex / 34 filaments as the front, warped with a draft rate of 80%, and knitted under the half fabric knitting conditions of the following conditions.
<Organization condition>
Knitting machine: 36 gauge / inch KARL MAYER Tricot knitting machine Organization: Front 10/23, back 12/10
Runner length: Front 120 cm / 480 course
Back 77.6 cm / 480 course Aircraft course: 100 course / inch 20 anti-knitted in the condition of 15 kg / 1 anti in this knitting process.
（９）＜生地品位の評価法＞
得られた経編生機を９０℃で１分間精錬し、プレセットとして、テンター仕上げ機を用いて熱処理条件として温度１９０℃、時間６０秒で処理した。次いで、液流染色機を用いて１００℃×６０分の条件で染色した。ファイナルセットとして、テンター仕上げ機を用いて、熱処理条件１８０℃×４５秒で処理して、経編地の染上げ反を得た。試験糸とナイロン糸を交編させて得られた経編地の生地品位を、以下の評価基準に従って５人の目視判定で総合評価した。
◎：経筋がほとんどなく大変美しい。
○：経筋が目立たず美しい。
△：経筋が僅かに目視される。
×：経筋が多く、美しくない。
(9) <Determination method of fabric quality>
The obtained warp knitting machine was refined at 90 ° C. for 1 minute and treated as a pre-set at a temperature of 190 ° C. for 60 seconds as a heat treatment condition using a tenter finisher. Then, it was stained at 100 ° C. for 60 minutes using a jet flow dyeing machine. As a final set, a tenter finishing machine was used, and heat treatment conditions were performed at 180 ° C. for 45 seconds to obtain a dyed reverse of a warp knitted fabric. The fabric quality of the warp knitted fabric obtained by interlacing the test yarn and the nylon yarn was comprehensively evaluated by visual judgment of five persons according to the following evaluation criteria.
◎: There is almost no striation and it is very beautiful.
○: The melancholy muscle is inconspicuous and beautiful.
Δ: Trans-muscular line slightly visible.
X: There are many threads and not beautiful.
［参考例１］（ポリウレタン弾性繊維用紡糸原液（Ａ）の製造）
平均分子量２０００のポリテトラメチレングリコール１６６．６重量部および４，４’−ジフェニルメタンジイソシアネート３１．２重量部を、窒素ガス気流中９５℃において８０分間攪拌しつつ反応させて、両末端がイソシアネート基残有のプレポリマーを得た。ついで、これを室温まで冷却した後、ジメチルアセトアミド２７０重量部を加え、溶解してプレポリマー溶液とした。
一方、エチレンジアミン２．３４重量部およびジエチルアミン０．３７重量部をジメチルアセトアミド１５７重量部に溶解し、これを前記プレポリマー溶液に室温で添加して、粘度２０５０ポイズ（３０℃）のポリウレタン溶液を得た。こうして得られた粘調なポリマー溶液に、ポリウレタン重合体固形物に対して、１，３，５−トリス（４−ターシャルブチル−３−ヒドロキシ−２、６−ジメチルベンジル）−１，３，５−トリアジン−２，４，６−（１Ｈ，３Ｈ，５Ｈ）−トリオン（商品名ＣＹＡＮＯＸ１７９０）１．５重量％、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロ−ベンゾトリアゾール０．５重量％を加えて紡糸原液（Ａ）を作成した。
[Reference Example 1] (Manufacture of spinning solution for polyurethane elastic fiber (A))
166.6 parts by weight of polytetramethylene glycol having an average molecular weight of 2000 and 31.2 parts by weight of 4,4'-diphenylmethane diisocyanate are reacted with stirring in a nitrogen gas stream at 95 ° C for 80 minutes, leaving isocyanate groups at both ends The obtained prepolymer was obtained. Then, after cooling to room temperature, 270 parts by weight of dimethylacetamide was added and dissolved to obtain a prepolymer solution.
On the other hand, 2.34 parts by weight of ethylene diamine and 0.37 parts by weight of diethylamine are dissolved in 157 parts by weight of dimethylacetamide and added to the prepolymer solution at room temperature to obtain a polyurethane solution with a viscosity of 2050 poise (30 ° C.). The The viscous polymer solution thus obtained is, based on polyurethane polymer solids, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,7. 5-triazine-2,4,6- (1H, 3H, 5H) -trione (trade name: CYANOX 1790) 1.5% by weight, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) 0.5 wt% of 5-chloro-benzotriazole was added to make a spinning stock solution (A).
［参考例２］（脂肪酸金属塩の分散液の製造１）
＜脂肪酸金属塩の分散液−１＞
１２−ヒドロキシステアリン酸マグネシウム（１２０ｇ）をジメチルアセトアミド（６８０ｇ）に加えて２０分撹拌して１５重量％分散溶液として分散させた。この溶液を、０．５ｍｍのジルコニアビーズの入ったアイメックス社製ＲＭＨ−０３型湿式ビーズミルを用いて、１パス循環処理して分散液を作成した。この分散液を粒度分布計で測定した結果、平均粒子径は２．０μｍであった。
[Reference Example 2] (Production of Dispersion of Fatty Acid Metal Salt 1)
<Dispersion liquid of fatty acid metal salt-1>
Magnesium 12-hydroxystearate (120 g) was added to dimethylacetamide (680 g) and stirred for 20 minutes to be dispersed as a 15% by weight dispersion. This solution was subjected to a 1-pass circulation process using an Imex RMH-03 wet bead mill containing 0.5 mm of zirconia beads to prepare a dispersion. As a result of measuring this dispersion with a particle size distribution analyzer, the average particle size was 2.0 μm.
［参考例３］（脂肪酸金属塩の分散液の製造２）
＜脂肪酸金属塩の分散液−２＞
ステアリン酸マグネシウム（１２０ｇ）をジメチルアセトアミド（６８０ｇ）に加えて２０分撹拌して１５重量％分散溶液として分散させた。この溶液を、前記参考例２と同様の方法で、湿式ビーズミル処理し、脂肪酸金属塩の分散液−２を作成した。平均粒径は、０．８μｍであった。
[Reference Example 3] (Production of Dispersion of Fatty Acid Metal Salt 2)
<Dispersion liquid of fatty acid metal salt-2>
Magnesium stearate (120 g) was added to dimethylacetamide (680 g) and stirred for 20 minutes to disperse as a 15% by weight dispersion. This solution was subjected to wet bead milling in the same manner as in Reference Example 2 to prepare a
［参考例４］（脂肪酸金属塩の分散液の製造３）
＜脂肪酸金属塩の分散液−３＞
前記参考例２と同様な方法で、１２−ヒドロキシステアリン酸マグネシウムを８４ｇ加え、１５重量％の分散溶液になるようにして、同様の湿式ビーズミルで３パス循環処理を行い、脂肪酸金属塩の分散液−３を作成した。平均粒径は、０．６μｍであった。
[Reference Example 4] (Production of Dispersion of Fatty Acid Metal Salt 3)
<Dispersion liquid of fatty acid metal salt-3>
In the same manner as in Reference Example 2, 84 g of magnesium 12-hydroxystearate was added to form a 15% by weight dispersion solution, and a 3-pass circulation process was carried out with the same wet bead mill to obtain a dispersion of fatty acid metal salt -3 was created. The average particle size was 0.6 μm.
［実施例１〜３、参考例５および比較例１〜３]
前記の紡糸用原液（Ａ）と前記記載の方法で作成した脂肪酸金属塩の分散液とを用いて、表１記載の組成になるように脂肪酸金属塩の分散液及び無機固形物を加えた分散液を、スタティックミキサーで紡糸用原液（Ａ）と均一に混合し各紡糸原液を作成した。
この各紡糸原液を脱泡した後、紡口フィルターとして４００メッシュの金網フィルターを用いて、紡糸ノズル（口金は４個又は２個の細孔を有す）の細孔から熱風中２１０℃に押し出して溶剤を蒸発させた。乾燥された糸条をリング仮撚り機に通過する過程で仮撚りし、ゴッデトローラを経てオイリングローラ上でポリアルキルシロキサン、鉱物油を主成分とする油剤成分をポリウレタン弾性繊維の重量に対して５重量％付着させて、１０２０ｍ／分の速度で、２２デシテックス／２フィラメント及び４４デシテックス／４フィラメント（単糸繊度１１デシテックス）のポリウレタン弾性繊維５００ｇを各々紙管に巻き取った。製造した糸の強伸度物性及び残留溶剤はポリウレタン弾性繊維として適性の範囲内であった。
この弾性繊維を用いて各種評価を行った結果を表１に示す。
[Examples 1 to 3, Reference Example 5 and Comparative Examples 1 to 3]
Dispersion obtained by adding a fatty acid metal salt dispersion and an inorganic solid so as to have the composition described in Table 1 using the above-mentioned stock solution for spinning (A) and the dispersion of fatty acid metal salt prepared by the method described above The solution was uniformly mixed with the spinning stock solution (A) with a static mixer to prepare each spinning stock solution.
After degassing each spinning solution, it is extruded at 210 ° C. in hot air from the pores of a spinning nozzle (the nozzle has 4 or 2 pores) using a 400 mesh wire mesh filter as a spinneret filter. The solvent was evaporated. The dried yarn is false-twisted in the process of passing it to a ring false twister, passes through a godet roller, and on the oiling roller, an oiling agent component composed mainly of polyalkylsiloxane and mineral oil is 5 weight to the polyurethane elastic fiber weight After adhesion, 500 g of polyurethane elastic fibers of 22 dtex / 2 filament and 44 dtex / 4 filament (single yarn fineness 11 dtex) were respectively wound on a paper tube at a speed of 1020 m / min. The strength and elongation physical properties of the produced yarn and the residual solvent were within the range of suitability as a polyurethane elastic fiber.
The results of various evaluations using this elastic fiber are shown in Table 1.
本発明のポリウレタン弾性繊維は、細糸生産においても長期間、安定に紡糸が可能であり、加工工程での糸切れも少なく、対金属摩擦特性も良好である。よって、本発明のポリウレタン弾性繊維を用いて作成された生地は表面品位が均一で商品価値が優れている。 The polyurethane elastic fiber of the present invention can be stably spun for a long time even in fine yarn production, has few yarn breakages in the processing step, and has good metal friction characteristics. Therefore, the fabric produced using the polyurethane elastic fiber of the present invention has uniform surface quality and excellent commercial value.
１ 試験糸
２ 送り出しローラー
３ テンションメーター
４ 編み針
５ 巻き取り部
６ 巻き取りローラー
７ 試験糸走行糸条
８ 編み針にかかる糸条がなす角度＝２９°
1
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