JP6021336B2 - Ultrafine fiber nonwoven fabric and method for producing the same - Google Patents
Ultrafine fiber nonwoven fabric and method for producing the same Download PDFInfo
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- 239000004745 nonwoven fabric Substances 0.000 title claims description 101
- 229920001410 Microfiber Polymers 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 20
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- 229920000642 polymer Polymers 0.000 claims description 83
- 239000007788 liquid Substances 0.000 claims description 48
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- 238000005345 coagulation Methods 0.000 claims description 18
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- 239000000243 solution Substances 0.000 description 58
- 238000009987 spinning Methods 0.000 description 57
- 238000000034 method Methods 0.000 description 39
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- 239000007789 gas Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
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- 238000002844 melting Methods 0.000 description 6
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- 238000005516 engineering process Methods 0.000 description 3
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- 239000002585 base Substances 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 229920002577 polybenzoxazole Polymers 0.000 description 2
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- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- LVGKZTVMAHRVFR-UHFFFAOYSA-N 4-(phenoxazine-10-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C2OC2=CC=CC=C21 LVGKZTVMAHRVFR-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- UATOFRZSCHRPBG-UHFFFAOYSA-N acetamide;hydrate Chemical compound O.CC(N)=O UATOFRZSCHRPBG-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 238000000113 differential scanning calorimetry Methods 0.000 description 1
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- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- KYKDOARTYFGHPC-UHFFFAOYSA-N n-propan-2-ylpropanamide Chemical compound CCC(=O)NC(C)C KYKDOARTYFGHPC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 238000005191 phase separation Methods 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、極細径繊維不織布およびその製造方法に関する。さらに詳細には、電池用セパレータやフィルターなどとして優れた性能を発揮する取扱い性に優れた極細径繊維不織布、および、ポリマー溶液を、細径を有する吐出孔より吐出し、伸張または細径化させた後、これを固化させた繊維からなる、強度に優れた極細径繊維不織布の製造方法に関するものである。 The present invention relates to an ultrafine fiber nonwoven fabric and a method for producing the same. More specifically, an ultrafine fiber nonwoven fabric with excellent handling properties that exhibits excellent performance as a battery separator, filter, etc., and a polymer solution are discharged from a discharge hole having a small diameter and stretched or reduced in diameter. Then, it is related with the manufacturing method of the ultrafine fiber nonwoven fabric excellent in intensity | strength which consists of the fiber which solidified this.
極細径繊維の製造方法としては、一般にメルトブロー法、海島型混合紡糸法、フラッシュ紡糸法、エレクトロスピニング法、爆裂紡糸法などが知られている。
メルトブロー法、海島型混合紡糸法は、溶融紡糸が可能なポリマーに対して適応される方法である。
また、フラッシュ紡糸法は、ポリマー溶液に対して適応される方法であり、高密度ポリエチレンやポリプロピレンと低沸点の溶剤（塩化フッ化炭化水素など）の混合溶液を紡糸孔から吐出する前に相分離させてから吐出するもので、低沸点の溶剤は急激にガス化膨張し、ポリマーは延伸されながら固化し、フィブリル化した極細の繊維からなる網状の連続繊維となり、これを拡げて集積しウェブを形成する方法である。ただし、この紡糸法が適用されるポリマーの種類は限られている。
Generally known methods for producing ultrafine fibers include a melt blow method, a sea-island type mixed spinning method, a flash spinning method, an electrospinning method, and an explosion spinning method.
The melt blow method and the sea-island type mixed spinning method are methods applied to polymers that can be melt-spun.
The flash spinning method is applied to polymer solutions, and phase separation is performed before discharging a mixed solution of high-density polyethylene or polypropylene and a low-boiling solvent (such as chlorofluorocarbon) from the spinning hole. The low-boiling point solvent is rapidly gasified and expanded, and the polymer is solidified while being stretched to form a continuous continuous fiber made of fibrillated ultrafine fibers. It is a method of forming. However, the types of polymers to which this spinning method is applied are limited.
エレクトロスピニング法は、ポリマー溶液の紡糸が可能であり、アラミドポリマー等にも適用されている（特許文献１〜２）が、一般にその生産性はメルトブロー法等に比べて低い。
これらの方法以外に、爆裂紡糸技術によるポリマー溶液からの糸の製造方法が知られている（特許文献３）。これは、ラバル管によって高速に加速された気流によって促進されるポリマー溶液の爆裂によって紡糸を行う方法であり、その生産性はエレクトロスピニング法に比べて一般に高い。
The electrospinning method can spin a polymer solution and is applied to an aramid polymer or the like (Patent Documents 1 and 2), but the productivity is generally lower than that of a melt blow method or the like.
In addition to these methods, a method for producing a yarn from a polymer solution by explosion spinning technology is known (Patent Document 3). This is a method in which spinning is performed by explosion of a polymer solution promoted by an air stream accelerated at high speed by a Laval tube, and its productivity is generally higher than that of electrospinning.
また、熱可塑性ポリマーをポリマー吐出孔から吐出させ、その吐出孔の外周から溶融したポリマーと並行に空気を随伴させ、さらに、ノズル端面から離れたエアスロットから噴射した高速の冷空気を吐出後のポリマーに作用させることによって、ポリマーを細径化させる装置が示されている（特許文献４）。
しかし、上記方法において製造される繊維は、繊維直径が細いだけでなく、延伸が不充分なため、繊維の強度が低く、得られる不織布シートの強力があまり高くないという欠点がある。このため、不織布を形成後に繊維中の溶剤除去のための水洗工程や、不織布中の水分除去の為の乾燥工程、および巻き取り工程で、不織布に少しでも張力がかかると、破断したり、形体が変形したりする問題があり、製造時の調整が非常に困難である。
In addition, the thermoplastic polymer is discharged from the polymer discharge hole, air is accompanied in parallel with the polymer melted from the outer periphery of the discharge hole, and high-speed cold air injected from an air slot away from the nozzle end surface is discharged. An apparatus for reducing the diameter of a polymer by acting on the polymer is disclosed (Patent Document 4).
However, the fiber produced by the above method has not only a thin fiber diameter but also insufficient stretching, so that the strength of the fiber is low and the strength of the resulting nonwoven sheet is not so high. For this reason, after forming the nonwoven fabric, if the nonwoven fabric is subjected to a water washing step for removing the solvent in the fiber, a drying step for removing moisture in the nonwoven fabric, and a winding step, if the nonwoven fabric is slightly tensioned, it will break or form There is a problem of deformation, and adjustment at the time of manufacture is very difficult.
本発明の目的は、上記問題点に鑑みなされたもので、力学特性が良好であり取扱い性に優れ、電池やキャパシタのセパレータ、フィルターなど用途にも好適に用いることができる極細径繊維不織布およびその製造方法を提供することにある。 The object of the present invention has been made in view of the above-mentioned problems, and has an excellent fine property, excellent handleability, and an ultra-fine fiber nonwoven fabric that can be suitably used for applications such as batteries and capacitor separators, filters, and the like. It is to provide a manufacturing method.
本発明者らは、上記課題を解決するため鋭意検討を重ねた結果、ポリマー溶液を、細径を有する吐出孔より吐出し、伸張または細径化させ、固化させて、極細径繊維からなる不織布を形成する際、該固化から不織布として捕集する工程で特定の方法を採用したとき、力学特性が良好であり取扱い性に優れた不織布が得られ、さらに該不織布が、フィルターや、電池、キャパシタ用のセパレータなどに適していることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have discharged a polymer solution from a discharge hole having a small diameter, stretched or reduced the diameter, and solidified to form a nonwoven fabric made of ultrafine fibers. When a specific method is employed in the process of collecting the solidified from the solidified as a nonwoven fabric, a nonwoven fabric having good mechanical properties and excellent handleability can be obtained. Further, the nonwoven fabric can be used as a filter, battery, capacitor, etc. As a result, the present invention has been completed.
かくして本発明によれば、ポリマー溶液から不織布を製造する方法であって、
（１）ポリマー溶液を、細径を有する吐出孔より吐出し、
（２）吐出孔の外側から噴出した気流を作用させて、該吐出したポリマー溶液を伸張または細径化させ、
（３）平均液滴径が１０００μｍ以下の凝固液を噴霧させて、該吐出したポリマー溶液を固化して、平均繊維直径が０．０１〜５μｍの繊維とし、
（４）該繊維の走行方向に従って流路が拡大しない流体整流板を通過させた後、
（５）該繊維を捕集して不織布とすることを特徴とする極細径繊維不織布の製造方法が提供される。
Thus, according to the present invention, a method for producing a nonwoven fabric from the port Rimmer solution,
(1) A polymer solution is discharged from a discharge hole having a small diameter,
(2) The air current ejected from the outside of the discharge hole is allowed to act to expand or reduce the diameter of the discharged polymer solution,
(3) Spraying a coagulating liquid having an average droplet diameter of 1000 μm or less to solidify the discharged polymer solution to obtain fibers having an average fiber diameter of 0.01 to 5 μm;
(4) After passing the fluid rectifying plate in which the flow path does not expand according to the traveling direction of the fiber,
(5) A method for producing an ultrafine fiber nonwoven fabric characterized by collecting the fiber to form a nonwoven fabric is provided.
本発明によれば、特定の方法で紡糸を行うことにより、極細の繊維径を有する繊維からなる極めて均質な不織布を提供することができる。また、本発明によれば、糸切れによる繊維の飛散を抑制できるため、工程ロスを抑え効率よく工業的に、上記の均質な極細径繊維不織布の製造を行うことができる。 According to the present invention, by performing spinning by a specific method, it is possible to provide a very homogeneous nonwoven fabric made of fibers having an extremely fine fiber diameter. Moreover, according to this invention, since the scattering of the fiber by yarn breakage can be suppressed, the above-mentioned homogeneous ultrafine fiber nonwoven fabric can be produced efficiently and industrially while suppressing process loss.
以下に、本発明を詳細に説明する。
本発明の極細径繊維不織布は、極細径繊維で構成された不織布からなり、該極細径繊維が、平均繊維直径が０．０１〜５μｍであり、該不織布が後述する（ａ）〜（ｃ）を満足することを特徴とし、これにより、不織布の均質な構造となり、フィルターや、電池、キャパシタ用のセパレータなどとして、優れた性能を発揮することができる。以下、平均繊維直径、（ａ）〜（ｃ）の要件について詳述する。
The present invention is described in detail below.
The ultrafine fiber nonwoven fabric of the present invention comprises a nonwoven fabric composed of ultrafine fibers, the ultrafine fiber has an average fiber diameter of 0.01 to 5 μm, and the nonwoven fabrics are described later (a) to (c). Thus, the nonwoven fabric has a homogeneous structure, and can exhibit excellent performance as a filter, a separator for a battery, a capacitor, or the like. Hereinafter, the average fiber diameter and the requirements (a) to (c) will be described in detail.
本発明において、上記のように、極細径繊維の平均繊維直径は０．０１〜５μｍである。平均繊維直径が５μｍより大きいと、不織布中の繊維構成本数が減少して、不織布の密度が減少するばかりでなく、不織布中に含まれる空間が大きくなり、フィルターとした場合は微細なダストを捕集できず捕集効率が低くなり、セパレータとした場合は薄くしかつ短絡防止性も向上させることが難しくなる。一方、平均繊維直径が０．０１μｍより小さいと、得られる強力が著しく低下し物理的な衝撃で破損し易くなる。平均繊維直径は好ましくは０．１〜４μｍ、より好ましくは０．５〜４μｍ、さらに好ましくは０．６〜３μｍである。 In the present invention, as described above, the average fiber diameter of the ultrafine fiber is 0.01 to 5 μm. When the average fiber diameter is larger than 5 μm, the number of fiber components in the nonwoven fabric decreases, not only the density of the nonwoven fabric decreases, but also the space contained in the nonwoven fabric increases, and when used as a filter, fine dust is trapped. It cannot be collected and the collection efficiency is lowered. When a separator is used, it is difficult to reduce the thickness and improve the short circuit prevention. On the other hand, when the average fiber diameter is smaller than 0.01 μm, the strength obtained is remarkably lowered and is easily damaged by a physical impact. The average fiber diameter is preferably 0.1 to 4 μm, more preferably 0.5 to 4 μm, and still more preferably 0.6 to 3 μm.
なお、本発明の不織布を構成する繊維の平均繊維直径は、不織布表面の電子顕微鏡写真で確認することのできる繊維の直径を意味し、任意に１００本の繊維を選びその巾を計測して平均することにより平均繊維直径を求めることができる。 The average fiber diameter of the fibers constituting the nonwoven fabric of the present invention means the diameter of the fiber that can be confirmed by an electron micrograph on the surface of the nonwoven fabric. By doing so, the average fiber diameter can be obtained.
本発明の目付ならびに厚みは、特に限定されるものではないが、目付は１ｇ／ｍ２以上、厚みは２μｍ以上であることが好ましい。目付が１ｇ／ｍ２より小さく、厚みが２μｍより小さいと、不織布に含まれる空間が小さく、後述する所望の平均見掛け密度や平均空隙径が得られにくくなる傾向にある。一方、セパレータの場合は、１ｇ／ｍ２以上、厚みは２μｍ以上であることが好ましい。フィルターの場合は、捕集性能の面から、目付は５ｇ／ｍ２以上、厚みは１０μｍ以上であることがより好ましい。 The basis weight and thickness of the present invention are not particularly limited, but the basis weight is preferably 1 g / m 2 or more and the thickness is preferably 2 μm or more. If the basis weight is smaller than 1 g / m 2 and the thickness is smaller than 2 μm, the space contained in the nonwoven fabric is small, and a desired average apparent density and average void diameter described later tend to be difficult to obtain. On the other hand, in the case of a separator, it is preferably 1 g / m 2 or more and a thickness of 2 μm or more. In the case of a filter, it is more preferable that the basis weight is 5 g / m 2 or more and the thickness is 10 μm or more from the viewpoint of collection performance.
（ａ）不織布の平均見かけ密度は０．０５〜１．５ｇ／ｃｍ３である。不織布の見掛け密度が０．０５ｇ／ｃｍ３未満であると、フィルターの場合、ダストの捕集効率が低下し、セパレータの場合、内部短絡が発生し易くなるため好ましくない。また、外圧がかかった時に、厚みの低下し易い傾向にあり、取扱い性が悪い。一方、不織布の見掛け密度が１．５ｇ／ｃｍ３を越えると、フィルターの場合、圧力損失が大きくなるため、目詰まりが早くなり、フィルターの寿命性能が短くなり、セパレータの場合、電解液保液性が低下する傾向にあり、好ましくない。また、所望の厚みを得るのに、繊維集積量を多くする必要があり、不経済である。不織布の平均見かけ密度は、好ましくは、０．０７５〜０．７５ｇ／ｃｍ３、より好ましくは、０．１〜０．５ｇ／ｃｍ３である。 (A) The average apparent density of the nonwoven fabric is 0.05 to 1.5 g / cm 3 . When the apparent density of the nonwoven fabric is less than 0.05 g / cm 3 , the dust collection efficiency is lowered in the case of a filter, and an internal short circuit is likely to occur in the case of a separator, which is not preferable. Further, when external pressure is applied, the thickness tends to decrease, and the handleability is poor. On the other hand, when the apparent density of the nonwoven fabric exceeds 1.5 g / cm 3 , the pressure loss increases in the case of a filter, so that clogging is accelerated and the life performance of the filter is shortened. It tends to decrease the properties, which is not preferable. Moreover, in order to obtain a desired thickness, it is necessary to increase the fiber accumulation amount, which is uneconomical. The average apparent density of the nonwoven fabric is preferably 0.075 to 0.75 g / cm 3 , more preferably 0.1 to 0.5 g / cm 3 .
（ｂ）不織布の平均空隙径は０．５〜１０μｍ、最大空隙径は２０μｍ以下である。平均空隙径が１０μｍより大きいか、または、最大空隙径が２０μｍより大きいと、フィルターの場合、微細なダストに対する捕集性能が劣り、セパレータの場合、内部短絡が発生し易くなるため好ましくない。一方、平均空隙径が０．５μｍ未満になると、フィルターの場合、圧力損失が大きくなるため、目詰まりが早く、フィルターの寿命性能が短くなり、セパレータの場合、電解液吸液性が低下する傾向にあり、好ましくない。不織布の平均空隙径は、好ましくは０．７５〜７．５μｍ、より好ましくは１〜５μｍであり、不織布の最大空隙径は、好ましくは１５μｍ、より好ましくは１０μｍ以下である。 (B) The average void diameter of the nonwoven fabric is 0.5 to 10 μm, and the maximum void diameter is 20 μm or less. If the average void diameter is larger than 10 μm or the maximum void diameter is larger than 20 μm, it is not preferable in the case of a filter because the performance of collecting fine dust is inferior, and in the case of a separator, an internal short circuit is likely to occur. On the other hand, when the average void diameter is less than 0.5 μm, the pressure loss increases in the case of a filter, so clogging is quick, the life performance of the filter is shortened, and in the case of a separator, the electrolyte solution absorbency tends to decrease. This is not preferable. The average void diameter of the nonwoven fabric is preferably 0.75 to 7.5 μm, more preferably 1 to 5 μm, and the maximum void diameter of the nonwoven fabric is preferably 15 μm, more preferably 10 μm or less.
（ｃ）不織布の一方の引張強度と該方向と垂直方向の引張強度の比が１．５〜１５である。上記の比が１．５未満では、不織布の巻き取りや、不織布をセパレータとして電池やキャパシタに加工する際、またはフィルターなど各種用途に応じた形状に加工する際、不織布が破断したり、変形したりし、好ましくない。一方、上記の比が１５未満では、他方の強度が低くなりすぎ、不織布が裂けたりして好ましくない。上記の比は、好ましくは１．５〜１０であり、より好ましくは１．５〜５であり、さらに好ましくは１．５〜３である。 (C) The ratio of one tensile strength of the nonwoven fabric to the tensile strength in the direction perpendicular to the direction is 1.5 to 15. When the ratio is less than 1.5, the nonwoven fabric breaks or deforms when the nonwoven fabric is wound, when the nonwoven fabric is processed into a battery or capacitor as a separator, or when it is processed into various shapes such as a filter. It is not preferable. On the other hand, if the ratio is less than 15, the other strength is too low, and the nonwoven fabric is torn, which is not preferable. Said ratio becomes like this. Preferably it is 1.5-10, More preferably, it is 1.5-5, More preferably, it is 1.5-3.
本発明においては、極細径繊維として、炭素繊維、ガラス繊維、セラミック繊維、アスベスト繊維等の無機繊維、アラミド繊維、ビニロン繊維、ポリアリレート繊維、ポリベンズオキサゾール（ＰＢＯ）繊維、ポリフェニレンサルファイド繊維、脂肪族ポリエステル繊維、全芳香族ポリエステル繊維、ポリアミド繊維、ポリオレフィン繊維、アクリル繊維、塩化ビニル繊維、ポリケトン繊維、セルロース繊維、パルプ繊維等の有機繊維等を挙げることができ、これらの一種を、または二種以上を組み合わせて使用することができる。 In the present invention, as the ultrafine fiber, carbon fiber, glass fiber, ceramic fiber, asbestos fiber and other inorganic fibers, aramid fiber, vinylon fiber, polyarylate fiber, polybenzoxazole (PBO) fiber, polyphenylene sulfide fiber, aliphatic Examples include polyester fibers, wholly aromatic polyester fibers, polyamide fibers, polyolefin fibers, acrylic fibers, vinyl chloride fibers, polyketone fibers, cellulose fibers, and organic fibers such as pulp fibers. Can be used in combination.
本発明においては、極細径繊維の融点または熱分解温度は、好ましくは３００℃以上、の融点または熱分解温度は、より好ましくは３５０℃以上、さらに好ましくは４００℃以上である。該融点または熱分解温度は、ＪＩＳ Ｋ ７１２１に準じて、示差熱分析により得られる示差熱分析曲線から求めることができる。上記極細径繊維としては、具体的には、前記繊維からこれを満たすものを選べばよいが、なかでも、アラミド繊維は、強力、耐性、難燃性、耐薬品性、絶縁性に優れており、フィルターやセパレータなどとしても高い性能を発揮し、特に好ましい。 In the present invention, the melting point or thermal decomposition temperature of the ultrafine fiber is preferably 300 ° C. or higher, and the melting point or thermal decomposition temperature is more preferably 350 ° C. or higher, and further preferably 400 ° C. or higher. The melting point or thermal decomposition temperature can be determined from a differential thermal analysis curve obtained by differential thermal analysis according to JIS K7121. As the ultrafine fiber, specifically, a fiber satisfying this can be selected from the above fibers. Among them, the aramid fiber is excellent in strength, resistance, flame resistance, chemical resistance, and insulation. It is particularly preferable because it exhibits high performance as a filter or separator.
上記アラミド繊維を構成するアラミドポリマーは、１種又は２種以上の２価の芳香族基が直接アミド結合により連結されているポリマーであって、該芳香族基は２個の芳香環が酸素、硫黄又はアルキレン基で結合されたものであってもよい。また、これらの２価の芳香族基には、メチル基やエチル基などの低級アルキル基、メトキシ基、クロル基などのハロゲン基等が含まれていてもよい。さらには、これらアミド結合は限定されず、パラ型、メタ型のどちらでもよい。 The aramid polymer constituting the aramid fiber is a polymer in which one or two or more divalent aromatic groups are directly linked by an amide bond, and the aromatic group has two aromatic rings as oxygen, It may be bonded with a sulfur or alkylene group. In addition, these divalent aromatic groups may include a lower alkyl group such as a methyl group or an ethyl group, a halogen group such as a methoxy group, or a chloro group. Furthermore, these amide bonds are not limited and may be either para-type or meta-type.
かかるアラミドポリマーとしては、ポリパラフェニレンテレフタルアミド、コポリパラフェニレン−３，４’オキシジフェニレン−テレフタルアミド、ポリメタフェニレンテレフタルアミド、ポリメタフェニレンイソフタルアミドなどが好ましく選択される。 As such an aramid polymer, polyparaphenylene terephthalamide, copolyparaphenylene-3,4'oxydiphenylene-terephthalamide, polymetaphenylene terephthalamide, polymetaphenylene isophthalamide and the like are preferably selected.
本発明おいては、前記の融点または熱分解温度を有する極細径繊維や、アラミドポリマーからなる極細径繊維を用いることにより、フィルターでは、ゴミ焼却炉、石炭ボイラー、あるいは金属溶鉱炉などから排出される排ガスは、１５０〜２００℃にもなり、これに耐えうる高い耐熱性を発揮できる。また、セパレータでは、例えばリチウムイオン電池用セパレータとして用いた場合、異常発熱によって電池内部温度が２００℃以上の高温になっても、セパレータが収縮することなく、セパレータ収縮による電極間ショートを防止することができる。さらに電気二重層キャパシタ用等、活性炭中の水分乾燥が重要な用途に用いた場合、素子乾燥温度を上げることができるため、効率良く乾燥することができる。 In the present invention, by using the ultrafine fiber having the melting point or the thermal decomposition temperature or the ultrafine fiber made of an aramid polymer, the filter is discharged from a garbage incinerator, a coal boiler, a metal blast furnace, or the like. The exhaust gas reaches 150 to 200 ° C. and can exhibit high heat resistance that can withstand this. In addition, when the separator is used as, for example, a lithium ion battery separator, even if the internal temperature of the battery reaches a high temperature of 200 ° C. or more due to abnormal heat generation, the separator does not contract and prevents the electrode from being short-circuited due to the separator contraction. Can do. Furthermore, when used for applications where moisture drying in activated carbon is important, such as for electric double layer capacitors, the element drying temperature can be raised, so that drying can be performed efficiently.
本発明においては、不織布の２００℃での乾熱収縮率は２％以下であることが好ましい。これにより、フィルターの場合、高温で使用される環境下において、フィルターが収縮し捕集したダストを拘束し払い落とし性が低下したり、圧力損失が大きくなったりすることがなく、フィルター寿命を長くできる。また、セパレータの場合は、セパレータの収縮による電極間ショートを防止することができる。不織布の２００℃での乾熱収縮率は好ましくは、１．７５％以下、より好ましくは１．５％以下である。 In the present invention, the dry heat shrinkage of the nonwoven fabric at 200 ° C. is preferably 2% or less. As a result, in the case of a filter, in a high-temperature environment, the filter shrinks and restrains the collected dust, so that the removal performance does not decrease and the pressure loss does not increase, extending the filter life. it can. In the case of a separator, it is possible to prevent a short circuit between electrodes due to the shrinkage of the separator. The dry heat shrinkage rate at 200 ° C. of the nonwoven fabric is preferably 1.75% or less, more preferably 1.5% or less.
本発明においては、上記極細径繊維が、例えば、後で詳述する方法によって得られる、ポリマー溶液を、細径を有する吐出孔より吐出し、伸張または細径化させた後、これを固化してなる繊維であることが好ましい。また、ポリマー溶液を、吐出孔よりバーストさせずに吐出するものであることが、均質な不織布となり好ましい。 In the present invention, the ultrafine fiber is obtained by, for example, a method described in detail later, and a polymer solution is discharged from a discharge hole having a small diameter and stretched or reduced in diameter, and then solidified. It is preferable that the fiber is formed. In addition, it is preferable that the polymer solution be discharged without bursting from the discharge holes because a homogeneous nonwoven fabric is obtained.
以上に説明した不織布の製造方法としては、ポリマー溶液をバーストさせ細繊化する爆裂紡糸技術（ＷＯ０２／０５２０７０記載）や、一般に溶融性ポリマーで行われているメルトブロー技術を改良し、効果的に細繊化する技術（ＵＳ６０１３２２３）や、特開２００５−２００７７９号公報のエレクトロスピニング法などが挙げられる。 The nonwoven fabric manufacturing method described above can be effectively refined by improving the explosive spinning technology (described in WO02 / 052070) in which a polymer solution is bursted into fine fibers and the melt-blowing technology generally used for meltable polymers. Examples thereof include a fiberizing technique (US Pat. No. 6,013,223) and an electrospinning method disclosed in Japanese Patent Application Laid-Open No. 2005-200779.
本発明は、その中でも、溶融性ポリマーで行われているメルトブロー技術を用い、細繊化する技術（ＵＳ６０１３２２３）を応用し、さらにこれを改良することによって、上記不織布を容易に製造できることを見出したものである。かかる方法では、ポリマー溶液をバーストさせることなく、連続した均一な繊維径を有する繊維とし易く、均質な不織布を得やすい。 Among others, the present invention has found that the nonwoven fabric can be easily produced by applying a technique for finer fiber (US 6013223) using the melt-blowing technique performed with a meltable polymer, and further improving the technique. Is. In such a method, it is easy to obtain a fiber having a continuous and uniform fiber diameter without bursting the polymer solution, and it is easy to obtain a homogeneous nonwoven fabric.
すなわち、本発明は、ポリマー溶液から不織布を製造する方法であって、
（１）ポリマー溶液を、細径を有する吐出孔より吐出し、
（２）吐出孔の外側から噴出した気流を作用させて、該吐出したポリマー溶液を伸張または細径化させ、
（３）平均液滴径が１０００μｍ以下の凝固液を噴霧させて、該吐出したポリマー溶液を固化して、平均繊維直径が０．０１〜５μｍの繊維とし、
（４）該繊維の走行方向に従って流路が拡大しない流体整流板を通過させた後、
（５）該繊維を捕集して不織布とすることを特徴とする極細径繊維不織布の製造方法である。
That is, the present invention is a method for producing a nonwoven fabric from a polymer solution,
(1) A polymer solution is discharged from a discharge hole having a small diameter,
(2) The air current ejected from the outside of the discharge hole is allowed to act to expand or reduce the diameter of the discharged polymer solution,
(3) Spraying a coagulating liquid having an average droplet diameter of 1000 μm or less to solidify the discharged polymer solution to obtain fibers having an average fiber diameter of 0.01 to 5 μm;
(4) After passing the fluid rectifying plate in which the flow path does not expand according to the traveling direction of the fiber,
(5) A method for producing an ultrafine fiber nonwoven fabric, wherein the fiber is collected to form a nonwoven fabric.
例えば、アラミドポリマーのポリマー溶液を用いる場合、アラミドを溶解する溶媒は、例えばＮ−メチル−２−ピロリドン（ＮＭＰ）、ジメチルアセトアミド（ＤＭＡｃ）、およびジメチルホルムアミド（ＤＭＦ）、ジメチルイミダゾリジノン、アルコキシ−Ｎ−イソプロピル−プロピオンアミドなどのアミド系極性溶媒を挙げることができる。ジメチルスルホキシド（ＤＭＳＯ）もまた、溶媒として使用される。ポリマーの溶解性を大きく損なわない程度に、上記溶媒以外のトルエン、アセトン等の溶媒を添加しても良い。中でもＮＭＰ、ＤＭＡｃが、アラミドポリマー溶液の安定性の観点から好ましい。 For example, when a polymer solution of an aramid polymer is used, solvents for dissolving aramid are, for example, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylimidazolidinone, alkoxy- Examples include amide polar solvents such as N-isopropyl-propionamide. Dimethyl sulfoxide (DMSO) is also used as a solvent. You may add solvents, such as toluene and acetone other than the said solvent, to such an extent that the solubility of a polymer is not impaired significantly. Among these, NMP and DMAc are preferable from the viewpoint of the stability of the aramid polymer solution.
また、曳糸性向上のために無機塩を添加しても良い。本方法で使用できる無機塩としては、カルシウム、リチウム、マグネシウムおよびアルミニウムよりなる群から選択されるカチオンを有する塩化物または臭化物等のハロゲン化物が挙げられ、特に塩化カルシウムまたは塩化リチウムが好ましい。これらの塩の混合物を使用することも可能である。 In addition, an inorganic salt may be added to improve the spinnability. Examples of the inorganic salt that can be used in the present method include halides such as chloride or bromide having a cation selected from the group consisting of calcium, lithium, magnesium and aluminum, and calcium chloride or lithium chloride is particularly preferable. It is also possible to use mixtures of these salts.
このような無機塩は必要に応じて添加することもあるが、溶液調製プロセス（例えば重合体製造プロセス）で必然的に生成するものであってもかまわない。無機塩の含有量は、アラミドポリマーを基準として４５重量％以下、好ましくは２０重量％以下、より好ましくは１０重量％以下である。 Such inorganic salts may be added as necessary, but they may be inevitably produced by a solution preparation process (for example, a polymer production process). The content of the inorganic salt is 45% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less based on the aramid polymer.
なお、上記のポリマー溶液には、本発明の目的を阻害しない範囲で水を含んでいても良い。ここで、水の含有量は、アラミドポリマーの重量を基準として７０重量％以下であり、好ましくは５０重量％以下、より好ましくは１５重量％以下である。 The polymer solution may contain water as long as the object of the present invention is not impaired. Here, the water content is 70% by weight or less, preferably 50% by weight or less, more preferably 15% by weight or less, based on the weight of the aramid polymer.
次に、前記の製造工程を図により詳細に説明するがこれに限定されるものではない。
図１に示すように、ダイ１によって適切な温度に温調されたキャビティー２に付属した紡糸ノズル３にポリマー溶液を供給する。こうしてノズル内管９を通ったポリマー溶液１０は、吐出孔の外側に設置されたガス吐出口７から噴出したガス気流によって、効果的に加速され、伸張または細化される。
Next, although the said manufacturing process is demonstrated in detail with figure, it is not limited to this.
As shown in FIG. 1, a polymer solution is supplied to a
ここで、ポリマー溶液１０の吐出量、ポリマー溶液を伸張または細径化させる圧空吐出量は、得ようとする不織布の繊維径など不織布形体により適宜選択できる。すなわち、不織布を構成する繊維の繊維径を小さくしたり、不織布の空隙径を小さくしたり、密度を大きくしたりする場合は、ポリマー溶液の吐出量を少なくし、または圧空吐出量を多くし、一方、不織布を構成する繊維の繊維径を大きくしたり、不織布の空隙径を大きくしたり、密度を小さくする場合は、ポリマー溶液の吐出量を多くし、または圧空吐出量を少なくする。このように、ポリマー溶液の吐出量と圧空吐出量を調整することで、前記の、平均繊維直径、平均見掛け密度、平均空隙径、最大空隙径を有する不織布を容易に得ることができる。 Here, the discharge amount of the polymer solution 10 and the compressed air discharge amount for extending or reducing the diameter of the polymer solution can be appropriately selected according to the nonwoven fabric shape such as the fiber diameter of the nonwoven fabric to be obtained. That is, when reducing the fiber diameter of the fibers constituting the nonwoven fabric, reducing the void diameter of the nonwoven fabric, or increasing the density, decrease the discharge amount of the polymer solution or increase the discharge amount of compressed air, On the other hand, when the fiber diameter of the fibers constituting the nonwoven fabric is increased, the void diameter of the nonwoven fabric is increased, or the density is decreased, the discharge amount of the polymer solution is increased or the discharge amount of compressed air is decreased. Thus, the nonwoven fabric which has the said average fiber diameter, an average apparent density, an average void diameter, and a largest void diameter can be obtained easily by adjusting the discharge amount of a polymer solution, and a pneumatic discharge amount.
前記凝固液としては、アラミドポリマーの場合、該ポリマーに対する貧溶媒が用いられ、水、水／アミド系極性溶媒の混合液、水／アルコール類の混合液、アルコール類等が挙げられる。水／アミド系極性溶媒の混合液に含まれるアミド系極性溶媒としては、アラミドポリマーを溶解し、水と良好に混和するものであれば任意のものを使用することができるが、特にＮＭＰ、ＤＭＡｃ、ＤＭＦを好適に用いることができる。なかでも、溶媒の回収等を考慮すると、紡糸用ポリマー溶液中のアミド系極性溶媒と同種のものが好ましい。上記凝固液の中でも、水、水／ＮＭＰ混合溶媒もしくは水／ＤＭＡｃ混合溶媒が好ましい。 As the coagulating liquid, in the case of an aramid polymer, a poor solvent for the polymer is used, and examples thereof include water, a mixed liquid of water / amide type polar solvent, a mixed liquid of water / alcohols, and alcohols. As the amide polar solvent contained in the water / amide polar solvent mixture, any solvent can be used as long as it dissolves the aramid polymer and is well mixed with water. DMF can be preferably used. Of these, in consideration of solvent recovery, the same kind as the amide polar solvent in the spinning polymer solution is preferable. Among the coagulating liquids, water, a water / NMP mixed solvent or a water / DMAc mixed solvent is preferable.
本発明においては、ポリマー溶液１０を吐出孔から吐出後、これに平均液滴径が１０００μｍ以下の凝固液を噴霧させて、該吐出したポリマー溶液を固化して、前記平均繊維直径の繊維とすることが重要である。上記平均液滴径が１０００μｍより大きいと、液滴の重量が重すぎて、後述する流体整流板での気流の制御ができず、不織布を構成する繊維の配向を調整できなくなる。より好ましくは、凝固液の平均液滴径は５００μｍ以下、さらに好ましくは２５０μｍ以下である。ここで、平均液滴径は、面積基準の平均液滴径はレーザー散乱／回折法（堀場製作所製ＬＡ−９１０等で測定可能）により測定できる。 In the present invention, after the polymer solution 10 is discharged from the discharge hole, a coagulating liquid having an average droplet diameter of 1000 μm or less is sprayed thereon, and the discharged polymer solution is solidified to obtain fibers having the average fiber diameter. This is very important. When the average droplet diameter is larger than 1000 μm, the weight of the droplet is too heavy to control the airflow in the fluid rectifying plate, which will be described later, and the orientation of the fibers constituting the nonwoven fabric cannot be adjusted. More preferably, the average droplet diameter of the coagulating liquid is 500 μm or less, and more preferably 250 μm or less. Here, the average droplet diameter can be measured by a laser scattering / diffraction method (measurable with LA-910 manufactured by Horiba, Ltd.).
本発明においては、上記の圧縮空気による凝固液の噴霧を、吐出孔から繊維として捕集される間の吐出ポリマー溶液の直線軸（以下、紡糸軸と称することがある）に対し、相対して、同じ位置、同じ噴射角度となるように配された少なくとも一対のスプレーノズルなどの凝固液供給装置により行うことが好ましい。なお、吐出孔から繊維として捕集される間の吐出ポリマー溶液が固化し繊維束となっている状態を以下、糸条と称することがある。また、不織布形状としてなった繊維の捕集を搬送ベルト等の搬送手段で連続的に行う場合、スプレーノズルは、該手段の搬送方向の反対側（川上側）と搬送方向側（川下側）に配置することが好ましい。スプレーノズルが、いずれか一方の側のみに設置されたり、もしくは、少なくとも一対で配置されても設置位置高さや凝固液噴射角度が異なったりすると、圧力空気と凝固液がスプレーノズルから吐出された際、糸条の流れ方向が乱され、糸切れが発生したり、得られる不織布の目付プロファイルを悪化させる原因となるため好ましくない。 In the present invention, the spray of the coagulating liquid by the compressed air is opposed to the linear axis of the discharged polymer solution (hereinafter sometimes referred to as a spinning axis) while being collected as fibers from the discharge holes. It is preferable to use a coagulating liquid supply device such as at least a pair of spray nozzles arranged at the same position and the same spray angle. Hereinafter, the state in which the discharged polymer solution is solidified as a fiber bundle while being collected as fibers from the discharge holes may be referred to as a yarn. In addition, when continuously collecting fibers in the form of a nonwoven fabric with a conveying means such as a conveying belt, the spray nozzle is on the opposite side of the conveying direction (upstream side) and the conveying direction side (downstream side) of the means. It is preferable to arrange. When the spray nozzle is installed only on one side, or when the installation position height or coagulation liquid injection angle is different even if it is arranged at least as a pair, the pressure air and the coagulation liquid are discharged from the spray nozzle. This is not preferable because the flow direction of the yarn is disturbed, yarn breakage occurs, or the basis weight profile of the resulting nonwoven fabric is deteriorated.
本発明では凝固液供給装置としてスプレーノズルを用いることができるが、具体的には、フルコーンスプレー、ホロコーンスプレー、フラットスプレー等の一流体スプレーや二流体スプレーが挙げられるが、少量の凝固液を糸条に均一に噴射でき、凝固液と同時に噴射される圧縮空気によって紡糸線上の気流の流れを乱すことなく、糸条に凝固液を接触させることが可能な二流体スプレーを使用するのが好ましい。 In the present invention, a spray nozzle can be used as the coagulation liquid supply device, and specific examples include one-fluid spray and two-fluid spray such as full-cone spray, holo-cone spray, and flat spray. It is possible to use a two-fluid spray that can evenly spray the yarn on the yarn, and can contact the coagulating liquid with the yarn without disturbing the flow of the air current on the spinning line by the compressed air injected simultaneously with the coagulating liquid. preferable.
上記凝固液供給装置は、ポリマー溶液の吐出孔から下方３００ｍｍの間の位置に設置するのが好ましい。この位置が吐出孔より上にある場合は、凝固液供給装置より噴霧された凝固液が、ポリマー溶液吐出孔にも付着することがあり、該吐出孔からポリマー溶液が吐出した時点で、凝固、固化してしまい、ポリマー溶液の吐出不良が起きてしまうことがある。一方、凝固液供給装置がポリマー溶液の吐出孔の下方３００ｍｍを越える位置に設置されると、紡糸線上での各繊維相互間の結着が顕著になり、不織布中にロープ状の繊維束が増加し、得られる不織布は不均質なものとなりやすい。 The coagulating liquid supply device is preferably installed at a position 300 mm below the polymer solution discharge hole. When this position is above the discharge hole, the coagulated liquid sprayed from the coagulation liquid supply device may also adhere to the polymer solution discharge hole, and when the polymer solution is discharged from the discharge hole, The polymer solution may solidify and cause poor discharge of the polymer solution. On the other hand, when the coagulating liquid supply device is installed at a position exceeding 300 mm below the discharge hole for the polymer solution, the binding between the fibers on the spinning line becomes remarkable, and the rope-like fiber bundle increases in the nonwoven fabric. However, the resulting nonwoven fabric tends to be heterogeneous.
前記凝固液供給装置は、ポリマー溶液の吐出孔から吐出され、周囲から吐出される気流で細化され捕集されるまでの紡糸線に対して直角から平行となる間の適当な噴射角度にて、均一に噴霧できるように１個、または複数個設置されるが、これはポリマー溶液の吐出孔の配列数、すなわち紡糸幅、凝固液供給装置の種類、性能等により適宜決められる。 The coagulating liquid supply device is discharged from the discharge hole of the polymer solution, and at an appropriate injection angle between being perpendicular and parallel to the spinning line until it is thinned and collected by the airflow discharged from the surroundings. One or a plurality of nozzles are provided so that they can be sprayed uniformly, and this is appropriately determined depending on the number of polymer solution discharge holes arranged, that is, the spinning width, the type of coagulation liquid supply device, the performance, and the like.
凝固液供給装置、例えばスプレーノズル先端から紡糸線までの距離は５〜３００ｍｍで設置するのが望ましい。上記距離が５ｍｍ未満では、凝固液供給装置から噴霧された圧縮空気が、紡糸線上を流れている糸条に強く接触して干渉し、糸切れが起きたり、得られる不織布の目付プロファイルを悪化させるため好ましくない。逆に、上記距離が３００ｍｍを越えて遠くなると、噴霧された凝固液は紡糸線上の広範囲に噴霧されることとなり好ましくない。すなわち、糸条の凝固を効率よく行うためには、糸条の細化が十分に行われた直後に液体と空気を送り込み糸条と接触させことが好ましいが、凝固液供給装置の紡糸線からの距離が３００ｍｍを越える場合、ノズルから噴霧された水溶液が紡糸線上の広範囲にわたって噴霧されるので、糸条を効率的に凝固させることが困難になるため、使用する凝固液量を多くする必要があり好ましくない。 It is desirable to install the coagulating liquid supply device, for example, the distance from the tip of the spray nozzle to the spinning line at 5 to 300 mm. If the distance is less than 5 mm, the compressed air sprayed from the coagulating liquid supply device strongly contacts and interferes with the yarn flowing on the spinning line, causing yarn breakage or worsening the basis weight profile of the obtained nonwoven fabric. Therefore, it is not preferable. On the other hand, when the distance exceeds 300 mm, the sprayed coagulating liquid is undesirably sprayed over a wide area on the spinning line. That is, in order to efficiently solidify the yarn, it is preferable to send liquid and air in contact with the yarn immediately after the yarn is sufficiently thinned. If the distance exceeds 300 mm, since the aqueous solution sprayed from the nozzle is sprayed over a wide area on the spinning line, it becomes difficult to efficiently solidify the yarn, so it is necessary to increase the amount of coagulating liquid to be used. There is not preferable.
凝固液供給装置としてスプレーノズル、特に二流体スプレーノズルを用いる場合、該スプレーノズルから噴射される圧縮空気の圧力は、０．１〜１．０ＭＰａの範囲が好ましい。圧縮空気圧が０．１ＭＰａ未満では、凝固液を細かい粒子の霧状にするのが難しくなり、繊維表面に均一に凝固液を接触させられない傾向にあり好ましくない。逆に、圧縮空気圧が１．０ＭＰａを越えると、圧縮空気が紡糸線上の糸条に強く接触して干渉し、得られる不織布の目付プロファイルを悪化させるとともに、空気によって細化中の極細繊維の相互間が結着し、ロープ欠点を形成し易くなるため好ましくない。スプレーノズルから噴霧される凝固液の量は、ポリマー溶液吐出孔から吐出されるポリマー溶液量、必要とする凝固の程度等により適宜調整することができる。 When a spray nozzle, particularly a two-fluid spray nozzle is used as the coagulation liquid supply device, the pressure of the compressed air injected from the spray nozzle is preferably in the range of 0.1 to 1.0 MPa. When the compressed air pressure is less than 0.1 MPa, it is difficult to make the coagulation liquid into a fine particle mist, and the coagulation liquid tends not to contact the fiber surface uniformly, which is not preferable. On the other hand, when the compressed air pressure exceeds 1.0 MPa, the compressed air strongly contacts and interferes with the yarn on the spinning line to deteriorate the basis weight profile of the obtained nonwoven fabric, and the mutual fine fibers being thinned by the air It is not preferable because the space is bound and it becomes easy to form a rope defect. The amount of the coagulation liquid sprayed from the spray nozzle can be appropriately adjusted depending on the amount of the polymer solution discharged from the polymer solution discharge hole, the required degree of coagulation, and the like.
本発明においては、前記のように凝固液を噴霧させて、該吐出したポリマー溶液を固化して繊維とした後、該繊維の走行方向に従って流路が拡大しない流体整流板を通過させることが重要である。これによって、繊維を一方の方向に配向させ、該方向において強度が向上した不織布とすることができる。このとき、繊維の捕集を搬送ベルト等の搬送手段で連続的に行う場合、これを連続した不織布として巻き取ったり、その後、巻き出して各用途で必要な形状に加工したりすることなどを考慮し、不織布の長さ方向、すなわち搬送ベルトの走行方向に繊維が配向し、強度が高くなっていることが好ましい。 In the present invention, it is important to spray the coagulating liquid as described above, solidify the discharged polymer solution to form a fiber, and then pass it through a fluid rectifying plate whose flow path does not expand according to the traveling direction of the fiber. It is. As a result, the fibers can be oriented in one direction, and a nonwoven fabric with improved strength in that direction can be obtained. At this time, when the fibers are continuously collected by a conveying means such as a conveying belt, it is wound up as a continuous nonwoven fabric, or is then unwound and processed into a shape necessary for each application. In consideration, it is preferable that the fibers are oriented in the length direction of the nonwoven fabric, that is, the running direction of the transport belt, and the strength is high.
流体整流板は、吐出孔から繊維として捕集される間の吐出ポリマー溶液の直線軸（紡糸軸）に対し、相対して、同じ位置、同じ角度となるように一対に配することが好ましい。また、不織布の長さ方向に繊維を配向させ、かつ上記のように繊維の捕集を搬送ベルト等の搬送手段で連続的に行う場合、気体整流板は、該手段の搬送方向の反対側（川上側）と搬送方向側（川下側）に配置することが好ましい。流体整流板が搬送方向の上流側または下流側のいずれか一方のみに設置されたり、もしくは、搬送方向の上流側と下流側の両方に設置されたとしても、設置位置が異なったり、設置角度が異なったりすると、ノズルから吐出された糸条の流れ方向が乱され糸切れが発生したり、得られる不織布の目付プロファイルを悪化させる原因となり易く、好ましくない。 The fluid rectifying plates are preferably arranged in pairs so as to be at the same position and at the same angle relative to the linear axis (spinning axis) of the discharged polymer solution while being collected as fibers from the discharge holes. Further, when the fibers are oriented in the length direction of the nonwoven fabric and the fibers are continuously collected by the conveying means such as the conveying belt as described above, the gas rectifying plate is opposite to the conveying direction of the means ( It is preferable to arrange on the upstream side) and the transport direction side (downstream side). Even if the fluid rectifying plate is installed only on either the upstream or downstream side in the transport direction, or installed on both the upstream and downstream sides in the transport direction, the installation position is different or the installation angle is If they are different, the flow direction of the yarn discharged from the nozzle is disturbed, and breakage of the yarn is likely to occur, or the basis weight profile of the obtained nonwoven fabric is likely to be deteriorated, which is not preferable.
流体整流板は、凝固液供給装置であるスプレーノズル等より下で、かつ、不織布を捕集する捕集面から１００ｍｍ以上、上に設置することが好ましい。流体整流板が凝固液装置であるスプレーノズル等より上にあると、一方に繊維が配向した不織布とするのが難しい。一方、捕集面からからの距離が１００ｍｍに満たない場合、捕集された不織布の一部が流体整流板に接触することがあり、得られる不織布は不均質なものとなりやすい。 It is preferable that the fluid rectifying plate is installed below a spray nozzle or the like which is a coagulating liquid supply device and at least 100 mm above the collecting surface for collecting the nonwoven fabric. If the fluid rectifying plate is above a spray nozzle or the like that is a coagulating liquid device, it is difficult to form a nonwoven fabric in which fibers are oriented on one side. On the other hand, when the distance from the collection surface is less than 100 mm, a part of the collected nonwoven fabric may come into contact with the fluid rectifying plate, and the resulting nonwoven fabric tends to be inhomogeneous.
また、本発明においては、流体整流板を、該吐出したポリマー溶液を固化して繊維とする、該繊維の走行方向に従って流路が拡大しない流体整流板を通過させることが重要である。具体的には、吐出孔から繊維として捕集される間の吐出ポリマー溶液の直線軸（紡糸軸）に対し、流体整流板を、該紡糸軸に対して平行（すなわち、紡糸軸と流体整流板との角度が０°）となるか、該紡糸軸に対して繊維の走行方向に従って次第に狭くなる（紡糸軸と流体整流板との角度が０°より大きく９０°未満）となるように、走行する繊維の外側に設置することが好ましい。なお、図１には、後者のように繊維の走行方向に従って次第に狭くなる態様を模式図で示した。流体整流板は、平板または湾曲したものを用いてもよく、後者のように流路の狭める場合、その狭め方としては直線状に狭めても良いし、流体の乱れが必要以上に大きくならないように緩やかなカーブを設けて狭めるようにしてもよい。上記のように、流路を紡糸線と平行、もしくは、次第に狭めることにより、気流の周囲へのランダムな拡散が抑制されるので、極細径繊維は不織布の一方向、すなわち、捕集された繊維不織布の搬送方向に配向しやすくなる。紡糸軸と流体整流板との角度は、より好ましくは０°〜４５°、より好ましくは０°〜３０°である。 Further, in the present invention, it is important that the fluid rectifying plate is passed through a fluid rectifying plate in which the discharged polymer solution is solidified into a fiber and the flow path does not expand in accordance with the traveling direction of the fiber. Specifically, the fluid straightening plate is parallel to the spinning axis (that is, the spinning shaft and the fluid straightening plate) with respect to the linear axis (spinning shaft) of the discharged polymer solution while being collected as fibers from the discharge holes. In such a way that the angle is 0 °) or gradually narrows in accordance with the fiber running direction with respect to the spinning axis (the angle between the spinning axis and the fluid flow regulating plate is greater than 0 ° and less than 90 °). It is preferable to install on the outside of the fiber. In addition, in FIG. 1, the aspect which becomes narrow gradually according to the running direction of a fiber like the latter was shown with the schematic diagram. The fluid rectifying plate may be a flat plate or a curved plate. When the flow path is narrowed as in the latter case, the fluid rectifying plate may be narrowed linearly, and the fluid turbulence may not be increased more than necessary. Alternatively, a gentle curve may be provided to narrow it. As mentioned above, by narrowing the flow path parallel to the spinning line or gradually narrowing, the random diffusion around the airflow is suppressed, so the ultrafine fiber is unidirectional in the nonwoven fabric, that is, the collected fiber It becomes easy to orient in the conveyance direction of the nonwoven fabric. The angle between the spinning shaft and the fluid rectifying plate is more preferably 0 ° to 45 °, and more preferably 0 ° to 30 °.
流体整流板の紡糸線からの距離は５０〜３００ｍｍの範囲で設置されるのが望ましい。紡糸線からの距離が５０ｍｍ未満では、気体整流板に糸条が接触してしまうため好ましくない。逆に、紡糸線からの距離が３００ｍｍを越えて遠くなると、紡糸線周辺の気流の整流ができなくなり、不織布を構成する繊維の配向を調整できなくなる。 The distance from the spinning line of the fluid rectifying plate is preferably set in the range of 50 to 300 mm. If the distance from the spinning line is less than 50 mm, the yarn contacts the gas rectifying plate, which is not preferable. Conversely, when the distance from the spinning line exceeds 300 mm, the airflow around the spinning line cannot be rectified, and the orientation of the fibers constituting the nonwoven fabric cannot be adjusted.
また、該気体整流板の素材は、金属、プラスチック、木、紙など特に限定されないが、極希にではあるが繊維が付着して、これにより紐状物を発生させることがあるため、表面にテトラフルオロエチレンなとのシートを貼りつけたり表面にコートするなどの処理を行うことが好ましい。 The material of the gas rectifying plate is not particularly limited to metal, plastic, wood, paper, etc., but very rarely fibers adhere to it, which may generate string-like objects. It is preferable to perform a treatment such as attaching a sheet of tetrafluoroethylene or coating the surface.
上記極細径繊維は、例えば、固定した捕集支持体や走行する搬送ベルト上に捕捉することによって、均質な不織布を得ることができる。その際、シート状基材の上に直接補足し、基材との積層体とすることもできる。このようにして得られた積層体をいったん巻き取り、再度この巻き取った積層体に該極細径繊維を捕捉し、三層構造にすることもできる。 The ultrafine fiber can be obtained on, for example, a fixed collection support or a traveling conveyor belt to obtain a homogeneous nonwoven fabric. In that case, it can supplement directly on a sheet-like base material, and can also be set as a laminated body with a base material. The laminated body thus obtained can be wound up once, and the ultrafine fiber can be captured again in the wound laminated body to form a three-layer structure.
吐出孔から捕集面までの距離（紡糸距離ということがある）は、１００〜８００ｍｍの範囲が好ましい。紡糸距離が１００ｍｍ未満では、スプレーノズルの配置が難しくなる、一方、紡糸距離が８００ｍｍを超えると、紡糸線上での各繊維相互間の結着が顕著になり、不織布中にロープ状の繊維束が増加するとともに、捕集面に達する際の糸条と糸条に随伴する圧空の速度が低下し、得られる不織布の強度が弱いものとなってしまう。紡糸距離は、より好ましくは２００〜７００ｍｍ、さらに好ましくは３００〜６００ｍｍである。 The distance from the discharge hole to the collection surface (sometimes referred to as spinning distance) is preferably in the range of 100 to 800 mm. When the spinning distance is less than 100 mm, it becomes difficult to dispose the spray nozzle. On the other hand, when the spinning distance exceeds 800 mm, the binding between the fibers on the spinning line becomes remarkable, and the rope-like fiber bundle is formed in the nonwoven fabric. While increasing, the speed | rate of the compressed air accompanying the thread | yarn at the time of reaching a collection surface and a thread | yarn falls, and the intensity | strength of the nonwoven fabric obtained will become a weak thing. The spinning distance is more preferably 200 to 700 mm, still more preferably 300 to 600 mm.
本発明において、不織布の目付は、ノズルからのポリマー溶液吐出量と捕集面の移動速度（ベルト速度）によって決定され、使用する目的によって適宜調整することができる。
得られた繊維およびそれらによって構成される不織布は洗浄しても良い。繊維もしくは不織布を洗浄する方法としては、繊維から溶媒および塩を除去するあらゆる手段または機器を使用しても良く、例えば、洗浄浴に浸漬する方法、洗浄液もしくはスチーム等を吹き付ける方法、乾燥機にて乾燥除去する方法等が挙げられる。中でも、洗浄浴に浸漬する方法は洗浄効率が高く好ましい。
In the present invention, the basis weight of the nonwoven fabric is determined by the polymer solution discharge amount from the nozzle and the moving speed (belt speed) of the collecting surface, and can be appropriately adjusted depending on the purpose of use.
You may wash | clean the obtained fiber and the nonwoven fabric comprised by them. As a method for washing fibers or non-woven fabrics, any means or equipment for removing the solvent and salt from the fibers may be used. For example, a method of immersing in a washing bath, a method of spraying a washing solution or steam, or a dryer Examples include a method of drying and removing. Among them, the method of immersing in a cleaning bath is preferable because of high cleaning efficiency.
次いで、必要に応じて乾燥し、水分並びに残留溶媒を除去する。乾燥された繊維もしくは不織布は、引き続いて熱処理工程にて１００〜５００℃の温度で熱処理しても良い。この際の熱処理は、熱板上、乾熱雰囲気下もしくは蒸気雰囲気下のいずれの条件で行っても良い。蒸気雰囲気を使用する場合、該蒸気中には水以外にアミド系極性溶媒が含まれていてもよい。 Subsequently, it is dried as necessary to remove moisture and residual solvent. The dried fiber or non-woven fabric may be subsequently heat-treated at a temperature of 100 to 500 ° C. in a heat treatment step. The heat treatment at this time may be performed under any conditions of a hot plate, a dry heat atmosphere, or a steam atmosphere. When a steam atmosphere is used, the steam may contain an amide polar solvent in addition to water.
ここで、熱処理温度は、１００〜５００℃で実施するのが好ましい。５００℃を超える場合には、得られる繊維は激しく劣化・着色し、場合によっては断糸する場合がある。一方、１００℃未満の場合には、繊維が十分に弛緩されない場合がある。なお、熱板にて熱処理する場合には、好ましくは２００〜４００℃、さらに好ましくは２５０〜３５０℃で実施するのが好ましい。また、乾熱雰囲気下の熱処理の場合には、２５０〜５００℃で実施するのが好ましい。蒸気雰囲気下の熱処理の場合に、１００〜４００℃で実施するのが好ましい。 Here, the heat treatment temperature is preferably 100 to 500 ° C. When the temperature exceeds 500 ° C., the obtained fiber is severely deteriorated and colored, and in some cases, the yarn may be broken. On the other hand, when the temperature is lower than 100 ° C., the fiber may not be sufficiently relaxed. In addition, when heat-processing with a hot plate, Preferably it is 200-400 degreeC, More preferably, it is preferable to implement at 250-350 degreeC. Moreover, in the case of the heat processing in a dry heat atmosphere, it is preferable to implement at 250-500 degreeC. In the case of heat treatment under a steam atmosphere, it is preferable to carry out at 100 to 400 ° C.
以下、実施例に基づいて本発明をさらに詳細に説明する。ただし、以下の実施例は、本発明を限定するものではない。なお、実施例中における各物性値は、下記の方法で測定した。 Hereinafter, the present invention will be described in more detail based on examples. However, the following examples do not limit the present invention. In addition, each physical-property value in an Example was measured with the following method.
＜繊維径（μｍ）＞
不織布を走査型電子顕微鏡ＪＳＭ６３３０Ｆ（ＪＥＯＬ社製）にて観察し、繊維１００本を任意に選出して繊維径を測定し、平均繊維径を算出した。なお、観察は３０００倍で行った。
<Fiber diameter (μm)>
The nonwoven fabric was observed with a scanning electron microscope JSM6330F (manufactured by JEOL), 100 fibers were arbitrarily selected, the fiber diameter was measured, and the average fiber diameter was calculated. The observation was performed at 3000 times.
＜目付（ｇ／ｍ２）＞
ＪＩＳ Ｌ １９０６の単位面積当りの重量試験方法に準じて測定を行った。
<Weight per unit (g / m 2 )>
Measurement was carried out according to the weight test method per unit area of JIS L 1906.
＜厚さ（ｍｍ）＞
小野測器 デジタルリニアゲージＤＧ−９２５（測定端子部の直径１ｃｍ）を用い、任意に選択した２０箇所において厚さを測定し、平均値を求めた。
<Thickness (mm)>
Ono Sokki Using a digital linear gauge DG-925 (diameter of the measurement terminal part 1 cm), the thickness was measured at 20 arbitrarily selected locations, and the average value was obtained.
＜見掛け密度（ｇ／ｃｍ３）＞
（目付）／（厚み）から算出し、単位容積あたりの重量を求めた。
<Apparent density (g / cm 3 )>
The weight per unit volume was calculated from (weight per unit area) / (thickness).
＜空隙径（μｍ）、最大空隙径（μｍ）＞
不織布の空隙径は、ＳＴＭ−Ｆ−３１６記載のバブルポイント法およびミーンフロー法により、平均空隙径、最大空隙径を求めた。単位はそれぞれμｍである。
<Void diameter (μm), maximum gap diameter (μm)>
As for the void diameter of the nonwoven fabric, the average void diameter and the maximum void diameter were determined by the bubble point method and the mean flow method described in STM-F-316. Each unit is μm.
＜融点もしくは熱分解温度（℃）＞
ＪＩＳ Ｋ ７１２１、または、ＪＩＳ Ｋ ７１２０に準じ、示差走査熱量測定により得られるＤＳＣ曲線の融解ピークの頂点の温度、もしくは、熱重量測定より得られるＴＧ曲線にて、試料の重量減少が始まる温度から求めた。
<Melting point or thermal decomposition temperature (℃)>
In accordance with JIS K 7121 or JIS K 7120, from the temperature at the top of the melting peak of the DSC curve obtained by differential scanning calorimetry, or from the temperature at which the weight loss of the sample begins on the TG curve obtained from thermogravimetry Asked.
＜熱収縮率（％）＞
ＪＩＳ Ｌ １９０６に準じて、無緊張の状態で、２００℃×１５分熱処理後の不織布の乾熱収縮率を求めた。
<Heat shrinkage (%)>
In accordance with JIS L 1906, the dry heat shrinkage of the nonwoven fabric after heat treatment at 200 ° C. for 15 minutes was determined in a no-tension state.
＜不織布の引張強力（％）＞
不織布の引張強度はＪＩＳ Ｐ８１１３に準拠して、不織布の経方向および横方向に、それぞれ試験巾１０ｍｍ、試験長１００ｍｍで試験サンプルを採取し、引張速度１００ｍｍ／ｍｉｎで不織布の経方向の引張強力と横方向の引張強力を測定し、それらの比、すなわち（経方向の引張強力／横方向の引張強力）の値を求めた。
<Tensile strength of non-woven fabric (%)>
In accordance with JIS P8113, the tensile strength of the nonwoven fabric was obtained by taking a test sample with a test width of 10 mm and a test length of 100 mm in the warp direction and the transverse direction of the nonwoven fabric, respectively. The tensile strength in the transverse direction was measured, and the ratio thereof, that is, the value of (tensile strength in the warp direction / tensile strength in the transverse direction) was determined.
＜平均液滴径（μｍ）＞
面積基準の平均液滴径を、レーザー散乱／回折法により測定した。
<Average droplet diameter (μm)>
The area-based average droplet diameter was measured by laser scattering / diffraction method.
［実施例１］
特公昭４７−１０８６３号公報記載の方法に準じた界面重合法により製造した固有粘度（ＩＶ）＝１．３５のポリメタフェニレンイソフタルアミド粉末（帝人テクノプロダクツ製、１．３８ｇ／ｃｍ３）２０重量部を、０℃に冷却したジメチルアセトアミド（ＤＭＡｃ）８０重量部中に投入し、スラリー状にした後、４０℃まで昇温して溶解させ、ポリマー溶液を得た。
上記のポリマー溶液を、ギアポンプを使ってＵＳ６０１３２２３の紡糸装置に１２０ｇ／ｍｉｎで供給し、紡糸温度４０℃とし、１０ｍ３／ｍｉｎで圧空を供給して紡糸を行った。ここで、ＵＳ６０１３２２３の紡糸装置は、ポリマー溶液吐出孔の孔径が０．３ｍｍで、ポリマー溶液吐出ノズルが、１００×５列の配列で５００本が、５ｍｍピッチで等間隔となるように配置されたものを使用した。
圧縮空気を用いた凝固液供給装置であるスプレーノズルとして、平均液滴径が２５０μｍであるスプレーノズル（株式会社いけうち製、ＶＶＰシリーズ）を用い、これを後述する不織布のベルトの搬送方向の反対側（上流側）と搬送方向側（下流側）の両方に、ポリマー溶液吐出孔から下方向に５０ｍｍ、紡糸線から５０ｍｍの位置に一対となるように設置し、吐出後のポリマー溶液に、ポリマー溶液吐出孔から紡糸線上の下方１５０ｍｍの地点で、細化された糸条と凝固液が接触するようにスプレーノズルの噴射角度を調整した。スプレーノズルから噴射させた凝固液の平均液滴径は２５０μｍであった。
凝固液として水を使用し、一対のスプレーノズルに供給した水は５Ｌ／ｍｉｎで、供給した圧縮空気圧は０．５ＭＰａとした。
ギアポンプによりポリマー溶液吐出孔から吐出された糸条は、直ちに周囲の圧空と凝固液と共に、紡糸線上の下方向に捕集面に向かって流下させながら細化と凝固を行い、紡糸装置の下方７００ｍｍに設置されたベルト上に、搬送速度を３．５ｍ／ｍｉｎとして、連続繊維を積層し、表１記載の繊維構成、目付の不織布を得た。
また、流体整流板は、ベルトの搬送方向の反対側（上流側）と、ベルトの搬送方向側（下流側）の両方に、凝固液供給スプレーの直下に紡糸線と平行（紡糸線に対して０度）となるように、巾５００×長さ５５０×厚さ７ｍｍのものを取り付けた。
得られた不織布を金属製カレンダーロールにて温度２５０℃、設定線圧５０ｋｇ／ｃｍで熱処理し、上下ロール間のクリアランスを設けることによって、任意に線圧を調整し、表１記載の厚みの不織布を得た。評価結果を表１に示す。
[Example 1]
Polymetaphenylene isophthalamide powder (invented by Teijin Techno Products, 1.38 g / cm 3 ) having an intrinsic viscosity (IV) of 1.35 produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863 A part was put into 80 parts by weight of dimethylacetamide (DMAc) cooled to 0 ° C. to form a slurry, and then heated to 40 ° C. and dissolved to obtain a polymer solution.
The above polymer solution was fed at 120 g / min to a spinning apparatus of US Pat. No. 6,013,223 using a gear pump, the spinning temperature was 40 ° C., and compressed air was fed at 10 m 3 / min for spinning. Here, in the spinning apparatus of US6031323, the hole diameter of the polymer solution discharge holes is 0.3 mm, and the polymer solution discharge nozzles are arranged in an array of 100 × 5 rows so that 500 pieces are equally spaced at a pitch of 5 mm. I used something.
As a spray nozzle that is a coagulating liquid supply device using compressed air, a spray nozzle (Ikeuchi Co., Ltd., VVP series) having an average droplet diameter of 250 μm is used, which is opposite to the non-woven belt conveyance direction described later. (Upstream side) and the conveying direction side (downstream side) are installed so as to form a pair at a position of 50 mm downward from the polymer solution discharge hole and 50 mm from the spinning line. The spray angle of the spray nozzle was adjusted so that the thinned yarn and the coagulation liquid were in contact with each other at a point 150 mm below the spinning line from the discharge hole. The average droplet diameter of the coagulation liquid sprayed from the spray nozzle was 250 μm.
Water was used as the coagulation liquid, the water supplied to the pair of spray nozzles was 5 L / min, and the supplied compressed air pressure was 0.5 MPa.
The yarn discharged from the polymer solution discharge hole by the gear pump is immediately refined and solidified together with the surrounding compressed air and coagulating liquid while flowing down toward the collecting surface in the downward direction on the spinning line, and 700 mm below the spinning device. A continuous fiber was laminated on the belt installed at a speed of 3.5 m / min to obtain a fiber structure and fabric weight as shown in Table 1.
In addition, the fluid rectifying plate is parallel to the spinning line (to the spinning line) immediately below the coagulating liquid supply spray, both on the side opposite to the belt conveying direction (upstream side) and on the belt conveying direction side (downstream side). 0 degree) was attached with a width of 500 × length of 550 × thickness of 7 mm.
The obtained non-woven fabric was heat-treated with a metal calender roll at a temperature of 250 ° C. and a set linear pressure of 50 kg / cm, and a clearance between the upper and lower rolls was provided to arbitrarily adjust the linear pressure. Got. The evaluation results are shown in Table 1.
［実施例２］
凝固液供給装置であるスプレーノズルを、平均液滴径が５００μｍであるスプレーノズル（株式会社いけうち製、ＶＶシリーズ）に変えた以外は、実施例１と同様にして、表１記載の繊維構成、目付の不織布を得た。評価結果を表１に示す。
[Example 2]
The fiber configuration described in Table 1 is the same as in Example 1, except that the spray nozzle that is the coagulation liquid supply device is changed to a spray nozzle (Ikeuchi Co., Ltd., VV series) having an average droplet diameter of 500 μm. A fabric with a basis weight was obtained. The evaluation results are shown in Table 1.
［実施例３］
流体整流板の角度を、紡糸線に対して２０度に変更した以外は、実施例１と同様にして、表１記載の繊維構成、目付の不織布を得た。評価結果を表１に示す。
[Example 3]
Except having changed the angle of the fluid baffle plate into 20 degree | times with respect to the spinning line, it carried out similarly to Example 1, and obtained the fiber structure of Table 1, and the fabric weight of a fabric weight. The evaluation results are shown in Table 1.
［比較例１］
流体整流板を取付けない以外は、実施例１と同様にして、表１記載の繊維構成、目付の不織布を得た。評価結果を表１に示す。
[Comparative Example 1]
Except not attaching a fluid baffle plate, it carried out similarly to Example 1, and obtained the fiber structure of Table 1, and the fabric weight of a fabric weight. The evaluation results are shown in Table 1.
［比較例２］
固液供給装置であるスプレーノズルを、平均液滴径が１１００μｍであるスプレーノズル（株式会社いけうち製、Ｖシリーズ）に変えた以外は、実施例１と同様の方法で紡糸を行い、表１記載の繊維構成、目付の不織布を得た。評価結果を表１に示す。
[Comparative Example 2]
Spinning was carried out in the same manner as in Example 1 except that the spray nozzle, which is a solid-liquid supply device, was changed to a spray nozzle (Ikeuchi Co., Ltd., V series) having an average droplet diameter of 1100 μm. A non-woven fabric having a fiber structure and basis weight was obtained. The evaluation results are shown in Table 1.
［比較例３］
固液供給装置であるスプレーノズルを、平均液滴径が１１００μｍであるスプレーノズル（株式会社いけうち製、Ｖシリーズ）に変えた以外は、実施例３と同様の方法で紡糸を行い、表１記載の繊維構成、目付の不織布を得た。評価結果を表１に示す。
[Comparative Example 3]
Spinning was performed in the same manner as in Example 3 except that the spray nozzle, which is a solid-liquid supply device, was changed to a spray nozzle having an average droplet diameter of 1100 μm (Ikeuchi Co., Ltd., V series). A non-woven fabric having a fiber structure and basis weight was obtained. The evaluation results are shown in Table 1.
［比較例４］
流体整流板を、繊維の走行方向に従い２０度で広がるもの（紡糸線に対して−２０度）に変更した以外は、実施例１と同様にして、表１記載の繊維構成、目付の不織布を得た。評価結果を表１に示す。
[Comparative Example 4]
Except having changed the fluid baffle plate into what spreads at 20 degree | times according to the running direction of a fiber (-20 degree | times with respect to a spinning line), it carried out similarly to Example 1, and the fiber structure of Table 1, and a fabric weight of a fabric weight are described. Obtained. The evaluation results are shown in Table 1.
表１から明らかなように、本発明によれば、吐出孔の外側から噴出した気流を作用させて、該吐出したポリマー溶液を細径化させ、さらに本発明で規定するように、所定の平均液滴径の凝固液を噴射させ、その後、気流を整流することにより、両方の効果により、不織布を構成する繊維の配向を制御することができ、一方向に強度が高い不織布を得ることができる。 As is apparent from Table 1, according to the present invention, the air current ejected from the outside of the discharge hole is acted to reduce the diameter of the discharged polymer solution, and as defined in the present invention, the predetermined average By injecting a coagulating liquid having a droplet diameter and then rectifying the air flow, the orientation of fibers constituting the nonwoven fabric can be controlled by both effects, and a nonwoven fabric having high strength in one direction can be obtained. .
本発明の極細径繊維不織布は、一定方向で、巻き取りや、それを巻き出して加工を行う際に、該方向における力学特性に優れ、かつ、平均見掛け密度や平均空隙径等においても、電池用セパレータ、キャパシタ用セパレータ、並びコンデンサ用セパレータ、エアフィルター、液体フィルターなどの各種フィルター用素材として極めて有用な特性を備えている。また、吸音材、吸油材、各種クリーナー、絶縁材、透湿防水膜、遮熱材など幅広い用途に利用できる。さらに、本発明の製造方法は上記の極細径繊維不織布を容易に製造することができる。 When the ultrafine fiber nonwoven fabric of the present invention is wound in a certain direction, or unwound and processed, it has excellent mechanical properties in the direction, and the battery has an average apparent density, an average void diameter, etc. It has extremely useful characteristics as various filter materials such as separators for capacitors, separators for capacitors, separators for capacitors, air filters, and liquid filters. It can also be used for a wide range of applications such as sound absorbing materials, oil absorbing materials, various cleaners, insulating materials, moisture permeable waterproof membranes, and heat insulating materials. Furthermore, the production method of the present invention can easily produce the ultrafine fiber nonwoven fabric.
１：ダイ
２：キャビティー
３：紡糸ノズル
４：紡糸口金
５：ガスキャビティー
６：吸気口
７：ガス吐出口
８：ガスの流れ
９：ノズル内管（吐出孔）
１０：ポリマー溶液
１１：凝固液供給装置（凝固液供給ノズル）
１２：凝固液
１４：大気
１５：ポリマー
１６：プレート
１７：気流整流板
１８：繊維と気流整流板との角度
1: Die 2: Cavity 3: Spinning nozzle 4: Spinneret 5: Gas cavity 6: Intake port 7: Gas discharge port 8: Gas flow 9: Inner tube (discharge hole)
10: Polymer solution 11: Coagulation liquid supply device (coagulation liquid supply nozzle)
12: Coagulating liquid 14: Air 15: Polymer 16: Plate 17: Airflow rectifying plate 18: Angle between fiber and airflow rectifying plate
Claims (3)
（１）ポリマー溶液を、細径を有する吐出孔より吐出し、
（２）吐出孔の外側から噴出した気流を作用させて、該吐出したポリマー溶液を伸張または細径化させ、
（３）平均液滴径が１０００μｍ以下の凝固液を噴霧させて、該吐出したポリマー溶液を固化して、平均繊維直径が０．０１〜５０μｍの繊維とし、
（４）該繊維の走行方向に従って流路が拡大しない流体整流板を通過させた後、
（５）該繊維を捕集して不織布とすることを特徴とする極細径繊維不織布の製造方法。 A method for producing a nonwoven fabric from a polymer solution comprising:
(1) A polymer solution is discharged from a discharge hole having a small diameter,
(2) The air current ejected from the outside of the discharge hole is allowed to act to expand or reduce the diameter of the discharged polymer solution,
(3) Spraying a coagulation liquid having an average droplet diameter of 1000 μm or less to solidify the discharged polymer solution to obtain fibers having an average fiber diameter of 0.01 to 50 μm;
(4) After passing the fluid rectifying plate in which the flow path does not expand according to the traveling direction of the fiber,
(5) A method for producing an ultrafine fiber nonwoven fabric, wherein the fiber is collected to form a nonwoven fabric.
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