JP5217190B2 - Manufacturing method of fiber assembly - Google Patents
Manufacturing method of fiber assembly Download PDFInfo
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- JP5217190B2 JP5217190B2 JP2007056775A JP2007056775A JP5217190B2 JP 5217190 B2 JP5217190 B2 JP 5217190B2 JP 2007056775 A JP2007056775 A JP 2007056775A JP 2007056775 A JP2007056775 A JP 2007056775A JP 5217190 B2 JP5217190 B2 JP 5217190B2
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- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Description
本発明は、繊維集合体の製造方法に関するものであり、更に詳しくは、均一で、品位に優れた極細繊維不織布を得るに適した製造方法に関する。 The present invention relates to a method for producing a fiber assembly, and more particularly to a production method suitable for obtaining a uniform and excellent fine fiber nonwoven fabric.
近年、ナノファイバーと呼ばれる極細繊維の開発が盛んに進められており、その一つの方法として静電紡糸の検討がなされている（例えば特許文献１参照）。かかる静電紡糸に用いた製造方法として、紡糸ノズルから吐出された繊維をステンレス等からなるローラーを捕集手段とするものが開示されている（例えば特許文献２参照）。しかしながら、かかる製造方法は、湾曲面に繊維が捕集されるため、湾曲面に沿った形で繊維が堆積され、ローラーより剥離した際、カールが発生し品位が安定しないという問題点があった。一方、一般的な不織布製造装置で用いられているベルトコンベアを捕集手段として用いた静電紡糸装置による製造方法も開示されている（例えば特許文献３〜５参照）。かかる捕集手段として、シリコーン樹脂やフッ素樹脂を含有する捕集表面に繊維を捕集することで捕集繊維の剥離性を高めている。捕集面が平面であるため、剥離した際のカールは解消されるが、捕集部はアースされているのみであり、安定した紡糸状態を得るには不十分である。かかる問題点は生産性を向上させるため、コンベアの速度を高めた場合、顕著に現われる。
本発明は、従来技術の課題を背景としてなされたもので、均一で、品位に優れた繊維集合体を得ることができる、生産性に優れた製造方法を提供することを課題とする。 The present invention has been made against the background of the problems of the prior art, and it is an object of the present invention to provide a production method excellent in productivity that can obtain a uniform and excellent fiber assembly.
本発明者らは上記課題を解決するため、鋭意研究した結果、ついに本発明を完成するに至った。すなわち、本発明は、（１）紡糸原液供給ノズルと電極を有し、該ノズルと該電極との間に捕集手段を備え、静電紡糸を行うことにより捕集手段上に繊維集合体を得ることを特徴とする繊維集合体の製造方法、（２）前記捕集手段がベルトコンベアであることを特徴とする（１）記載の繊維集合体の繊維集合体の製造方法、（３）前記捕集手段を繊維集合体積層物の基材層とすることを特徴とする（１）記載の繊維集合体の製造方法、（４）前記原液供給ノズルに印加される電圧と前記電極に印加される電圧が正負異なることを特徴とする（１）〜（３）いずれかに記載の繊維集合体の製造方法、（５）前記捕集手段と電極との間に、立体障害手段を備えていることを特徴とする（１）〜（４）いずれかに記載の繊維集合体の製造方法、（６）前記電極と前記立体障害手段が電気的に繋がっていることを特徴とする（１）〜（５）いずれかに記載の繊維集合体の製造方法、（７）前記立体障害手段が１個又は複数個のローラーであることを特徴とする（５）記載の繊維集合体の製造方法、である。 As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention includes (1) a spinning dope supply nozzle and an electrode, a collecting means is provided between the nozzle and the electrode, and a fiber assembly is formed on the collecting means by performing electrostatic spinning. (2) The method for producing a fiber assembly of a fiber assembly according to (1), wherein the collecting means is a belt conveyor, and (3) (1) The method for producing a fiber assembly according to (1), wherein the collecting means is a base layer of the fiber assembly laminate, and (4) a voltage applied to the stock solution supply nozzle and the electrode. (1) The manufacturing method of the fiber assembly according to any one of (1) to (3), wherein the voltage is different between positive and negative, and (5) a steric hindrance means is provided between the collection means and the electrode. (6) The method for producing a fiber assembly according to any one of (1) to (4), The method for producing a fiber assembly according to any one of (1) to (5), wherein the electrode and the steric hindrance means are electrically connected, and (7) one or a plurality of the steric hindrance means. (5) The method for producing a fiber assembly according to (5), wherein the roller assembly is a single roller.
本発明によると、高い生産性で、品位に優れた極細繊維集合体が得られるという利点を有する。 According to the present invention, there is an advantage that an ultrafine fiber assembly excellent in quality can be obtained with high productivity.
以下、本発明を詳細に記述する。
本発明の製造方法は、紡糸原液供給ノズルと電極を有し、該ノズルと該電極との間に捕集手段を備えていることが好ましい。かかる構成の製造方法であれば、極めて高い品位の極細繊維布帛が得られるからである。すなわち、静電紡糸法にて、高電圧に印加されたノズルから紡出される繊維は帯電しており、これを捕集手段の背後に設置した電極によって積極的に引き寄せることにより、捕集手段に対し安定して接触し、均一で欠点が少ない極細繊維布帛が得られる。
Hereinafter, the present invention will be described in detail.
The production method of the present invention preferably includes a spinning dope supply nozzle and an electrode, and a collecting means is provided between the nozzle and the electrode. This is because an extremely fine fiber fabric of extremely high quality can be obtained with the manufacturing method having such a configuration. That is, in the electrospinning method, the fiber spun from the nozzle applied with a high voltage is charged, and by actively attracting it with the electrode installed behind the collecting means, On the other hand, it is possible to obtain an ultrafine fiber fabric that is stably contacted and uniform and has few defects.
本発明の製造方法から繊維集合体を製造する場合の紡糸溶液は、少なくとも高分子化合物と溶媒からなる紡糸原液を用いる。 As a spinning solution for producing a fiber assembly from the production method of the present invention, a spinning solution comprising at least a polymer compound and a solvent is used.
高分子化合物としては特に限定されるものではないが、例えば、ポリアクリロニトリル、ポロエチレン、ポリプロピレン、ポリエチレングリコール、ポリグリコール酸、ポリメタクリル酸、ポリメタクリル酸メチル、ポリビニルアルコール、ポリカーボネート、ポリスチレン、ポリアミド、ポリイミド、ポリアミドイミド、ポリイミドベンザゾール、ポリベンゾイミダゾール、ポリグリコール酸、ポリ乳酸、ポリエチレンテレフタレート、ポリウレタン、セルロース、ポリペプチド、ポリヌクレオシド、ポリヌクレオチド、タンパク質、酵素などを使用することができる。これらの以外の高分子化合物も使用可能であり、これらの高分子化合物を含め、２種以上の高分子化合物を混合して用いることも可能である。 The polymer compound is not particularly limited. For example, polyacrylonitrile, polyethylene, polypropylene, polyethylene glycol, polyglycolic acid, polymethacrylic acid, polymethyl methacrylate, polyvinyl alcohol, polycarbonate, polystyrene, polyamide, polyimide Polyamideimide, polyimide benzazole, polybenzimidazole, polyglycolic acid, polylactic acid, polyethylene terephthalate, polyurethane, cellulose, polypeptide, polynucleoside, polynucleotide, protein, enzyme, and the like can be used. Polymer compounds other than these can also be used, and two or more kinds of polymer compounds including these polymer compounds can be mixed and used.
溶媒としては、使用する高分子によって変わるため、特に限定するものではない。例えば、水、アセトン、メタノール、エタノール、プロパノール、イソプロピルアルコール、メチルエチルケトン、テトラヒドロフラン、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン、１，４−ジオキサン、ピリジン、蟻酸、ベンゼン、トルエン、キシレン、シクロヘキサン、シクロヘキサノン、四塩化炭素、塩化メチレン、クロロホルム、トリクロロエタン、エチレンカーボネート、ジエチレンカーボネート、プロピレンカーボネート、などを使用することができる。これら以外の溶媒も使用可能であり、これらの溶媒を含め、２種以上の溶媒を混合して用いることも可能である。 The solvent is not particularly limited because it varies depending on the polymer used. For example, water, acetone, methanol, ethanol, propanol, isopropyl alcohol, methyl ethyl ketone, tetrahydrofuran, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,4-dioxane, Pyridine, formic acid, benzene, toluene, xylene, cyclohexane, cyclohexanone, carbon tetrachloride, methylene chloride, chloroform, trichloroethane, ethylene carbonate, diethylene carbonate, propylene carbonate, and the like can be used. Solvents other than these can also be used, and it is also possible to use a mixture of two or more solvents including these solvents.
紡糸状態、得られる極細繊維の性能を高めるために無機塩、有機塩、酸化防止剤、光触媒などの添加剤を加えることが可能である。 Additives such as inorganic salts, organic salts, antioxidants and photocatalysts can be added to improve the spinning state and the performance of the resulting ultrafine fibers.
本発明の製造方法を行う紡糸環境空間の水分量（絶対湿度）が２ｇ／ｍ３〜１２ｇ／ｍ３が好ましい。 The water content of the spinning environment space for performing the production method of the present invention (absolute humidity) is preferably 2g / m 3 ~12g / m 3 .
本発明の製造方法は、前記捕集手段がベルトコンベアであることが好ましい。ベルトコンベアを採用することにより、連続生産に適する生産性が高い製造方法となるからである。また、ベルトコンベアのベルトは、導電性であることが好ましい。導電性であることにより、紡糸原液供給ノズルから紡出された繊維を、電極が有効に引き寄せることができるからである。また、ベルトコンベアのベルトは、ベルト自体は導電性であっても、材料自体が絶縁性、不帯電性であるもの、例えば合成ゴム等を材料とする空隙を有するベルト、例えばメッシュ、寒冷紗等が好ましい。かかるベルトであれば、紡糸原液供給ノズルから紡出された繊維を、捕集手段に向けて有効に引き寄せ、捕集手段に捕集後、不織布を搬送する際、ベルトから剥離しやすく、トラブルが発生し難いからである。 In the production method of the present invention, the collecting means is preferably a belt conveyor. This is because the use of a belt conveyor provides a highly productive method suitable for continuous production. The belt of the belt conveyor is preferably conductive. This is because the electrode can effectively draw the fiber spun from the spinning dope supply nozzle by being conductive. Further, the belt of the belt conveyor may be a belt having a gap made of synthetic rubber or the like, for example, a mesh, a cold chill, etc., even though the belt itself is conductive, but the material itself is insulative or uncharged. preferable. With such a belt, the fibers spun from the spinning dope supply nozzle are effectively drawn toward the collecting means, and after being collected by the collecting means, when transporting the nonwoven fabric, it is easy to peel off from the belt, causing trouble. This is because it is difficult to occur.
本発明の製造方法は、前記捕集手段が、極細繊維を積層する基材層であることも好ましい形態の一つである。すなわち、積層することになり、積層工程が簡略できると共に、基材層が保護層となって、最終製品となるまでの工程中でも極細繊維層を有効に保護することができるからである。
基材層の形態は特に限定されず、編物、織物、不織布、多孔膜、紙、フィルム等の形態であってもよいが、表面平滑性、通気性、極細繊維保護性能のバランスから不織布であることが特に好ましい。また、材質は特に限定されず、ポリアクリロニトリル、ポロエチレン、ポリプロピレン、ポリエチレングリコール、ポリグリコール酸、ポリメタクリル酸、ポリメタクリル酸メチル、ポリビニルアルコール、ポリカーボネート、ポリスチレン、ポリアミド、ポリイミド、ポリアミドイミド、ポリイミドベンザゾール、ポリベンゾイミダゾール、ポリグリコール酸、ポリ乳酸、ポリエチレンテレフタレート、ポリウレタン、セルロースなどのような高分子化合物やアルミニウム、鉄などのような金属類、炭素を使用することができる。また、これらを組み合わせたものも使用することができる。用いられる用途に応じて適宜使用する。
In a preferred embodiment of the production method of the present invention, the collecting means is a base material layer on which ultrafine fibers are laminated. That is, since the lamination process is simplified, the lamination process can be simplified, and the ultrafine fiber layer can be effectively protected even during the process until the base material layer becomes a protective layer and becomes the final product.
The form of the base material layer is not particularly limited, and may be a knitted fabric, a woven fabric, a nonwoven fabric, a porous membrane, paper, a film, or the like, but is a nonwoven fabric in terms of the balance of surface smoothness, air permeability, and ultrafine fiber protection performance. It is particularly preferred. The material is not particularly limited, and polyacrylonitrile, polyethylene, polypropylene, polyethylene glycol, polyglycolic acid, polymethacrylic acid, polymethyl methacrylate, polyvinyl alcohol, polycarbonate, polystyrene, polyamide, polyimide, polyamideimide, polyimide benzazole Polymer compounds such as polybenzimidazole, polyglycolic acid, polylactic acid, polyethylene terephthalate, polyurethane, and cellulose, metals such as aluminum and iron, and carbon can be used. A combination of these can also be used. It is used appropriately according to the intended use.
本発明の製造方法は、捕集手段と電極との間に、立体障害手段を備えていることが好ましい。本発明は、電極により、紡出された極細繊維を引き寄せて安定に捕集することを要旨とするところ、電極の作用により、捕集手段自体が引き寄せられ、捕集面が湾曲化して不安定となることを防止して平面を維持し、高い品位の極細繊維布帛又はその積層体が得られるからである。なお、本発明でいう立体障害手段は、物理的に捕集手段が電極に引き寄せることを物理的に防止するもので足り、例えば布帛や紙のような形状のものを、張ってもよい。 The production method of the present invention preferably includes steric hindrance means between the collecting means and the electrode. The gist of the present invention is to attract and stably collect the spun ultrafine fibers by the electrode, and the action of the electrode attracts the collecting means itself, and the collecting surface is curved and unstable. This is because a flat fiber is maintained while preventing the occurrence of a high quality, and a high-quality ultrafine fiber fabric or a laminate thereof is obtained. The steric hindrance means referred to in the present invention is sufficient to physically prevent the collection means from being attracted to the electrode. For example, the steric hindrance means may be stretched in a shape such as cloth or paper.
本発明の製造方法は、原液供給ノズルに印加される電圧と電極に印加される電圧が正負異なることが好ましい。ノズルより紡出された繊維は高電荷を有しており、繊維が捕集手段に捕集された際、捕集手段に電荷が蓄えられる。この電荷を積極的に除去することは安定した紡糸状態を作り上げる。そのためには原液供給ノズルに印加される電圧と正負異なる電圧を電極に印加されることが好ましい。 In the production method of the present invention, the voltage applied to the stock solution supply nozzle and the voltage applied to the electrode are preferably different from each other. The fiber spun from the nozzle has a high charge, and when the fiber is collected by the collecting means, the charge is stored in the collecting means. Removing this charge positively creates a stable spinning state. For this purpose, it is preferable that a voltage different from the voltage applied to the stock solution supply nozzle is applied to the electrode.
本発明の製造方法に用いる立体障害手段は、前記立体障害手段が１個又は複数個のローラーであることが好ましい。ローラーであれば、ベルト又は基材層との摩擦が小さく、これらの摩耗がし難くなるからである。 It is preferable that the steric hindrance means used in the production method of the present invention is one or a plurality of rollers. This is because if the roller is used, the friction with the belt or the base material layer is small and it is difficult to wear them.
本発明の製造方法は、極細繊維集合体を製造する際、特に効果を発揮する。極細繊維は、比表面積が大きいため荷電し易く、周辺物の帯電に敏感であり、更に気流乱れ等の外乱の影響を受けやすいため、捕集手段に接触する点が乱れ易いところ、ノズルより紡出された高度に荷電された繊維を、電極を設置して、これにより引き寄せる本発明の製造方法によれば、捕集手段の接触点を安定化させることができるからである。ここでいう極細繊維とは０．００１μｍ〜１μｍをいい、より本発明が効果を発揮するのは、０．００５μｍ〜０．５μｍ、更に効果を発揮するのは、０．０１μｍ〜０．２μｍである。 The production method of the present invention is particularly effective when producing an ultrafine fiber assembly. Ultrafine fibers are easily charged due to their large specific surface area, are sensitive to the charging of surrounding objects, and are also susceptible to disturbances such as airflow turbulence. This is because the contact point of the collecting means can be stabilized according to the production method of the present invention in which the electrode is placed and the drawn out highly charged fiber is drawn. The ultrafine fiber here means 0.001 μm to 1 μm, and the present invention is more effective when it is 0.005 μm to 0.5 μm, and the effect is more effective when it is 0.01 μm to 0.2 μm. is there.
以下、実施例によって本発明を具体的に説明するが、これらは本発明の範囲を限定するものではない。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.
（参考例）
（ポリアクリロニトリル溶液の作製）
ポリアクリロニトリル（Ｐｏｌｙｓｃｉｅｎｓｅ製、重量平均分子量：１５万）をＮ，Ｎ−ジメチルホルムアミドに１０重量％になるように溶解し、ポリアクリロニトリル溶液を作製した。これを紡糸溶液とした。
(Reference example)
(Preparation of polyacrylonitrile solution)
Polyacrylonitrile (manufactured by Polyscience, weight average molecular weight: 150,000) was dissolved in N, N-dimethylformamide so as to be 10% by weight to prepare a polyacrylonitrile solution. This was used as a spinning solution.
（極細繊維積層体の作製）
（実施例１）
図１に示すような製造装置にて、溶液槽１にシリンジ、紡糸ノズル２に先端がフラットな内径０．９ｍｍのステンレス製針、捕集手段３にポリエチレンテレフタレート不織布、立体障害手段７にステンレス製ローラを用いた。参考例に示すポリアクリロニトリル溶液を溶液槽１に入れ、ノズル２に１４ｋＶの正電圧を印加し、電極６に２ｋＶの負電圧を印加し、図１に示す方向に進行した不織布３上に平均繊維径０．１５μｍの繊維を紡糸した。不織布上に集中して紡出され、品位の高いものが得られた。
(Preparation of ultrafine fiber laminate)
Example 1
In the manufacturing apparatus as shown in FIG. 1, a syringe is used for the solution tank 1, a stainless steel needle having an inner diameter of 0.9 mm with a flat tip on the spinning
（比較例１）
電極６の負電圧を印加しない以外は実施例１と同様に行った。ノズルから吐出された紡糸液は、ノズル直下中心に紡出されず、広範囲に散逸するように紡出され、品位の悪いものであった。
(Comparative Example 1)
The same operation as in Example 1 was performed except that the negative voltage of the electrode 6 was not applied. The spinning solution discharged from the nozzle was not spun around the center of the nozzle, spun so as to dissipate over a wide area, and had poor quality.
（比較例２）
立体障害手段７を有せず、電極６の負電圧を印加しない以外は実施例１と同様に行った。ノズルから吐出された紡糸液は、ノズル直下中心に紡出されず、広範囲に散逸するように紡出され、品位の悪いものであった。
(Comparative Example 2)
The same procedure as in Example 1 was performed except that the steric hindrance means 7 was not provided and the negative voltage of the electrode 6 was not applied. The spinning solution discharged from the nozzle was not spun around the center of the nozzle, spun so as to dissipate over a wide area, and had poor quality.
本発明の製造方法によれば、高い生産性で、品位の高い極細繊維布帛又はその積層体をえることが可能となり、高い品位が求められる用途においても使用することが可能となり、産業界に寄与すること大である。 According to the production method of the present invention, it is possible to obtain a high-quality, ultra-fine fiber fabric or a laminate thereof with high productivity, and it can be used in applications requiring high quality, contributing to the industry. It is great to do.
１：溶液槽
２：紡糸ノズル
３：捕集手段
４：巻出ロール
５：巻取ロール
６：電極
７：立体障害手段
1: Solution tank 2: Spinning nozzle 3: Collection means 4: Unwinding roll 5: Winding roll 6: Electrode 7: Three-dimensional obstacle means
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