JP3833287B2 - Method for producing polyurethane elastic yarn - Google Patents
Method for producing polyurethane elastic yarn Download PDFInfo
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- JP3833287B2 JP3833287B2 JP25576095A JP25576095A JP3833287B2 JP 3833287 B2 JP3833287 B2 JP 3833287B2 JP 25576095 A JP25576095 A JP 25576095A JP 25576095 A JP25576095 A JP 25576095A JP 3833287 B2 JP3833287 B2 JP 3833287B2
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- elastic yarn
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- 229920002635 polyurethane Polymers 0.000 title claims description 43
- 239000004814 polyurethane Substances 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 50
- 238000009987 spinning Methods 0.000 claims description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 38
- 125000000962 organic group Chemical group 0.000 claims description 26
- 125000005442 diisocyanate group Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 208000012886 Vertigo Diseases 0.000 description 38
- 239000003921 oil Substances 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 229920005749 polyurethane resin Polymers 0.000 description 10
- 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 9
- -1 for example Chemical group 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 5
- 239000004632 polycaprolactone Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- SYEOWUNSTUDKGM-YFKPBYRVSA-N 3-methyladipic acid Chemical compound OC(=O)C[C@@H](C)CCC(O)=O SYEOWUNSTUDKGM-YFKPBYRVSA-N 0.000 description 1
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ポリウレタン弾性糸の製造方法及びその製造方法により得られたポリウレタン弾性糸に関し、詳しくは特定構造のオルガノポリシロキサンと有機ジイソシアネートの反応物を含有させることにより、紡糸油剤の使用量を低減することを特徴とするポリウレタン弾性糸の製造方法及びその製造方法により得られたポリウレタン弾性糸に関するものである。
【０００２】
【従来の技術】
ポリウレタン弾性糸の製造には、一般的に、プレポリマーをＤＭＦ中でイソシアネート／ヒドラジン付加体などと反応させた後脱ＤＭＦ工程で紡糸する乾式紡糸、プレポリマーをＭＥＫなどに溶解して紡糸する湿式紡糸、又はプレポリマーに架橋剤を加えて加熱反応させて特殊装置で紡糸する溶融紡糸などの方法がある。いずれの場合においても ポリウレタンの耐熱性の低さ、高温時の変形、繊維相互の膠着を防止する目的で、紡糸する際には主にシリコーン系の油剤が、例えば、ポリウレタン１００重量部に対して紡糸油剤１０重量部以上といった多量に用いられてきた。
【０００３】
しかしながら、多量の紡糸油剤によって上記の高温時の変形、繊維相互の膠着を防止することができても、これが残留すると、後工程での汚れや染色などの工程での疎外要因となるため、洗浄する工程が必要となる。この時、紡糸油剤が多量のため、洗浄用薬剤量が多くなり、また洗浄時間にも長時間を費やし、さらに洗浄の廃液量も多いなどの問題があった。
【０００４】
また、ポリウレタン弾性糸は混紡で使用されることが多いため、近年、繊維の耐久性の向上を目的として、紡糸後の滑り性が要求されている。
【０００５】
【発明が解決しようとする課題】
本発明は、上記したように従来ポリウレタン弾性糸の製造段階で多量に使用されていた紡糸油剤の軽減と、紡糸後の滑り性を得ることを目的とし、特には、これらの目的を得るためのポリウレタン弾性糸の製造方法を与えることを課題とする。
【０００６】
【課題を解決するための手段】
本発明者等は上記課題について鋭意検討した結果、ポリウレタン弾性糸の製造時に特定構造のオルガノポリシロキサンと有機ジイソシアネートの反応物を含有させることによって、優れた紡糸性が発現し、これまで提案されたポリウレタン弾性糸の製造方法よりも紡糸油剤の軽減が可能であり、しかもその方法により得られたポリウレタン弾性糸は滑り性が優れていることを見出し、更に検討して本発明を完成させた。
【０００７】
【発明の概要】
即ち、本発明は、
（イ）次式（１）：
【化５】
で示される、１分子中に平均で少なくとも１個の水酸基を含有するオルガノポリシロキサン、有機ジイソシアネート及びポリオール成分を反応させてなるポリウレタン１００重量部に対し、紡糸油剤１０重量部以下を付与して紡糸することを特徴とするポリウレタン弾性糸の製造方法、
（ロ）上記（イ）の方法により製造されたポリウレタン弾性糸、
（ハ）式（１）において、Ａ基が次式：
【化６】
（ニ）上記（ハ）の方法により製造されたポリウレタン弾性糸、
（ホ）次式（１）：
【化７】
【化８】
で示され、１分子中に平均で少なくとも１個の水酸基を含有し、平均分子量が５００〜１００，０００であるオルガノポリシロキサン、有機ジイソシアネート及びポリオール成分を反応させてなるポリウレタン１００重量部に対し、紡糸油剤１０重量部以下を付与して紡糸することを特徴とするポリウレタン弾性糸の製造方法、並びに、
（へ）上記（ホ）の方法により製造されたポリウレタン弾性糸
に関する。
【０００８】
【発明の実施の形態】
さらに、本発明で用いられる水酸基を含有するオルガノポリシロキサンを説明する。上記式（１）中のＲ1 は炭素原子数１〜１０の１価炭化水素基、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、フェニル基、トリル基、フェネチル基等であるが、好ましくはメチル基である。
上記式中のＲ2 及びＲ5 は、２〜４価の有機基であり、例えば、−ＣＨ2 −、−ＣＨ2 ＣＨ2 −、−ＣＨ2 ＣＨ2 ＣＨ2 −、−ＣＨ（ＣＨ3 ）ＣＨ2 −、−（ＣＨ2 ）4 −、−（ＣＨ2 ）6 −、−（ＣＨ2 ）8 −、−ＣＨ2 ＣＨ2 Ｃ6 Ｈ4 −、−（ＣＨ2 ）12−、−（ＣＨ2 ）16−、−ＣＯ（ＣＨ2 ）5 −、−ＣＨ、−ＣＨ（ＣＨ2 ）2 、−Ｃ、−Ｃ（ＣＨ2 −）3 、−Ｃ（ＣＨ2 −）2 （Ｃ2 Ｈ4 ）、−（ＣＨ2 ）3 ＯＣＨ（Ｃ2 Ｈ4 −）2 、−Ｃ（ＣＨ2 −）（Ｃ2 Ｈ4 −）2 等である。
Ｒ3 、Ｒ6 は２価の有機基であり例えば、−ＣＨ2 −、−ＣＨ2 ＣＨ2 −、−ＣＨ2 ＣＨ2 ＣＨ2 −、−ＣＨ（ＣＨ3 ）ＣＨ2 −、−（ＣＨ2 ）4 −、−（ＣＨ2 ）6 −、−（ＣＨ2 ）8 −、−ＣＨ2 ＣＨ2 Ｃ6 Ｈ4 −、−（ＣＨ2 ）12−、−（ＣＨ2 ）16−、−ＣＯ（ＣＨ2 ）5 −等である。
上記式中のＲ4 は水素原子又は１価の有機基、例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基、ドデシル基、フェニル基、フェネチル基、アセチル基等である。
ｐ及びｑは１〜３であり、対応するＲ2 、Ｒ5 の有機基の価数に連動し、価数から１を減じた数となる。ｍは正の整数、ｎは０又は１以上の整数、ａ、ｂは０又は１以上の整数である。
ＡはＲ1 又は−Ｒ5 ｛（ＯＲ6 ）b −ＯＲ7 ｝q 又は水酸基又は例えばメトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基等のアルコキシ基であり、−Ｒ5 ｛（ＯＲ6 ）b −ＯＲ7 ｝q は、一般式に示すとおり、側鎖に存在しても分子末端に存在しても、その両方に存在してもよい。
【０００９】
さらに、本発明で用いられる水酸基を含有するオルガノポリシロキサンの平均分子量は５００〜１００，０００であり、好ましくは平均分子量が５００〜１０，０００であり、さらに好ましくは平均分子量が５００〜５，０００である。水酸基を含有するオルガノポリシロキサンの平均分子量が大きすぎると、ウレタン化率が低下するため得られるポリウレタン弾性糸の強度等の物理特性が低下し、また、平均分子量が小さすぎると、紡糸性・滑り性の向上が十分発現しないのでそれぞれ好ましくない。
【００１０】
本発明で用いられる水酸基を含有するオルガノポリシロキサンの具体例としては、以下のものを挙げることができるが、これらに限定されるものではない。
平均分子量が２，６００である下記構造で示される水酸基含有オルガノポリシロキサン。
【化９】
【化１０】
【化１１】
【化１２】
【化１３】
【化１４】
【化１５】
【化１６】
本発明で用いられる水酸基を含有するオルガノポリシロキサン、有機ジイソシアネート及びポリオール成分を反応させてポリウレタンを製造する場合には、これらの成分をジメチルホルムアミドのような有機溶剤中で溶液重合させ、又は直接混合し溶融重合させることができる。このときに第三アミンや有機錫化合物のようなポリウレタン製造用触媒を用いても又は用いなくともよい。
【００１２】
本発明で用いられる水酸基を含有するオルガノポリシロキサンと反応させる有機ジイソシアネートとしては、アルキレンジイソシアネート及びアリーレンジイソシアネート、例えばｐ，ｐ’−ジフェニルメタンジイソシアネート、２，４−又は２，６−トルイレンジイソシアネート、１，３−ジイソシアナト−ｏ，ｍ又はｐ−キシレン、水素化ｐ，ｐ’−ジフェニルメタンジイソシアネート、テトラメチレンジイソシアネート、１，５−ナフタレンジイソシアネート、イソホロンジイソシアネート等を用いることができる。
【００１３】
本発明で用いられる水酸基を含有するオルガノポリシロキサンと有機ジイソシアネートの反応物を含有するポリウレタンを製造するために、ポリオール成分として、エチレングリコール、プロピレングリコール、ブタンジオール、ヘキサンジオール、グリセリン、トリメチロールプロパンなどのポリオール、そしてこれらのポリオール、カプロラクトン、ポリカプロラクトンなどのアルキレンオキシド付加物を使用することができる。例えば、ポリ−３−メチルアジペートグリコール、ポリテトラメチレングリコール、ポリプロピレングリコール、ポリブチレンジオール、ポリカプロラクトンジオール、ポリカーボネートジオール等の２官能ジオール、カプロラクタムとトリメチロールプロパンよりなる３官能ポリオール等を好適に用いることができる。
【００１４】
本発明に従って製造された水酸基を含有するオルガノポリシロキサンと有機ジイソシアネートの反応物を含有するポリウレタンには、その他の添加剤、例えばシラン化合物、架橋剤、帯電防止剤、塩類並びにジメチルポリシロキサン、エポキシ基含有オルガノポリシロキサン、カルボキシ基含有オルガノポリシロキサン、ポリシロキサン・ポリオキシアルキレン共重合体、アミノ基含有オルガノポリシロキサン等の各種ポリシロキサン類を本発明の効果が損なわれない範囲で含有させることができる。
【００１５】
本発明に従って製造された水酸基を含有するオルガノポリシロキサンと有機ジイソシアネートの反応物を含有するポリウレタンを紡糸する方法としては、乾式紡糸、湿式紡糸、又は溶融紡糸法など一般的な方法を使用することができる。
【００１６】
本発明に従って製造された水酸基を含有するオルガノポリシロキサンと有機ジイソシアネートの反応物を含有するポリウレタンを紡糸する場合、本発明のポリウレタン１００重量部に対し、紡糸油剤を１０重量部以下として付与して紡糸することを特徴とする。
【００１７】
本発明で用いられる紡糸油剤は特に限定されず、従来公知のポリウレタン用紡糸油剤として市販されているものが使用できる。例えば、鉱物油と２〜２０重量％の金属石鹸の微粒子からなる水を含まない油剤、低粘度パラフィンに低重合度ポリエチレンを含有した油剤、ポリジメチルシロキサン系油剤、ポリオキシアルキレン変性ポリシロキサンを含有した油剤が使用できる。
【００１８】
【実施例】
次に、本発明を実施例に基づいて説明するが、本発明はこれらに限定されるものではない。配合量は重量％である。なお、実施例に先立ち評価法を以下に示す。
紡糸油剤の付与量
紡糸油剤としてシリコーン系油剤Ａ（５％ジメチルポリシロキサンを配合した鉱物油が主成分であるもの）を樹脂に対し２％、５％、１０％又は１５％付与して紡糸を行った。
試験布の作成方法
紡糸されたポリウレタン弾性糸を更にナイロンと５０／５０の比で混紡し、試験布を作成した。
紡糸性能評価
紡糸工程における糸の様子を、以下の基準で評価した。
テスターが、試験布を以下の基準で官能評価した。
（滑り性） ◎：非常に滑らか ○：滑らか △：やや滑らか ×：滑りにくい
摩擦係数評価
試験布をカトーテック（株）製繊維物性計測システムＫＥＳ−ＦＢ４の表面試験機にて表面特性（摩擦係数）を６回測定しその平均値を求める。
【００１９】
実施例１
平均分子量１４００のポリ−３−メチルペンタンアジペートグリコール６０重量部、４，４’−ジフェニルメタンジイソシアネート２０重量部、１，４−ブタンジオール１０重量部、水酸基含有オルガノポリシロキサンとして、平均分子量が２，６００である下記構造式で示されるものを１重量部用いて溶融重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【化１７】
実施例２
平均分子量１１００のポリテトラメチレンエーテルグリコール１１０重量部、４，４’−ジフェニルメタンジイソシアネート７５重量部、１，４−ブタンジオール１８重量部、水酸基含有オルガノポリシロキサンとして、平均分子量が２，７００である下記構造式で示されるものを１重量部用い、溶媒としてジメチルホルムアミドを用いて溶液重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【化１８】
実施例３（参考例）
平均分子量１１００のポリテトラメチレンエーテルグリコール１１０重量部、４，４’−ジフェニルメタンジイソシアネート１００重量部、１，４−ブタンジオール２７重量部、水酸基含有オルガノポリシロキサンとして、平均分子量が６００である下記構造式で示されるものを１重量部用い、溶媒としてジメチルホルムアミドを用いて溶液重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【化１９】
実施例４
平均分子量１４５０のポリカプロラクトンジオール１４５重量部、４，４’−ジフェニルメタンジイソシアネート５０重量部、１，４−ブタンジオール９重量部、水酸基含有オルガノポリシロキサンとして、平均分子量が７７，０００である下記構造式で示されるものを１重量部用い、溶媒としてジメチルホルムアミドを用いて溶液重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【化２０】
実施例５（参考例）
平均分子量１４５０のポリカプロラクトンジオール１４５重量部、４，４’−ジフェニルメタンジイソシアネート７５重量部、１，４−ブタンジオール１８重量部、水酸基含有オルガノポリシロキサンとして、平均分子量が１，３００である下記構造式で示されるものを１重量部用い、溶媒としてジメチルホルムアミドを用いて溶液重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【化２１】
実施例６
平均分子量１４５０のポリカプロラクトンジオール１４５重量部、４，４’−ジフェニルメタンジイソシアネート１００重量部、１，４−ブタンジオール２７重量部、水酸基含有オルガノポリシロキサンとして、平均分子量が１４，０００である下記構造式で示されるものを１重量部用い、溶媒としてジメチルホルムアミドを用いて溶液重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【化２２】
実施例７
平均分子量１４００のポリ−３−メチルペンタンアジペートグリコール６０重量部、４，４’−ジフェニルメタンジイソシアネート２０重量部、１，４−ブタンジオール１０重量部、水酸基含有オルガノポリシロキサンとして、平均分子量が３，７００である下記構造式で示されるものを１重量部用いて溶融重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【化２３】
比較例１
水酸基含有オルガノポリシロキサンを用いない以外は実施例１と同様にして重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【００２７】
比較例２
水酸基含有オルガノポリシロキサンに換えて下記構造式で示される平均分子量が７，６００のジメチルポリシロキサンを用いて実施例１と同様にして重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【化２４】
比較例３
水酸基含有オルガノポリシロキサンに換えて下記構造式で示される平均分子量が１１０，０００のジメチルポリシロキサンを用いて実施例１と同様にして重合させ、得られたポリウレタン樹脂に所定量のシリコーン系油剤Ａを付与して紡糸を行った。
【化２５】
実施例１〜７並びに比較例１〜３において紡糸されたポリウレタン弾性糸の紡糸性能、滑り性及び摩擦係数の評価を行い、その結果を表−１にまとめた。
【表１】
表−１から明らかなように、本発明の水酸基を含有するオルガノポリシロキサン、有機ジイソシアネート及びポリオール成分を反応させてなるポリウレタン弾性糸は、製造段階での紡糸油剤の軽減と紡糸後の滑り性を得ることが明らかにわかる。
【００３１】
【発明の効果】
本発明の特定の水酸基を含有するオルガノポリシロキサン、有機ジイソシアネート及びポリオール成分を反応させてなるポリウレタン弾性糸の製造方法により、従来紡糸段階で多量に使用されていた紡糸油剤を軽減でき、滑り性の優れたポリウレタン弾性糸を得ることができるので、産業上非常に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polyurethane elastic yarn and a polyurethane elastic yarn obtained by the production method, and more specifically, by containing a reaction product of an organopolysiloxane having a specific structure and an organic diisocyanate, the amount of spinning oil used is reduced. The present invention relates to a method for producing a polyurethane elastic yarn, and a polyurethane elastic yarn obtained by the production method.
[0002]
[Prior art]
Generally, polyurethane elastic yarns are produced by dry spinning in which a prepolymer is reacted with an isocyanate / hydrazine adduct in DMF and then spinning in a de-DMF step, or wet in which a prepolymer is dissolved in MEK or the like and spun. There are methods such as spinning or melt spinning, in which a crosslinking agent is added to a prepolymer and subjected to a heat reaction to spin with a special apparatus. In any case, in order to prevent low heat resistance of polyurethane, deformation at high temperature, and sticking between fibers, silicone oil is mainly used for spinning, for example, with respect to 100 parts by weight of polyurethane. It has been used in large quantities such as 10 parts by weight or more of spinning oil.
[0003]
However, even though a large amount of spinning oil can prevent the deformation at high temperatures and the mutual sticking of the fibers, if this remains, it will become an alienation factor in processes such as soiling and dyeing in the subsequent process. The process to do is needed. At this time, since the amount of the spinning oil was large, there was a problem that the amount of the cleaning chemical was increased, the cleaning time was long, and the amount of cleaning waste liquid was also large.
[0004]
In addition, since polyurethane elastic yarns are often used in blend spinning, in recent years, slip properties after spinning have been required for the purpose of improving the durability of fibers.
[0005]
[Problems to be solved by the invention]
The present invention aims to reduce the amount of spinning oil that has been used in large amounts in the production stage of polyurethane elastic yarns as described above, and to obtain the slipperiness after spinning, and in particular, to achieve these purposes. It is an object to provide a method for producing a polyurethane elastic yarn.
[0006]
[Means for Solving the Problems]
As a result of intensive studies on the above-mentioned problems, the present inventors have developed an excellent spinnability by including a reaction product of an organopolysiloxane having a specific structure and an organic diisocyanate during the production of a polyurethane elastic yarn. The inventors found that the spinning oil agent can be reduced more than the production method of the polyurethane elastic yarn, and that the polyurethane elastic yarn obtained by the method is excellent in slipperiness, and further studied and completed the present invention.
[0007]
Summary of the Invention
That is, the present invention
(I) The following formula (1):
[Chemical formula 5]
And 100 parts by weight of a polyurethane obtained by reacting an organopolysiloxane having an average of at least one hydroxyl group in one molecule, an organic diisocyanate, and a polyol component. A method for producing a polyurethane elastic yarn, characterized in that
(B) polyurethane elastic yarn produced by the method of (a) above,
(C) In the formula (1), the A group is represented by the following formula:
[Chemical 6]
(D) polyurethane elastic yarn produced by the method of (c) above,
(E) The following formula (1) :
[Chemical 7]
[Chemical 8]
In an average of at least one hydroxyl group in one molecule and 100 parts by weight of polyurethane obtained by reacting an organopolysiloxane having an average molecular weight of 500 to 100,000, an organic diisocyanate and a polyol component, A method for producing a polyurethane elastic yarn, characterized in that spinning is carried out by applying 10 parts by weight or less of a spinning oil, and
( F ) The present invention relates to a polyurethane elastic yarn produced by the method ( e ).
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Furthermore, the organopolysiloxane containing a hydroxyl group used in the present invention will be described. R 1 in the above formula (1) is a monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group. , A decyl group, a phenyl group, a tolyl group, a phenethyl group, etc., preferably a methyl group.
R 2 and R 5 in the above formula are divalent to tetravalent organic groups, for example, —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH (CH 3 ). CH 2 -, - (CH 2 ) 4 -, - (CH 2) 6 -, - (CH 2) 8 -, - CH 2 CH 2 C 6 H 4 -, - (CH 2) 12 -, - (CH 2) 16 -, - CO ( CH 2) 5 -, - CH, -CH (CH 2) 2, -C, -C (CH 2 -) 3, -C (CH 2 -) 2 (C 2 H 4 ), - (CH 2) 3 OCH (C 2 H 4 -) 2, -C (CH 2 -) (C 2 H 4 -) which is 2 or the like.
R 3 and R 6 are divalent organic groups, for example, —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH (CH 3 ) CH 2 —, — (CH 2 ) 4 -, - (CH 2 ) 6 -, - (CH 2) 8 -, - CH 2 CH 2 C 6 H 4 -, - (CH 2) 12 -, - (CH 2) 16 -, - CO ( , and the like - CH 2) 5.
R 4 in the above formula is a hydrogen atom or a monovalent organic group such as methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, phenyl group, phenethyl group, acetyl group and the like.
p and q are 1 to 3, which is a number obtained by subtracting 1 from the valence in conjunction with the valence of the corresponding organic group of R 2 and R 5 . m is a positive integer, n is 0 or an integer of 1 or more, and a and b are 0 or an integer of 1 or more.
A is R 1 or —R 5 {(OR 6 ) b —OR 7 } q or a hydroxyl group or an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and the like, and —R 5 {( OR 6 ) b -OR 7 } q may be present in the side chain, at the molecular end, or at both, as shown in the general formula.
[0009]
Furthermore, the average molecular weight of the organopolysiloxane containing a hydroxyl group used in the present invention is 500 to 100,000, preferably the average molecular weight is 500 to 10,000, and more preferably the average molecular weight is 500 to 5,000. It is. If the average molecular weight of the organopolysiloxane containing a hydroxyl group is too large, the physical properties such as the strength of the polyurethane elastic yarn obtained will decrease because the urethanization rate will decrease, and if the average molecular weight is too small, the spinnability and slippage will be reduced. Since the improvement of property is not fully expressed, it is not preferable respectively.
[0010]
Specific examples of the organopolysiloxane containing a hydroxyl group used in the present invention include the following, but are not limited thereto.
Hydroxyl group-containing organopolysiloxane represented by the following structure having an average molecular weight of 2,600.
[Chemical 9]
[Chemical Formula 10]
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When a polyurethane is produced by reacting an organopolysiloxane containing a hydroxyl group used in the present invention, an organic diisocyanate and a polyol component, these components are solution-polymerized in an organic solvent such as dimethylformamide, or directly mixed. And can be melt polymerized. At this time, a polyurethane production catalyst such as a tertiary amine or an organic tin compound may or may not be used.
[0012]
Examples of the organic diisocyanate to be reacted with the organopolysiloxane containing a hydroxyl group used in the present invention include alkylene diisocyanate and arylene diisocyanate such as p, p′-diphenylmethane diisocyanate, 2,4- or 2,6-toluylene diisocyanate, 1, 3-diisocyanato-o, m or p-xylene, hydrogenated p, p′-diphenylmethane diisocyanate, tetramethylene diisocyanate, 1,5-naphthalenediisocyanate, isophorone diisocyanate, and the like can be used.
[0013]
In order to produce a polyurethane containing a reaction product of an organopolysiloxane containing a hydroxyl group and an organic diisocyanate used in the present invention, as a polyol component, ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, etc. Polyols, and alkylene oxide adducts such as these polyols, caprolactone, polycaprolactone, and the like can be used. For example, it is preferable to use a bifunctional diol such as poly-3-methyladipate glycol, polytetramethylene glycol, polypropylene glycol, polybutylene diol, polycaprolactone diol, or polycarbonate diol, or a trifunctional polyol composed of caprolactam and trimethylolpropane. Can do.
[0014]
Polyurethane containing the reaction product of organopolysiloxane containing hydroxyl group and organic diisocyanate produced according to the present invention includes other additives such as silane compounds, crosslinking agents, antistatic agents, salts, dimethylpolysiloxane, epoxy groups Various polysiloxanes such as a containing organopolysiloxane, a carboxy group-containing organopolysiloxane, a polysiloxane / polyoxyalkylene copolymer, and an amino group-containing organopolysiloxane can be contained within a range in which the effects of the present invention are not impaired. .
[0015]
As a method for spinning a polyurethane containing a reaction product of an organopolysiloxane containing a hydroxyl group and an organic diisocyanate produced according to the present invention, a general method such as dry spinning, wet spinning, or melt spinning may be used. it can.
[0016]
In the case of spinning a polyurethane containing a reaction product of an organopolysiloxane containing a hydroxyl group and an organic diisocyanate produced according to the present invention, the spinning oil is added in an amount of 10 parts by weight or less to 100 parts by weight of the polyurethane of the present invention. It is characterized by doing.
[0017]
The spinning oil used in the present invention is not particularly limited, and those commercially available as conventionally known spinning oils for polyurethane can be used. For example, water-free oil consisting of fine particles of mineral oil and 2 to 20% by weight of metal soap, oil containing low viscosity polyethylene in low viscosity paraffin, polydimethylsiloxane oil, polyoxyalkylene modified polysiloxane Used oil agent.
[0018]
【Example】
Next, although this invention is demonstrated based on an Example, this invention is not limited to these. The blending amount is% by weight. Prior to the examples, evaluation methods are shown below.
Application amount of spinning oil 2%, 5%, 10%, or 15% of silicone oil A (based on mineral oil containing 5% dimethylpolysiloxane) as a spinning oil And spinning.
Method for preparing test cloth A spun polyurethane elastic yarn was further blended with nylon at a ratio of 50/50 to prepare a test cloth.
Evaluation of spinning performance The state of yarn in the spinning process was evaluated according to the following criteria.
(Slipperiness) ◎: Very smooth ○: Smooth △: Slightly smooth ×: Non-slip
Friction coefficient evaluation The surface property (friction coefficient) of the test cloth is measured six times with a surface testing machine of a fiber property measuring system KES-FB4 manufactured by Kato Tech Co., Ltd., and the average value is obtained.
[0019]
Example 1
The average molecular weight is 2,600 as poly-3-methylpentaneadipate glycol 60 parts by weight, 4,4′-diphenylmethane diisocyanate 20 parts by weight, 1,4-butanediol 10 parts by weight, and hydroxyl group-containing organopolysiloxane. Then, 1 part by weight of the compound represented by the following structural formula was melt polymerized, and a predetermined amount of the silicone-based oil A was applied to the obtained polyurethane resin for spinning.
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Example 2
110 parts by weight of polytetramethylene ether glycol having an average molecular weight of 1100, 75 parts by weight of 4,4′-diphenylmethane diisocyanate, 18 parts by weight of 1,4-butanediol, and an average molecular weight of 2,700 Using 1 part by weight of the compound represented by the structural formula, solution polymerization was performed using dimethylformamide as a solvent, and a predetermined amount of a silicone-based oil A was applied to the obtained polyurethane resin, and spinning was performed.
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Example 3 (Reference Example)
110 parts by weight of polytetramethylene ether glycol having an average molecular weight of 1100, 100 parts by weight of 4,4′-diphenylmethane diisocyanate, 27 parts by weight of 1,4-butanediol, and the following structural formula having an average molecular weight of 600 as a hydroxyl group-containing organopolysiloxane Was used for solution polymerization using dimethylformamide as a solvent, and a predetermined amount of silicone-based oil A was applied to the obtained polyurethane resin to perform spinning.
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Example 4
145 parts by weight of polycaprolactone diol having an average molecular weight of 1450, 50 parts by weight of 4,4′-diphenylmethane diisocyanate, 9 parts by weight of 1,4-butanediol, and the following structural formula having an average molecular weight of 77,000 as a hydroxyl group-containing organopolysiloxane Was used for solution polymerization using dimethylformamide as a solvent, and a predetermined amount of silicone-based oil A was applied to the obtained polyurethane resin to perform spinning.
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Example 5 (Reference Example)
145 parts by weight of polycaprolactone diol having an average molecular weight of 1450, 75 parts by weight of 4,4′-diphenylmethane diisocyanate, 18 parts by weight of 1,4-butanediol, and the following structural formula having an average molecular weight of 1,300 as a hydroxyl group-containing organopolysiloxane Was used for solution polymerization using dimethylformamide as a solvent, and a predetermined amount of silicone-based oil A was applied to the obtained polyurethane resin to perform spinning.
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Example 6
145 parts by weight of polycaprolactone diol having an average molecular weight of 1450, 100 parts by weight of 4,4′-diphenylmethane diisocyanate, 27 parts by weight of 1,4-butanediol, and the following structural formula having an average molecular weight of 14,000 as a hydroxyl group-containing organopolysiloxane Was used for solution polymerization using dimethylformamide as a solvent, and a predetermined amount of silicone-based oil A was applied to the obtained polyurethane resin to perform spinning.
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Example 7
As an average molecular weight of 1,400 poly-3-methylpentane adipate glycol 60 parts by weight, 4,4′-diphenylmethane diisocyanate 20 parts by weight, 1,4-butanediol 10 parts by weight, and a hydroxyl group-containing organopolysiloxane having an average molecular weight of 3,700 Then, 1 part by weight of the compound represented by the following structural formula was melt polymerized, and a predetermined amount of the silicone-based oil A was applied to the obtained polyurethane resin for spinning.
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Comparative Example 1
Polymerization was carried out in the same manner as in Example 1 except that the hydroxyl group-containing organopolysiloxane was not used, and a predetermined amount of the silicone-based oil A was applied to the obtained polyurethane resin for spinning.
[0027]
Comparative Example 2
Polymerization was carried out in the same manner as in Example 1 using dimethylpolysiloxane having an average molecular weight of 7,600 represented by the following structural formula instead of the hydroxyl group-containing organopolysiloxane, and a predetermined amount of silicone-based oil A was added to the obtained polyurethane resin. Was applied for spinning.
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Comparative Example 3
Polymerization was carried out in the same manner as in Example 1 using dimethylpolysiloxane having an average molecular weight of 110,000 represented by the following structural formula instead of the hydroxyl group-containing organopolysiloxane, and a predetermined amount of silicone oil A was added to the obtained polyurethane resin. Was applied for spinning.
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The spinning performance, slipperiness and friction coefficient of the polyurethane elastic yarn spun in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated, and the results are summarized in Table 1.
[Table 1]
As is clear from Table 1, the polyurethane elastic yarn obtained by reacting the organopolysiloxane containing the hydroxyl group of the present invention, the organic diisocyanate, and the polyol component has reduced spinning oil agent at the production stage and slipperiness after spinning. You can clearly see that you get.
[0031]
【The invention's effect】
According to the method for producing a polyurethane elastic yarn obtained by reacting an organopolysiloxane containing a specific hydroxyl group, an organic diisocyanate and a polyol component of the present invention, the amount of spinning oil that has been used in a large amount in the conventional spinning stage can be reduced. Since an excellent polyurethane elastic yarn can be obtained, it is very useful industrially.
Claims (6)
で示される、１分子中に平均で少なくとも１個の水酸基を含有するオルガノポリシロキサン、有機ジイソシアネート及びポリオール成分を反応させてなるポリウレタン１００重量部に対し、紡糸油剤１０重量部以下を付与して紡糸することを特徴とするポリウレタン弾性糸の製造方法。The following formula (1):
And 100 parts by weight of a polyurethane obtained by reacting an organopolysiloxane containing at least one hydroxyl group on average in one molecule, an organic diisocyanate, and a polyol component. A method for producing a polyurethane elastic yarn, comprising:
で示され、１分子中に平均で少なくとも１個の水酸基を含有し、平均分子量が５００〜１００，０００であるオルガノポリシロキサン、有機ジイソシアネート及びポリオール成分を反応させてなるポリウレタン１００重量部に対し、紡糸油剤１０重量部以下を付与して紡糸することを特徴とするポリウレタン弾性糸の製造方法。 The following formula (1) :
In an average of at least one hydroxyl group in one molecule and 100 parts by weight of polyurethane obtained by reacting an organopolysiloxane having an average molecular weight of 500 to 100,000, an organic diisocyanate and a polyol component, A method for producing a polyurethane elastic yarn, comprising spinning by applying 10 parts by weight or less of a spinning oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25576095A JP3833287B2 (en) | 1995-09-08 | 1995-09-08 | Method for producing polyurethane elastic yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25576095A JP3833287B2 (en) | 1995-09-08 | 1995-09-08 | Method for producing polyurethane elastic yarn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0978348A JPH0978348A (en) | 1997-03-25 |
| JP3833287B2 true JP3833287B2 (en) | 2006-10-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25576095A Expired - Fee Related JP3833287B2 (en) | 1995-09-08 | 1995-09-08 | Method for producing polyurethane elastic yarn |
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| JP (1) | JP3833287B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19824333A1 (en) * | 1998-06-02 | 1999-12-09 | Bayer Ag | Elastane threads and process for their manufacture |
| JP4369590B2 (en) * | 2000-01-27 | 2009-11-25 | 松本油脂製薬株式会社 | Elastic fiber with excellent antistatic properties |
| CN100537859C (en) | 2003-07-16 | 2009-09-09 | 李绍光 | A kind of melt spinning method of making polyurethane elastomeric fiber |
| CN115948813B (en) * | 2023-01-31 | 2023-08-25 | 露乐健康科技股份有限公司 | Material with traceless tightening prevention function and preparation method and application thereof |
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1995
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| JPH0978348A (en) | 1997-03-25 |
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