JP2007039817A - Method for producing elastic yarn of polyether-ester block copolymer - Google Patents
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000003921 oil Substances 0.000 claims abstract description 37
- -1 ester salt Chemical class 0.000 claims abstract description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002480 mineral oil Substances 0.000 claims abstract description 11
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 238000002074 melt spinning Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 abstract description 13
- 230000005611 electricity Effects 0.000 abstract description 12
- 229920001296 polysiloxane Polymers 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 238000004804 winding Methods 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000004611 light stabiliser Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- RQINQJTUMGQYOB-UHFFFAOYSA-N 6-methylheptyl dihydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(O)=O RQINQJTUMGQYOB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Abstract
Description
本発明は、ポリエーテルエステルブロック共重合体弾性糸の製造方法に関する。さらに詳しくは、本発明は、製糸時の油剤(以下「処理剤」と称することがある)の飛散もなく、かつ油剤付着斑や張力変動斑も少なく安定したパッケージが得られると共に、巻取パッケージからの解舒性に優れ、また糸の走行時においては静電気の発生が少なく、スカムの発生も抑制された取扱い性が極めて良好なポリエーテルエステルブロック共童合体弾性糸を製造する方法に関するものである。 The present invention relates to a method for producing a polyetherester block copolymer elastic yarn. More specifically, the present invention provides a stable package with no scattering of oil agent (hereinafter sometimes referred to as "treatment agent") at the time of yarn production, less oil agent adhesion spots and tension fluctuation spots, and a winding package. This method relates to a method for producing a polyetherester block co-op elastic yarn that has excellent unwinding properties and has low static generation during running of the yarn and is extremely easy to handle with reduced scum generation. is there.
従来、弾性糸としては、ゴム、ポリウレタン系の弾性糸が使用され、身体へのフィット性が要求される分野、例えば海水着、スキーズボン、トレーニングパンツなどの多方面に利用されている。
近年、ポリブチレンテレフタレートのようなポリエステルをハードセグメントとし、ポリテトラメチレングリコールをソフトセグメントとするポリエーテルエステルブロック共重合体からの弾性糸は、その化学構造がポリエステル繊維に類似していることから、従来の弾性糸では耐熱性、耐薬品性不足でポリエステル繊維と同等の条件で後加工(例えば、アルカリ減量加工など)するには耐えられなかった問題を解決するものとして期待され、種々実用化検討がなされてきている。しかしながら、かかるポリエーテルエステルブロツク共重合体弾性糸は、大量に商業生産、使用する場合、製糸時にローラーや巻取機周辺に油剤が飛散したり、張力変動班による巻取パッケージ不良(綾落ち)の発生、および糸走行時静電気が発生したり、合糸、カバリング、製編織工程でスカムの発生に伴う各種のトラブルを惹起するという間題があった。
Conventionally, rubber and polyurethane-based elastic yarns are used as elastic yarns, which are used in various fields such as swimwear, ski trousers, training pants and the like that require fit to the body.
In recent years, an elastic yarn from a polyether ester block copolymer having a polyester such as polybutylene terephthalate as a hard segment and a polytetramethylene glycol as a soft segment has a similar chemical structure to a polyester fiber. It is expected to solve the problems that conventional elastic yarns could not withstand post-processing (for example, alkali weight loss processing) under the same conditions as polyester fiber due to insufficient heat resistance and chemical resistance, and various practical application studies Has been made. However, such a polyetherester block copolymer elastic yarn is used in large quantities for commercial production and use. And the occurrence of static electricity during yarn running, and various problems associated with the occurrence of scum in the yarn joining, covering, and weaving processes.
従来、ポリウレタン系弾性糸においては、シリーコンや鉱物油を主体成分とし、これに種々の高級脂肪酸エステル、高級アルコールのエチレンオキサイド付加物、高級脂肪酸金属塩、変性シリコーンなどを配合した非水系処理剤が数多く提案されている。かかる処理剤は、ウレタン系弾性糸の解舒性向上絡果をもたらすものの、ポリエーテルエステルブロック共重合体弾性糸に適用しても、該弾性糸自体はウレタン弾性糸に比べて静電気が発生しやすいため、静電気によるトラブルが発生する。また、ウレタン系弾性糸では、通常、非水系の処理剤として付与されるが、非水系では給油時の処理剤粘度の調整が難しく、巻取張力の変動が大きくなって巻取パッケージの綾落ち(綾外れ)が発生しやすくなるという問題もある。 Conventionally, in polyurethane-based elastic yarns, there are non-aqueous treatment agents that mainly contain silicone and mineral oils, which are blended with various higher fatty acid esters, higher alcohol ethylene oxide adducts, higher fatty acid metal salts, modified silicones, and the like. Many proposals have been made. Although such a treatment agent brings about the effect of improving the unwinding property of the urethane-based elastic yarn, even when applied to the polyetherester block copolymer elastic yarn, the elastic yarn itself generates static electricity compared to the urethane elastic yarn. It is easy to cause troubles due to static electricity. Urethane elastic yarns are usually applied as non-aqueous processing agents, but in non-aqueous systems, it is difficult to adjust the viscosity of the processing agent during refueling, and the winding tension fluctuates greatly, causing the winding package to fall off. There is also a problem that (twilling off) is likely to occur.
一方、特許文献１（特開平４-３５２８７８号公報）には、ポリジメチルシリコーンに代えてポリジメチルシロキサンジオール(重合度５０以下の低分子量)を主体成分とする水系処理剤が提案されている。しかし、このものは、ポリジメチルシロキサンジオールが多分に反応性を有しているため、糸上に付着した状熊で重合が進行し、走行摩擦が経時的に増加して、後加工時に断糸発生が増加するという問題がある。 On the other hand, Patent Document 1 (Japanese Patent Application Laid-Open No. 4-352878) proposes an aqueous treatment agent mainly composed of polydimethylsiloxanediol (low molecular weight having a polymerization degree of 50 or less) instead of polydimethylsilicone. However, in this case, polydimethylsiloxane diol is highly reactive, so polymerization progresses with the bear attached to the yarn, running friction increases over time, and yarn breaks during post-processing. There is a problem that the occurrence increases.
また、特許文献２（特開平８−２９６１２６号公報）には、鉱物油および／またはポリジメチルシリコーンを７０重量%以上、ならびに高級アルコールのエチレンオキサイド付加物の部分リン酸エステル塩を１０〜２０重量％含有する油剤を、２５℃における粘度が４〜１５ｍｍ２／ｓの水系エマルジョンとして付与する方法が提案されている。これにより、大部分の用途で安定に使用できるが、上記油剤を付与した弾性糸を長期間経時した後に使用した場合に、スカムの発生により糸切れなどのトラブルを引き起こす問題が残されていた。
本発明は、上記従来技術に鑑みなされたもので、その目的とするところは、製糸時の処理剤飛散が少なく、かつ張力変動斑による巻取パッケージ不良(綾落ち)の発生もなく、また走行時の摩擦が小さくて静電気の発生が少なく、スカムの発生も抑制された取扱い性に優れたれたポリエーテルエステルブロツク共重合体弾性糸を製造する方法を提供することにある。 The present invention has been made in view of the above-described prior art, and the purpose thereof is that there is little scattering of the processing agent at the time of yarn production, and there is no occurrence of winding package defects (falling) due to uneven tension, and traveling It is an object of the present invention to provide a method for producing a polyetherester block copolymer elastic yarn excellent in handleability in which friction at the time is small, generation of static electricity is small, and generation of scum is suppressed.
本発明は、ポリエーテルエステルブロック共重合体を溶融紡糸するに際し、鉱物油および／またはポリジメチルシリコーンを８０重量％以上、ならびに高級アルコールのエチレンオキサイド付加物の部分リン酸エステル塩を０.５〜３重量％含有する油剤を、粘度が２〜１０ｍｍ２／ｓの水系エマルジョンとして付与することを特徴とするポリエーテルエステルブロック共重合体弾性糸の製造方法に関する。
ここで、上記油剤の付与量は、繊維重量を基準として１．５〜４．０重量％であることが好ましい。
また、本発明に適用されるポリエーテルエステルブロック共重合体弾性糸の横断面形状は、中央部の断面部Ａとその周囲におのおの独立して該断面部Ａに接合した３〜５個の円形の断面部Ｂとくびれた接合部Ｃとから構成され、かつ下記（１）〜(２)を満足する形状であることが好ましい。
（１）弾性糸横断面の、外接円の直径Ｄと内接円の直径ｄとの比(Ｄ／ｄ)が１．５〜４．０
(２)断面部Ｂの最大幅Ｗと接合部Ｃの最小幅ｗとの比(Ｗ／ｗ)が０．９〜３．０
In the present invention, when melt-spinning a polyetherester block copolymer, mineral oil and / or polydimethylsilicone is 80% by weight or more, and a partial phosphate ester salt of a higher alcohol ethylene oxide adduct is 0.5 to 0.5%. The present invention relates to a method for producing a polyetherester block copolymer elastic yarn, wherein an oil agent containing 3% by weight is applied as a water-based emulsion having a viscosity of 2 to 10 mm 2 / s.
Here, the application amount of the oil is preferably 1.5 to 4.0% by weight based on the fiber weight.
In addition, the cross-sectional shape of the polyetherester block copolymer elastic yarn applied to the present invention is 3-5 circles joined to the cross-section A independently at the cross-section A at the center and the periphery thereof. The cross-sectional portion B and the constricted joint portion C are preferable, and the shape satisfies the following (1) to (2).
(1) The ratio (D / d) of the diameter D of the circumscribed circle to the diameter d of the inscribed circle in the cross section of the elastic yarn is 1.5 to 4.0.
(2) The ratio (W / w) between the maximum width W of the cross section B and the minimum width w of the joint C is 0.9 to 3.0.
本発明で用いられる油剤は、鉱物油および／またはポリジメチルシリコーンを主体成分とし、これにエチレンオキサイド付加物の部分リン酸エステル塩を適当量配合したものであり、またこれを水系エマルジョンとして弾性糸に付与しているので、処理剤の付着斑が防止されて巻取パッケージ不良の発生が抑制されると共に、平滑性および静電気発生防止性能も良好で、極めて品位の良好な弾性糸を工業的に安定して得ることができる。また、特定の弾性糸の横断面を特定の形状とすることにより、走行糸と各工程でのガイドなどとの接触面積が最低限に抑えられるため、エチレンオキサイド付加物の部分リン酸エステル塩の含有量を少なくしても静電気によるトラプルが発生しない。また、長期問の経時によりエチレンオキサイド付加物の部分リン酸エステル塩が弾性糸中の光安定剤を抽出してスカムを発生させることもなく、安定に使用することができる。 The oil used in the present invention contains mineral oil and / or polydimethyl silicone as a main component, and is blended with an appropriate amount of a partial phosphate ester salt of an ethylene oxide adduct. As a result, the adhesion of the treatment agent is prevented and the occurrence of defective winding packages is suppressed, and the smoothness and static electricity generation prevention performance is also good. It can be obtained stably. In addition, by making the cross section of a specific elastic yarn into a specific shape, the contact area between the running yarn and the guide in each process can be minimized, so the partial phosphate ester salt of ethylene oxide adduct Even if the content is reduced, traps due to static electricity do not occur. Moreover, the partial phosphate ester salt of ethylene oxide adduct can be used stably without extracting scum by extracting the light stabilizer in the elastic yarn over a long period of time.
本発明は、高級アルコールにエチレンオキサイドを付加した化合物の部分リン酸エステル塩（以下「エチレンオキサイド付加アルキルホスフェート塩」と称することがある）は、ポリジメチルシリコーンや鉱物油を主体成分とする油剤中に含有させても、平滑性能を損なうことなく制電性能を発揮すること、さらに、その含有量を極力抑えることで、後に述べるポリエーテルエステルブロック共重合体弾性糸中に含まれる光安定剤を抽出することを最低限に抑えることでスカムの発生を抑制できることを見出したものである。 In the present invention, a partial phosphate ester salt of a compound obtained by adding ethylene oxide to a higher alcohol (hereinafter sometimes referred to as “ethylene oxide-added alkyl phosphate salt”) is an oil agent mainly composed of polydimethyl silicone or mineral oil. Even if it is contained, the light stabilizer contained in the polyether ester block copolymer elastic yarn described later is exhibited by suppressing the content as much as possible to exhibit the antistatic performance without impairing the smoothness performance. It has been found that the occurrence of scum can be suppressed by minimizing the extraction.
本発明が対象とするポリエーテルエステルブロック共重合体は、テレフタル酸を主とするジカルボン酸成分と、1,４−ブタンジオールまたはエチレングリコールを主とするグリコール成分と、平均分子量が４００〜４,０００のポリオキシアルキレングリコールを構成成分とする共重合体である。なかでも、ポリオキシアルキレングリコールとしては、平均分子量が１，０００〜３,０００のポリテトラメチレングリコールまたはポリエチレングリコールが好ましい。
ポリエーテルエステルブロック共重合体中のポリオキシアルキレングリコールの含有量は５０〜８０重量%の範囲にあることが好ましく、８０重量％を超えると、弾性的には性能の優れた弾性糸が得られるものの、該共重合体の融点が低くなりすぎるため、乾熱処理、湿熱処理時の弾性的性能が急激に低下し耐久性の劣る弾性糸となってしまう。一方、５０重量％未満では、永久歪が大きく弾性的性質に劣る弾性糸しか得られない。
The polyether ester block copolymer targeted by the present invention includes a dicarboxylic acid component mainly composed of terephthalic acid, a glycol component mainly composed of 1,4-butanediol or ethylene glycol, and an average molecular weight of 400 to 4, 000 polyoxyalkylene glycol as a constituent component. Especially, as polyoxyalkylene glycol, polytetramethylene glycol or polyethylene glycol having an average molecular weight of 1,000 to 3,000 is preferable.
The content of the polyoxyalkylene glycol in the polyetherester block copolymer is preferably in the range of 50 to 80% by weight, and if it exceeds 80% by weight, an elastic yarn excellent in performance can be obtained elastically. However, since the melting point of the copolymer becomes too low, the elastic performance at the time of dry heat treatment and wet heat treatment is drastically lowered and the elastic yarn is inferior in durability. On the other hand, if it is less than 50% by weight, only an elastic yarn having a large permanent strain and inferior elastic properties can be obtained.
さらに、耐紫外線、耐熱性などの耐久性を向上するため、上述のポリエーテルエステルブロック共重合体には、酸化防止剤、光安定剤、紫外線吸収剤などを添加するのが好ましい。かかる光安定剤としては、例えばヒンダードフェノール系化合物、ヒンダードアミン系化合物、硫黄原子含有エステル化合物などを、また、紫外線吸収剤としては、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サシレート系化合物などが例示される。 Furthermore, in order to improve durability such as ultraviolet resistance and heat resistance, it is preferable to add an antioxidant, a light stabilizer, an ultraviolet absorber, etc. to the above-mentioned polyether ester block copolymer. Examples of such light stabilizers include hindered phenol compounds, hindered amine compounds, and sulfur atom-containing ester compounds, and examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, and succinate compounds. The
本発明においては、上述のポリエーテルエステルブロック共重合体からなる弾性糸に、鉱物油および／またはポリジメチルシリコーン、ならびにエチレンオキサイド付加アルキルホスフェート塩を含有する油剤を付与することが必要である。 In the present invention, it is necessary to impart an oil containing a mineral oil and / or polydimethyl silicone and an ethylene oxide-added alkyl phosphate salt to the elastic yarn made of the above-mentioned polyether ester block copolymer.
ここで用いられるポリジメチルシリコーンは、２５℃における粘度が３〜２０ｍｍ２／s、特に５〜1５ｍｍ２／ｓ程度であることが好ましい。３ｍｍ２／ｓ未満の場合には、後述するエチレンオキサイド付加アルキルホフェート塩を用いても該シリコーンの揮発性を抑制することが困難となり、保存中に該シリコーン成分が揮散して弾性糸上の油剤組成比率が変化して平滑性が不充分となる。一方、２０ｍｍ２／ｓを超える場合には、得られる弾性糸の平滑性が不充分となるので好ましくない。
また、鉱物油は、２５℃における粘度が８〜１６ｍｍ２／ｓ程度であることが好ましく、この範囲未満ではポリジメチルシリコーンの場合と同様に揮散の問題が発生しやすい。一方、１６ｍｍ２／ｓを超える場合には、油剤系の粘度を高め糸への給油が不均一になりやすく、糸の平滑性も低下しやすい。
The polydimethylsilicone used here preferably has a viscosity at 25 ° C. of 3 to 20 mm 2 / s, particularly about 5 to 15 mm 2 / s. In the case of less than 3 mm 2 / s, it becomes difficult to suppress the volatility of the silicone even if an ethylene oxide-added alkyl phosphate salt described later is used, and the silicone component is volatilized during storage and is on the elastic yarn. The oil agent composition ratio changes and the smoothness becomes insufficient. On the other hand, if it exceeds 20 mm 2 / s, the smoothness of the resulting elastic yarn becomes insufficient, such being undesirable.
Further, the mineral oil preferably has a viscosity at 25 ° C. of about 8 to 16 mm 2 / s, and if it is less than this range, the problem of volatilization is likely to occur as in the case of polydimethylsilicone. On the other hand, when it exceeds 16 mm 2 / s, the viscosity of the oil agent system is increased and the oil supply to the yarn is likely to be uneven, and the smoothness of the yarn is likely to be lowered.
次に、上記成分と併用されるエチレンオキサイド付加アルキルホスフェート塩のエチレンオキサイド付加モル数は、あまりに多いと静電気発生防止能力が低下しやすく、逆に少なすぎると平滑性が低下しやすい。したがって、エチレンオキサイドの付加モル数は、高級アルコール１モルに対して２〜１Oモルの範囲が好ましい。
一方、高級アルコールのアルキル基の炭素数は、その静電気発生防止の観点から８〜１８が好ましく、またホスフェート塩の対イオンとしてはＮａ、Ｋなどのアルカリ金属イオン、アンモニウムカチオンなどを例示することができ、特にＮａ、Ｋは静電気発生防止能力が大きいので好ましい。
好ましく用いられるエチレンオキサイド付加アルキルホスフェート塩としては、エチレンオキサイド付加(以下「ＥＯ付加」と略記することがある)イソオクチルホスフェートＫ塩、ＥＯ付加ラウリルホスフェートＫ塩、ＥＯ付加セカンダリーアルコール(炭素数１６〜１８のアルコール)ホスフェートＫ塩などを挙げることができる。
Next, if the number of moles of ethylene oxide added in the ethylene oxide-added alkyl phosphate salt used in combination with the above components is too large, the ability to prevent generation of static electricity tends to decrease, and conversely if too small, the smoothness tends to decrease. Therefore, the number of moles of ethylene oxide added is preferably in the range of 2 to 10 moles per mole of higher alcohol.
On the other hand, the number of carbon atoms of the alkyl group of the higher alcohol is preferably 8 to 18 from the viewpoint of preventing the generation of static electricity, and examples of the counter ion of the phosphate salt include alkali metal ions such as Na and K, ammonium cations, and the like. In particular, Na and K are preferable because they have a large ability to prevent generation of static electricity.
Examples of the ethylene oxide-added alkyl phosphate salt preferably used include ethylene oxide addition (hereinafter sometimes referred to as “EO addition”) isooctyl phosphate K salt, EO addition lauryl phosphate K salt, EO addition secondary alcohol (having 16 to 16 carbon atoms). 18 alcohol) phosphate K salts and the like.
本発明において用いられる油剤には、上記に詳述した鉱物油とジメチルシリコーンの合計量が油剤有効成分に対して８０重量％以上、好ましくは８５〜９５重量％含まれている必要がある。この含有量が８０重量％未満の場合には、平滑性が不充分となって糸の走行安定性が低下し、糸の異常伸長力が発生するので好ましくない。 In the oil agent used in the present invention, the total amount of the mineral oil and dimethyl silicone detailed above must be 80% by weight or more, preferably 85 to 95% by weight, based on the active ingredient of the oil agent. When the content is less than 80% by weight, the smoothness becomes insufficient, the running stability of the yarn is lowered, and an abnormal elongation force of the yarn is generated, which is not preferable.
また、エチレンオキサイド付加アルキルホスフェート塩の含有量は、油剤有効成分に対して０．５〜３重量％である必要がある。好ましくは、１．５〜３重量％である。この含有量が０．５重量％未満の場合には、制電性能が不充分となり、一方３重量％を超える場合にはポリエーテルエステルブロツク共重体弾性糸中の光安定剤などを徐々に抽出しスカムの発生原因となるため好ましくない。 Moreover, content of ethylene oxide addition alkyl phosphate salt needs to be 0.5 to 3 weight% with respect to an oil agent active ingredient. Preferably, it is 1.5 to 3% by weight. When the content is less than 0.5% by weight, the antistatic performance becomes insufficient. On the other hand, when the content exceeds 3% by weight, the light stabilizer in the polyetherester block copolymer elastic yarn is gradually extracted. However, this is not preferable because it causes scum.
本発明における油剤は、上記の成分を基剤とするものであるが、必要に応じて他の配合剤、例えば酸化防止剤、防腐剤、紫外線吸収剤などの安定性向上剤などや、脂肪酸またはアルコールで変性したシリコーン化合物などの平滑助剤を、本発明の目的を損なわない範囲で添加してもよい。 The oil agent in the present invention is based on the above components, but if necessary, other compounding agents, for example, stability improvers such as antioxidants, preservatives, ultraviolet absorbers, fatty acids or A smoothing aid such as a silicone compound modified with alcohol may be added within a range not impairing the object of the present invention.
本発明においては、以上に説明した油剤を公知の乳化剤を用いて水で乳化させて使用する。油剤の弾性糸への付与は、従来公知の手段いずれをも採用することができるが、なかでも糸に与える抵抗を少なくするオイリングノズルを介して計量された量を付与する方法が、より好ましい方法として採られる。 In the present invention, the oil agent described above is used by emulsifying with water using a known emulsifier. For applying the oil agent to the elastic yarn, any conventionally known means can be adopted, but among them, a method of giving a measured amount through an oiling nozzle that reduces resistance given to the yarn is more preferable. Taken as.
本発明においては、以上に説明した油剤を水で乳化させ、粘度が２〜１０ｍｍ２／ｓ、好ましくは２．５〜５ｍｍ２／ｓのエマルジョンとして弾性糸に付着させることが肝要である。エマルジョンの粘度が２ｍｍ２／ｓ未満の場合には、油剤が非常に飛散しやすく、巻取り機周辺やローラーを著しく汚染し、ひどい場合には製糸時の断糸を引き起こすので好ましくない。一方、１０ｍｍ２／ｓを超える場合には、油剤の付着斑による張カ変動が発生し、巻取りパッケージ不良(綾落ち)が発生するという問題が生じる。
いずれにしても、本発明の油剤では、上記範囲に近い粘度となるが状況に応じて油剤付与および巻取り部分の例えば室温を調整することで適正な粘度範囲としてやることが重要である。例えば、季節によって室温が変化する、昼夜の温度差が生じる、といった原因で粘度範囲が適正値から外れると、飛散増加や綾落ちにつながるので好ましくない。
In the present invention, it is important to emulsify the oil agent described above with water and adhere it to the elastic yarn as an emulsion having a viscosity of 2 to 10 mm 2 / s, preferably 2.5 to 5 mm 2 / s. When the viscosity of the emulsion is less than 2 mm 2 / s, the oil agent is very likely to scatter, and the periphery of the winder and the roller are significantly contaminated. On the other hand, if it exceeds 10 mm 2 / s, the tension variation due to the adhesion spots of the oil agent occurs, and there arises a problem that a winding package defect (falling) occurs.
In any case, the oil agent of the present invention has a viscosity close to the above range, but it is important to adjust the oil agent to an appropriate viscosity range by adjusting, for example, the room temperature of the oil application and winding part according to the situation. For example, if the viscosity range deviates from an appropriate value due to a change in room temperature depending on the season or a temperature difference between day and night, it is not preferable because it leads to increased scattering and falling.
油剤の弾性糸への付与量は、繊維重量を基準として１．５〜４．０重量％(有効成分として)が好ましく、付与量がこの範囲未満になると平滑性や制電性が低下して糸切れやスカム発生のトラブルが起こりやすくなり、逆にこの範囲を超えると過剰の油剤が糸導などを汚染しやすくなり商業的にも得策でない。 The amount of the oil agent applied to the elastic yarn is preferably 1.5 to 4.0% by weight (as an active ingredient) based on the fiber weight, and if the amount applied is less than this range, the smoothness and antistatic properties are reduced. Troubles of thread breakage and scum are likely to occur. Conversely, if this range is exceeded, excessive oil will easily contaminate the thread guide and the like, which is not commercially viable.
なお、本発明のポリエーテルエステルブロック共重合体弾性糸の横断面形状は、中央部の断面部Ａとその周囲におのおの独立して該断面部Ａに接合した３〜５個の円形の断面部Ｂとくびれた接合部Ｃとから構成され、かつ下記(１)〜(２)を満足する多葉断面形状であることが好ましい。
(1)弾性糸横断面の、外接円の直径Ｄと内接円の直径ｄとの比(Ｄ／ｄ)が１．５〜４．０
(２)断面部Ｂの最大幅Ｗと接合部Ｃの最小幅ｗとの比（ｗ／ｗ)が０．９〜３．０
このような断面を有することで、弾性糸を合糸、カバリング、製編織工程において使用する際、走行糸と各工程でのガイドなどとの接触面積が最低限に抑えられるため、エチレンオーキサイド付加アルキルホスフェート塩の含有量を少なくしても静電気によるトラブルが発生しない。また、長期間の経時によりエチレンオキサイド付加アルキルホスフェート塩が弾性糸中の光安定剤を抽出してスカムを発生させることもなく、安定に使用することができるのである。
In addition, the cross-sectional shape of the polyetherester block copolymer elastic yarn of the present invention is 3-5 circular cross-sections that are joined to the cross-section A independently at the cross-section A at the center and the periphery thereof. It is preferable that the multi-leaf cross-sectional shape is composed of B and the constricted joint C and satisfies the following (1) to (2).
(1) The ratio (D / d) of the diameter D of the circumscribed circle to the diameter d of the inscribed circle in the cross section of the elastic yarn is 1.5 to 4.0.
(2) The ratio (w / w) between the maximum width W of the cross section B and the minimum width w of the joint C is 0.9 to 3.0.
By having such a cross section, when using the elastic yarn in the combined yarn, covering and weaving processes, the contact area between the running yarn and the guide in each process is minimized, so the ethylene alkoxide addition Troubles due to static electricity do not occur even if the content of alkyl phosphate salt is reduced. Further, the ethylene oxide-added alkyl phosphate salt can be used stably without extracting scum by extracting the light stabilizer from the elastic yarn over a long period of time.
本発明の弾性糸は、モノフィラメントとするのが、耐光性、耐塩素性の面で好ましい。その単繊維繊度は、好ましくは５〜１００ｄｔｅｘ、より好ましくは１０〜８０ｄｔｅｘが弾性糸として適切である。
また、本発明の弾性糸は、例えば、以下の方法で製造することができる。すなわち、熱可塑性エラストマーを常法で乾燥し、通常の溶融紡糸装置に導入し、該熱可塑性エラストマーの耐熱特性に応じた溶融温度で溶融し、紡糸口金より吐出し、冷却し、上記本発明の紡糸油剤を付与して、８００〜１,５００ｍ／ｍｉｎの速度で紡糸引き取りし、ワインダーにてチーズ状のパッケージとして巻き取る。
The elastic yarn of the present invention is preferably a monofilament in terms of light resistance and chlorine resistance. The single fiber fineness is preferably 5 to 100 dtex, more preferably 10 to 80 dtex as the elastic yarn.
Moreover, the elastic yarn of this invention can be manufactured with the following method, for example. That is, the thermoplastic elastomer is dried by a conventional method, introduced into a normal melt spinning apparatus, melted at a melting temperature corresponding to the heat resistance characteristics of the thermoplastic elastomer, discharged from a spinneret, cooled, and A spinning oil agent is applied, the yarn is taken up at a speed of 800 to 1,500 m / min, and wound as a cheese-like package by a winder.
以下、実施例により本発明をより具体的に説明する。なお、実施例における各評価項目は下記方法にしたがって測定した。
1.油剤エマルジョン粘度
一定温度に設定した恒温水槽中、キャノンフェスケ粘度管を用いて定法により粘度を測定した(単位:ｍｍ２／Ｓ)。
Hereinafter, the present invention will be described more specifically with reference to examples. In addition, each evaluation item in an Example was measured in accordance with the following method.
1. Oil Emulsion Viscosity Viscosity was measured in a constant temperature water tank set at a constant temperature using a Canon Fesuke viscosity tube by a conventional method (unit: mm 2 / S).
２.油剤飛散性
オイリング後のローラー上に飛散した油滴を一般濾過用ろ紙(６０ｍｍx２０７ｍｍ、３枚重ね)に吸い取って２４時間当りの重量増をg単位で表した。
３.油剤揮散性
径８ｃｍのステンレス皿中に油剤２gを精秤し、５０℃の熱風乾燥器中２４時間放置後の重量減少率を測定し、次の基準で評定した。
○:１５％未満
△:１５％以上、３０％未満
×:３０％以上
2. Oil Agent Scattering The oil droplets scattered on the roller after oiling were sucked up on a filter paper for general filtration (60 mm x 207 mm, 3 layers), and the weight increase per 24 hours was expressed in g.
3. Volatility of oil agent 2 g of oil agent was precisely weighed in a stainless steel dish having a diameter of 8 cm, and the weight reduction rate after being left in a hot air dryer at 50 ° C. for 24 hours was measured and evaluated according to the following criteria.
○: Less than 15% △: 15% or more, less than 30% ×: 30% or more
４.綾落ち
巻取パッケージ１００本を外観検査し、端面に綾外れを発生しているパッケージの発生率を求め、次の基準で評定した。
○:綾外れなし
△:３％未満
×:３%以上
4. Twill fall 100 winding packages were visually inspected to determine the occurrence rate of packages with treads on the end faces, and evaluated according to the following criteria.
○: No treading △: Less than 3% ×: 3% or more
５．解舒性
巻取パッケージから、第1糸導ガイドまでの距離を25cmとし、この糸導を通して１０ｍ／分の速度で弾性糸(原糸)を引き出した。この時の解舒性を３段階評価した。
○:全く問題なく安定に解箭できる。
△:やや引き出す糸に抵抗感あるも糸切れの発生なし。
×:引き出す糸に抵抗感大きく、断糸が頻発する。
5. Unwindability The distance from the winding package to the first yarn guide was 25 cm, and the elastic yarn (raw yarn) was drawn through this yarn guide at a speed of 10 m / min. The unraveling property at this time was evaluated in three stages.
○: Can be solved stably without any problem.
Δ: Slight resistance to the drawn-out thread, but no thread breakage.
X: A feeling of resistance is great in the thread to be pulled out, and breakage occurs frequently.
６．平滑性
得られた弾性糸を１５ｍ／分の速度で解舒し、途中径６０ｍｍ、表面粗度１１Ｓの梨地クロムピンを１８０°の接触角で接触して巻取った。このときのピンの前後の張力(各々Ｔ１,Ｔ２:単位ｇ)から次式により摩擦係数(μ)を算出した。なお、Ｔ１は約５ｇに調整した。
μ=１／π[１ｎ(Ｔｌ／ｔ２)]
評価は次の基準で評定した。
○:０．３５未満
△:０．３５以上、０．４０未満
×:０．４０以上
6). Smoothness The obtained elastic yarn was unwound at a speed of 15 m / min, and a satin chrome pin having a diameter of 60 mm and a surface roughness of 11S was contacted at a contact angle of 180 ° and wound. The friction coefficient (μ) was calculated from the tension before and after the pin at this time (respectively T1, T2: unit g) by the following equation. T1 was adjusted to about 5 g.
μ = 1 / π [1n (Tl / t2)]
Evaluation was based on the following criteria.
○: Less than 0.35 △: 0.35 or more, less than 0.40 ×: 0.40 or more
７.制電性
得られた弾性糸を、１０本の枠立てにより整経機にかけ、経糸用ビームとして２０ｍ／分の速度で２０,０００ｍ巻取った。このとき、静電気発生状況を春日式集電気式電位測定器で測定した。なお、評価は下記の基準により評定した。
○:帯電圧１ＫＶ未満
△:帯電圧１ＫＶ以上、３ＫＶ未満
×:帯電圧３ＫＶ以上
7. Antistatic property The obtained elastic yarn was passed through a warping machine by 10 frame stands, and wound up to 20,000 m as a warp beam at a speed of 20 m / min. At this time, the state of static electricity generation was measured with a Kasuga-type collector potential measuring device. Evaluation was made according to the following criteria.
○: Charge voltage less than 1KV △: Charge voltage 1KV or more, less than 3KV ×: Charge voltage 3KV or more
８.スカム
得られた弾性糸を混繊機にて約２倍に伸長しながら約６００ｍ／ｍｉｎの速度で混繊巻取りし、5万m走行後のガイド上に堆積するスカムの量を目視確認し、下記の基準により評定した。
○:スカムの発生が全く認められない。
△:わずかにスカムの発生が認められるが糸の走行に影響はない。
×:スカムが大量に発生し場合によっては糸切れを起こすことがある。
8. Scum While the obtained elastic yarn is stretched about twice with a blending machine, the blended fiber is wound at a speed of about 600 m / min, and the amount of scum deposited on the guide after traveling 50,000 m is visually confirmed. The rating was based on the following criteria.
○: No occurrence of scum.
Δ: Scum is slightly generated, but there is no influence on the running of the yarn.
X: A large amount of scum is generated, and in some cases, thread breakage may occur.
実施例1〜４、比較例１〜２
ブチレンテレフタレートをハードセグメントとし、ポリテトラメチレングリコールをソフトセグメントとする、ハードセグメントの含有量が４０重量％であるポリエーテルエステルブロック共重合体を、２２５℃で溶融し、紡糸口金より押出し、８００ｍ／分の速度で巻取り４０デシテックス、1フィラメントの弾性糸を得た。この際、紡出糸には計量ノズルを介して表1記載の油剤を、２０重量％の水系エマルジョンとして、繊維重量を基準として油剤有効成分付着量が３重量%となるように付与した。評価結果を表1にまとめて示す。
Examples 1-4, Comparative Examples 1-2
A polyether ester block copolymer having a hard segment content of 40% by weight, butene terephthalate as a hard segment and polytetramethylene glycol as a soft segment, is melted at 225 ° C., extruded from a spinneret, and 800 m / Winding at a speed of 40 minutes, 40 decitex, 1 filament elastic yarn was obtained. At this time, the oil agent shown in Table 1 was applied to the spun yarn through a metering nozzle as a 20% by weight aqueous emulsion so that the amount of oil active ingredient adhesion was 3% by weight based on the fiber weight. The evaluation results are summarized in Table 1.
＊１）２５℃における粘度が１２ｍｍ２／ｓの鉱物油
＊２）２５℃における粘度が１０ｍｍ２／ｓのジメチルシリコーン
＊３）エチレンオキサイド付加ラウリルフォスフェートＫ塩
＊４）エチレンオキサイド付加ラウリルエーテル
* 1) Mineral oil with a viscosity of 12 mm 2 / s at 25 ° C. * 2) Dimethyl silicone with a viscosity of 10 mm 2 / s at 25 ° C. * 3) Ethylene oxide-added lauryl phosphate K salt * 4) Ethylene oxide-added lauryl ether
Claims (3)
（１）弾性糸横断面の、外接円の直径Ｄと内接円の直径ｄとの比(Ｄ／ｄ)が１．５〜４．０
(２)断面部Ｂの最大幅Ｗと接合部Ｃの最小幅ｗとの比(Ｗ／ｗ)が０．９〜３．０
The cross-sectional shape of the polyetherester block copolymer elastic yarn is a constricted joint with a cross-section A at the center and 3 to 5 circular cross-sections B that are independently joined to the cross-section A around the cross-section A. 3. The method for producing a polyetherester block copolymer elastic yarn according to claim 1, which has a shape composed of part C and satisfies the following (1) to (2):
(1) The ratio (D / d) of the diameter D of the circumscribed circle to the diameter d of the inscribed circle in the cross section of the elastic yarn is 1.5 to 4.0.
(2) The ratio (W / w) between the maximum width W of the cross section B and the minimum width w of the joint C is 0.9 to 3.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005222299A JP2007039817A (en) | 2005-08-01 | 2005-08-01 | Method for producing elastic yarn of polyether-ester block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005222299A JP2007039817A (en) | 2005-08-01 | 2005-08-01 | Method for producing elastic yarn of polyether-ester block copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007039817A true JP2007039817A (en) | 2007-02-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005222299A Pending JP2007039817A (en) | 2005-08-01 | 2005-08-01 | Method for producing elastic yarn of polyether-ester block copolymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103637446A (en) * | 2013-11-30 | 2014-03-19 | 江苏金泰针织有限责任公司 | Swimsuit knitted fabric weaving process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03174013A (en) * | 1989-12-01 | 1991-07-29 | Teijin Ltd | Elastic filament having multilobar section |
| JPH04146276A (en) * | 1990-10-01 | 1992-05-20 | Teijin Ltd | Elastic yarn of polyether ester block copolymer |
| JPH04352878A (en) * | 1991-05-23 | 1992-12-07 | Nippon Ester Co Ltd | Production of polyether-ester elastic fiber |
| JPH07207575A (en) * | 1994-01-10 | 1995-08-08 | Teijin Ltd | Polyether-ester block copolymer-based elastic yarn |
| JPH08296126A (en) * | 1995-04-25 | 1996-11-12 | Teijin Ltd | Production of polyether-ester block copolymer elastic yarn |
| JP2004124306A (en) * | 2002-10-03 | 2004-04-22 | Teijin Fibers Ltd | Elastic filament with multilobal cross section |
-
2005
- 2005-08-01 JP JP2005222299A patent/JP2007039817A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03174013A (en) * | 1989-12-01 | 1991-07-29 | Teijin Ltd | Elastic filament having multilobar section |
| JPH04146276A (en) * | 1990-10-01 | 1992-05-20 | Teijin Ltd | Elastic yarn of polyether ester block copolymer |
| JPH04352878A (en) * | 1991-05-23 | 1992-12-07 | Nippon Ester Co Ltd | Production of polyether-ester elastic fiber |
| JPH07207575A (en) * | 1994-01-10 | 1995-08-08 | Teijin Ltd | Polyether-ester block copolymer-based elastic yarn |
| JPH08296126A (en) * | 1995-04-25 | 1996-11-12 | Teijin Ltd | Production of polyether-ester block copolymer elastic yarn |
| JP2004124306A (en) * | 2002-10-03 | 2004-04-22 | Teijin Fibers Ltd | Elastic filament with multilobal cross section |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103637446A (en) * | 2013-11-30 | 2014-03-19 | 江苏金泰针织有限责任公司 | Swimsuit knitted fabric weaving process |
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