JPWO2017115876A1 - Spinning method and apparatus - Google Patents
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D4/00—Spinnerette packs; Cleaning thereof
- D01D4/02—Spinnerettes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
ノズルと、ノズルに高分子溶液を供給してノズル先端からそれを噴出させる高分子溶液供給手段と、少なくとも噴出直後における高分子溶液の周囲に、高分子溶液の溶媒と同一の溶媒の蒸気を含む気体を供給する溶媒蒸気供給手段と、を備える紡糸用ノズル装置、ならびに当該紡糸用ノズル装置を用いた紡糸方法。紡糸液を吐出するノズル先端での紡糸液の固化が抑制される。A nozzle, a polymer solution supply means for supplying the polymer solution to the nozzle and ejecting the polymer solution from the nozzle tip, and at least surrounding the polymer solution immediately after the ejection includes a vapor of the same solvent as the solvent of the polymer solution A spinning nozzle apparatus comprising: a solvent vapor supply means for supplying a gas; and a spinning method using the spinning nozzle apparatus. Solidification of the spinning solution at the nozzle tip that discharges the spinning solution is suppressed.
Description
本発明は、ノズル先端から高分子溶液を噴出させる工程を含む高分子を含む繊維の紡糸方法であって、噴出直後における高分子溶液の周囲に、高分子溶液の溶媒と同一の溶媒の蒸気を含む気体を供給しつつ紡糸する紡糸方法、及びそのための装置に関する。 The present invention is a fiber spinning method including a step of ejecting a polymer solution from the tip of a nozzle, and a vapor of the same solvent as the solvent of the polymer solution is provided around the polymer solution immediately after ejection. The present invention relates to a spinning method for spinning while supplying a gas containing the gas, and an apparatus therefor.
近年、ナノファイバーからなるシート等の成形体が、その比表面積の高さから、従来の繊維成形体にはない特性を有する素材として注目されている。こうしたナノファイバーの製造方法（紡糸方法）としては、エレクトロスピニング法がよく知られている。
エレクトロスピニング法は、ポリマーを溶媒に溶解させた溶液（ドープ液）を、ドープ液吐出ノズルの先端に供与し、ノズル先端と電極（コレクター）間に高電圧を印加することで、コレクター上に繊維成形体を得る方法である。その工程としては、高分子を溶媒に溶解させて溶液（ドープ液）を製造する工程と、該ドープ液をノズル先端に供与し高電圧を印加する工程と、該ドープ液をノズル先端より電極（コレクター）方向に噴出させる工程と、噴出させドープ液から溶媒を蒸発させて繊維成形体を形成させる工程と、任意に実施しうる工程として形成された繊維成形体の電荷を消失させる工程と、電荷消失によって繊維成形体をコレクター上に累積させる工程とを含む。
エレクトロスピニング法においては、ドープ液に揮発性溶媒を使用する場合でも連続生産を可能にするという課題がある。この点、特許文献１には、従来技術における一重管ノズル近傍において、生成しつつあるナノファイバーを溶媒で取り囲むことで、生成したナノファイバーのノズルへの吸着を溶媒流により物理的に防止および／または洗浄することで、連続生産を可能にする技術が開示されている。In recent years, molded articles such as sheets made of nanofibers have attracted attention as materials having characteristics not found in conventional fiber molded articles because of their high specific surface area. As a method for producing such nanofiber (spinning method), an electrospinning method is well known.
In the electrospinning method, a solution (dope solution) in which a polymer is dissolved in a solvent is supplied to the tip of a dope solution discharge nozzle, and a high voltage is applied between the nozzle tip and an electrode (collector), whereby fibers are collected on the collector. This is a method for obtaining a molded body. As the steps, a step of dissolving a polymer in a solvent to produce a solution (dope solution), a step of applying the high voltage by supplying the dope solution to the tip of the nozzle, and an electrode ( A step of ejecting in the direction of the collector), a step of ejecting and evaporating the solvent from the dope solution to form a fiber molded body, a step of eliminating the charge of the fiber molded body formed as an optional process, And accumulating the fiber molded body on the collector by disappearance.
The electrospinning method has a problem that continuous production is possible even when a volatile solvent is used for the dope solution. In this regard, Patent Document 1 discloses that the nanofibers that are being produced are surrounded by a solvent in the vicinity of the single-tube nozzle in the prior art, so that adsorption of the produced nanofibers to the nozzle is physically prevented and / or Alternatively, a technology that enables continuous production by washing is disclosed.
本発明者らは、エレクトロスピニング法においてドープ液の溶媒に揮発性のものを用いる場合、ドープ液をノズル先端より噴出させる工程において、ノズル先端で形成されるテーラーコーン（ノズル先端で紡糸時に生じるもので、ノズル先端に供与された液滴にその表面張力を超えた電圧が印加されることで液滴が電圧方向に引き伸ばされることで生じる、通常コーン形状のもの）の固化を生じ、この固形物が時間とともに成長することが、紡糸安定性の悪化や紡糸収率の低下、さらには連続生産ができなくなる問題の原因であることを突き止めた。そしてかかる問題は、エレクトロスピニング法に限られず、気中に高分子溶液を紡出させる紡糸法に共通して発生することがわかった。
本発明の目的は、こうした問題を解決することであり、例えばエレクトロスピニングにおけるテーラーコーンの固化、成長を抑制するなど、気中に高分子溶液を紡出させる紡糸法におけるノズル先端での紡糸液の固化を抑制する方法及び装置を提供することである。In the electrospinning method, when a volatile solvent is used as the solvent of the dope solution, the present inventors have developed a tailor cone formed at the tip of the nozzle in the step of ejecting the dope solution from the tip of the nozzle. In this case, the liquid applied to the tip of the nozzle is applied with a voltage exceeding its surface tension, causing the liquid droplet to be stretched in the direction of the voltage. It has been found that the fact that the growth over time is the cause of problems such as deterioration in spinning stability, reduction in spinning yield, and inability to perform continuous production. It has been found that such a problem occurs not only in the electrospinning method but in common with the spinning method in which the polymer solution is spun in the air.
An object of the present invention is to solve these problems. For example, the spinning solution at the tip of a nozzle in a spinning method in which a polymer solution is spun in the air, for example, suppressing the solidification and growth of a tailor cone in electrospinning. It is to provide a method and apparatus for suppressing solidification.
上記課題に鑑み、本発明者らは鋭意研究した結果、紡糸機器におけるノズル装置として、ノズルに繊維の原料となる高分子溶液を供給する手段と、該ノズルの先端に該高分子溶液の溶媒蒸気を供給する手段とを備えるノズル装置とし、該ノズルの先端近傍に該高分子溶液の溶媒蒸気を供給しつつ、該ノズルに繊維の原料となる高分子溶液を供給して繊維を製造することにより、気中に紡糸液を吐出する紡糸方法におけるノズル先端での紡糸液の固化が抑制されることを見出し、本発明を完成した。
すなわち、本発明は以下のものである。
〔１〕ノズルと、ノズルに高分子溶液を供給してノズル先端からそれを噴出させる高分子溶液供給手段と、少なくとも噴出直後における高分子溶液の周囲に、高分子溶液の溶媒と同一の溶媒の蒸気を含む気体を供給する溶媒蒸気供給手段と、を備える紡糸用ノズル装置。
〔２〕ノズルである内管と、それを囲む外管との二重管構造部分を有し、高分子溶液の溶媒と同一の溶媒の蒸気を含む気体が内管と外管との間の空間から供給されるよう構成された〔１〕に記載の紡糸用ノズル装置。
〔３〕ノズル先端から高分子溶液を噴出させる工程を含む高分子を含む繊維の紡糸方法であって、少なくとも噴出直後における高分子溶液の周囲に、高分子溶液の溶媒と同一の溶媒の蒸気を含む気体を供給しつつ紡糸する、紡糸方法。
〔４〕供給する気体が紡糸時の条件で気相である物質を含み、供給する気体中、高分子溶液の溶媒と同一の溶媒の蒸気が飽和している〔３〕に記載の紡糸方法。In view of the above problems, as a result of intensive research, the present inventors have, as a nozzle device in a spinning machine, a means for supplying a polymer solution that is a raw material for fibers to the nozzle, and a solvent vapor of the polymer solution at the tip of the nozzle. And supplying a polymer solution as a fiber raw material to the nozzle while producing a fiber while supplying a solvent vapor of the polymer solution in the vicinity of the tip of the nozzle. The present inventors have found that solidification of the spinning solution at the nozzle tip in the spinning method in which the spinning solution is discharged into the air is suppressed, and the present invention has been completed.
That is, the present invention is as follows.
[1] A nozzle, a polymer solution supply means for supplying the polymer solution to the nozzle and ejecting the polymer solution from the nozzle tip, and at least around the polymer solution immediately after the ejection, the same solvent as the solvent of the polymer solution A spinning nozzle device comprising: a solvent vapor supply unit configured to supply a gas containing vapor.
[2] A double-pipe structure portion having an inner tube as a nozzle and an outer tube surrounding the inner tube, and a gas containing vapor of the same solvent as the solvent of the polymer solution is interposed between the inner tube and the outer tube The spinning nozzle device according to [1], which is configured to be supplied from a space.
[3] A spinning method of a fiber containing a polymer including a step of ejecting a polymer solution from a nozzle tip, wherein a vapor of the same solvent as the solvent of the polymer solution is provided at least around the polymer solution immediately after ejection. A spinning method in which spinning is performed while supplying a gas containing the same.
[4] The spinning method according to [3], wherein the gas to be supplied contains a substance that is in a gas phase under the spinning conditions, and the vapor of the same solvent as the solvent of the polymer solution is saturated in the gas to be supplied.
本発明の効果は、気中に高分子溶液を紡出させる紡糸法において、紡糸液を吐出するノズル先端での紡糸液の固化が抑制されることである。これにより、繊維成分のノズル先端での詰まりや噴出不良が軽減され、ひいては紡糸安定性や紡糸収率が向上し、また連続生産が可能となる。 The effect of the present invention is that, in a spinning method in which a polymer solution is spun in the air, solidification of the spinning solution at the nozzle tip that discharges the spinning solution is suppressed. As a result, clogging and ejection failure of the fiber component at the nozzle tip are reduced, and as a result, spinning stability and spinning yield are improved, and continuous production becomes possible.
図１は、本発明のノズル装置の一例として二重管ノズルを用いた、エレクトロスピニング法による繊維製造機器の全体図である。
図２は、本発明のノズル装置の一例としての二重管構造を有するノズル装置である。FIG. 1 is an overall view of a fiber manufacturing apparatus using an electrospinning method using a double tube nozzle as an example of the nozzle device of the present invention.
FIG. 2 is a nozzle device having a double tube structure as an example of the nozzle device of the present invention.
本発明のノズル装置において、ノズルに繊維の原料となる高分子溶液（ドープ液）を供給する手段としては、気中に高分子溶液を紡出させる紡糸装置におけるノズル装置として通常のものを採用することができる。また、該ノズルの先端にドープ液の溶媒蒸気を供給する手段にも特に制限はないが、エレクトロスピニング法においては紡糸時の紡糸方向へのテーラーコーン形成を妨げないものが好ましく、例えば、ノズルとしてドープ液が供給される内管と、それを囲む外管とを有し、ドープ液溶媒の蒸気を含む気体が内管と外管との間の空間から、ノズルから紡糸液が噴出される方向とほぼ同じ方向に、供給されるように構成したものを採用することができる。これにより、少なくとも噴出直後の高分子溶液は、当該溶媒蒸気の雰囲気下におかれる。
本発明の製造方法では、ノズル先端から高分子溶液を噴出させる工程としては、気中に高分子溶液を紡出させる紡糸方法における通常の方法を採用することができる。また、少なくとも噴出直後における高分子溶液の周囲（近傍）に、高分子溶液の溶媒と同一の溶媒の蒸気を含む気体を供給する工程としては、エレクトロスピニング法においては紡糸時の紡糸方向へのテーラーコーン形成を妨げない方法が好ましく、例えば、ノズルから紡糸液が噴出される方向とほぼ同じ方向に、噴出される紡糸液の周囲に紡糸液の溶媒を含む気体を吹き付ける方法を採用することができる。
本発明は、紡糸液からその溶媒が気化されることにより繊維が生成する紡糸技術であればいずれのものでも適用でき、例えばエレクトロスピニング法、ソリューションブロウスピニング法、あるいはフォーススピニング法で用いられるが、なかでもエレクトロスピニング法で好適に用いられる。
本発明において使用できるポリマーの種類としては、ポリフッ化ビニリデン、ポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体、ポリアクリロニトリル、ポリアクリロニトリル−メタクリレート共重合体、ポリメタクリル酸メチル、ポリ塩化ビニル、ポリ塩化ビニリデン−アクリレート共重合体、ポリエチレン、ポリプロピレン、ナイロン１２、ナイロン−４，６などのナイロン系、アラミド、ポリベンズイミダゾール、ポリビニルアルコール、セルロース、酢酸セルロース、酢酸セルロースブチレート、ポリビニルピロリドン−酢酸ビニル、ポリ（ビス−（２−（２−メトキシ−エトキシエトキシ））ホスファゼン）、ポリプロピレンオキサイド、ポリエチレンイミド、ポリこはく酸エチレン、ポリアニリン、ポリエチレンサルファイド、ポリオキシメチレン−オリゴ−オキシエチレン、ＳＢＳ共重合体、ポリヒドロキシ酪酸、ポリ酢酸ビニル、ポリエチレンテレフタレート、ポリエチレンオキサイド、コラーゲン、ポリ乳酸、ポリグリコール酸、ポリＤ，Ｌ−乳酸−グリコール酸共重合体、ポリアリレート、ポリプロピレンフマラート、ポリカプロラクトンなどの生分解性高分子、ポリペプチド、タンパク質などのバイオポリマー、コールタールピッチ、石油ピッチなどのピッチ系などの何らかの溶媒に溶解可能な様々な高分子が挙げられる。
高分子溶液の溶媒と溶媒蒸気として用いる溶媒は同一であり、使用できる溶媒種としては、例えばアセトン、クロロホルム、エタノール、２−プロパノール、メタノール、トルエン、テトラヒドロフラン、水、ベンゼン、ベンジルアルコール、１，４−ジオキサン、１−プロパノール、四塩化炭素、シクロヘキサン、シクロヘキサノン、ジクロロメタン、フェノール、ピリジン、トリクロロエタン、酢酸、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルアセトアミド、１−メチル−２−ピロリドン、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、アセトニトリル、Ｎ−メチルモルホリン−Ｎ−オキシド、ブチレンカーボネート、１，４−ブチロラクトン、ジエチルカーボネート、ジエチルエーテル、１，２−ジメトキシエタン、１，３−ジメチル−２−イミダゾリジノン、１，３−ジオキソラン、エチルメチルカーボネート、メチルホルマート、３−メチルオキサゾリジン−２−オン、メチルプロピオネート、２−メチルテトラヒドロフラン、スルホラン、及びこれらの溶媒群から選択される２種類以上の混合溶媒を用いることができる。
本発明の２重管構造を有するノズルの構造として、ノズル内径は０．１５〜１．０７ｍｍが好ましく、さらに好ましくは０．３４〜０．８４ｍｍである。また溶媒蒸気の噴出される部分となる二重管ノズルの外輪の内径は１．００〜２．００ｍｍが好ましく、更に好ましくは１．３０〜１．７０ｍｍである。ノズルの内径及び外輪の内径が当該範囲から外れるとノズル先端に固化物が発生しやすくなる。
高分子溶液の流量範囲としては、紡糸可能な範囲の流量であれば特に限定されるものではないが、好ましくは〜２０ｍｌ／ｈの範囲で設定することができる。
使用される溶媒蒸気分圧に関しては、例えば溶媒の飽和蒸気圧の１／２以上の範囲で用いることができるが、溶媒蒸気が飽和していることが好ましい。溶媒飽和蒸気が当該範囲から外れるとノズル先端に固化物が発生しやすくなる。
溶媒蒸気のガス流量としては１００〜１０００ｍｌ／ｍｉｎが好ましく、さらに好ましくは２００〜８００ｍｌ／ｍｉｎである。ガス流量が当該範囲から外れるとノズル先端に固化物が発生しやすくなる。In the nozzle device of the present invention, as a means for supplying a polymer solution (dope solution) as a fiber raw material to the nozzle, a normal nozzle device in a spinning device for spinning the polymer solution in the air is employed. be able to. In addition, there is no particular limitation on the means for supplying the solvent vapor of the dope solution to the tip of the nozzle, but in the electrospinning method, one that does not interfere with the formation of the tailor cone in the spinning direction during spinning is preferable. A direction in which a spinning solution is ejected from a nozzle from a space between an inner tube and an outer tube, which includes an inner tube to which a dope solution is supplied and an outer tube that surrounds the inner tube, It is possible to adopt a configuration configured to be supplied in substantially the same direction. As a result, at least the polymer solution immediately after ejection is placed in an atmosphere of the solvent vapor.
In the production method of the present invention, as the step of ejecting the polymer solution from the nozzle tip, a usual method in a spinning method in which the polymer solution is spun in the air can be employed. In the electrospinning method, a tailor in the spinning direction at the time of spinning is used as a step of supplying a gas containing vapor of the same solvent as the solvent of the polymer solution at least around (around) the polymer solution immediately after ejection. A method that does not interfere with cone formation is preferable. For example, a method of spraying a gas containing a solvent of the spinning solution around the spinning solution to be ejected in the same direction as the direction in which the spinning solution is ejected from the nozzle can be employed. .
The present invention can be applied to any spinning technology in which fibers are produced by the evaporation of the solvent from the spinning solution, and is used in, for example, the electrospinning method, solution blow spinning method, or force spinning method. Of these, the electrospinning method is preferred.
Examples of the polymer that can be used in the present invention include polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polyacrylonitrile-methacrylate copolymer, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride- Acrylate copolymers, nylons such as polyethylene, polypropylene, nylon 12, nylon-4,6, aramid, polybenzimidazole, polyvinyl alcohol, cellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone-vinyl acetate, poly (bis -(2- (2-methoxy-ethoxyethoxy)) phosphazene), polypropylene oxide, polyethylene imide, polysuccinic acid ethylene, polyaniline, polyethylene sal Side, polyoxymethylene-oligo-oxyethylene, SBS copolymer, polyhydroxybutyric acid, polyvinyl acetate, polyethylene terephthalate, polyethylene oxide, collagen, polylactic acid, polyglycolic acid, poly D, L-lactic acid-glycolic acid copolymer Biodegradable polymers such as coalesced, polyarylate, polypropylene fumarate, polycaprolactone, biopolymers such as polypeptides and proteins, various polymers that can be dissolved in some solvents such as pitch systems such as coal tar pitch and petroleum pitch Is mentioned.
The solvent of the polymer solution and the solvent used as the solvent vapor are the same, and usable solvent species are, for example, acetone, chloroform, ethanol, 2-propanol, methanol, toluene, tetrahydrofuran, water, benzene, benzyl alcohol, 1, 4 -Dioxane, 1-propanol, carbon tetrachloride, cyclohexane, cyclohexanone, dichloromethane, phenol, pyridine, trichloroethane, acetic acid, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, Ethylene carbonate, propylene carbonate, dimethyl carbonate, acetonitrile, N-methylmorpholine-N-oxide, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, die Ether, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dioxolane, ethyl methyl carbonate, methyl formate, 3-methyl oxazolidine-2-one, methyl propionate, 2 -Two or more types of mixed solvents selected from methyltetrahydrofuran, sulfolane, and these solvent groups can be used.
As the structure of the nozzle having the double tube structure of the present invention, the inner diameter of the nozzle is preferably 0.15 to 1.07 mm, more preferably 0.34 to 0.84 mm. In addition, the inner diameter of the outer ring of the double tube nozzle that is the portion from which the solvent vapor is ejected is preferably 1.00 to 2.00 mm, more preferably 1.30 to 1.70 mm. If the inner diameter of the nozzle and the inner diameter of the outer ring are out of the range, solidified substances are likely to be generated at the nozzle tip.
The flow rate range of the polymer solution is not particularly limited as long as the flow rate is within a range in which spinning is possible, but it can be preferably set in the range of ˜20 ml / h.
Regarding the solvent vapor partial pressure used, for example, it can be used in a range of 1/2 or more of the saturated vapor pressure of the solvent, but the solvent vapor is preferably saturated. When the solvent saturated vapor is out of the range, a solidified product is likely to be generated at the nozzle tip.
The gas flow rate of the solvent vapor is preferably 100 to 1000 ml / min, more preferably 200 to 800 ml / min. If the gas flow rate is out of the range, solidified substances are likely to be generated at the nozzle tip.
［製造装置］
図１は、本発明のノズル装置を用いた、エレクトロスピニング法による繊維製造機器の全体構成図の一例である。図２は、本発明のノズル装置の一例の断面概念図である。これらの図において、ノズル装置はノズルとその外管とからなり、ノズルは繊維の原料溶液供給装置に繋がっており、外管は該原料溶液の溶媒蒸気の供給装置に繋がっており、ノズルから繊維の原料溶液が吐出され、ノズルと外管との間の空間から該原料溶液の溶媒の蒸気が該吐出溶液を囲むように放出される構成となっている。
［紡糸用高分子溶液の調製］
ポリ乳酸グルコース酸共重合体（Ｐｕｒａｃ社製ＰＵＲＡＳＯＲＢ ＰＤＬＧ５０１０）１重量部、エタノール（和光純薬 試薬特級）１重量部、及び色素Ｄ＆Ｃ Ｖｉｏｌｅｔ ＮＯ．２（Ｓｐｅｃｔｒｕｍ Ｃｈｅｍ．ＭＦＧ．Ｃｏｒｐ）０．００４２重量部を秤量してメディウム瓶に投入後、ボルテックスミキサーＳＩ０２８６にて１０目盛で５分間撹拌した。その後、ジクロロメタン８重量部を添加し、ボルテックスミキサーＳＩ０２８６にて１０目盛で１分間撹拌し、高粘度スターラーＳＮＦ−０１で１０００ｒｐｍにて１０分間撹拌することで均一な紡糸用高分子溶液を得た。
［紡糸用高分子溶液による紡糸］
上記により得られた紡糸溶液を用いてエレクトロスピニングを行った。ノズル内径０．４７ｍｍ、外輪内径１．４５ｍｍの構成の二重管ノズルを用い、ノズル本数１２本で各ノズル間ピッチ間隔を７０ｍｍとし、紡糸間距離４００ｍｍ、ドープ流量４ｍｌ／ｈ、紡糸印加電圧３５ｋＶで紡糸を行った。繊維捕集側はＳＵＳ３０４製の捕集板３３０ｍｍ×４４０ｍｍを使用し、捕集板に−５ｋＶの電圧を印加した。紡糸の際に５００ｍｌジクロロメタンを封入した３Ｌのガラス製密閉容器を介して３００ｍｌ／ｈの圧縮空気を供給し（０．３ＭＰａ）、これを各ノズルと外管との間の空間に３００ｍｌ／ｈの飽和ジクロロメタン蒸気を供給した。この条件では、２５分間紡糸を継続してもノズル先端に固形物は発生しなかった。
［比較例］
紡糸時のノズルと外管との間の空間に飽和ジクロロメタン蒸気を供給しないこと以外は上記実施例と同一の条件で紡糸を行った。この条件では、紡糸開始直後よりノズル先端に固形分が発生し、紡糸開始４０秒後にはノズル先端の固形分成長により紡糸が継続できなくなった。[manufacturing device]
FIG. 1 is an example of an overall configuration diagram of a fiber manufacturing apparatus using an electrospinning method using the nozzle device of the present invention. FIG. 2 is a conceptual cross-sectional view of an example of the nozzle device of the present invention. In these drawings, the nozzle device is composed of a nozzle and its outer tube, the nozzle is connected to a fiber raw material solution supply device, and the outer tube is connected to a solvent vapor supply device for the raw material solution, from the nozzle to the fiber. The raw material solution is discharged, and the vapor of the solvent of the raw material solution is discharged from the space between the nozzle and the outer tube so as to surround the discharged solution.
[Preparation of polymer solution for spinning]
1 part by weight of polylactic acid glucose acid copolymer (PURASORB PDLG5010 manufactured by Purac), 1 part by weight of ethanol (Wako Pure Chemicals reagent special grade), and Dye D & C Violet NO. 2 (Spectrum Chem.MFG.Corp) 0.0042 part by weight was weighed and placed in a medium bottle, and then stirred for 10 minutes on a vortex mixer SI0286 at 10 scales. Thereafter, 8 parts by weight of dichloromethane was added, and the mixture was stirred for 1 minute at 10 scales with a vortex mixer SI0286, and stirred for 10 minutes at 1000 rpm with a high-viscosity stirrer SNF-01 to obtain a uniform polymer solution for spinning.
[Spinning with polymer solution for spinning]
Electrospinning was performed using the spinning solution obtained above. A double tube nozzle having a nozzle inner diameter of 0.47 mm and an outer ring inner diameter of 1.45 mm is used. The number of nozzles is 12, the pitch interval between nozzles is 70 mm, the inter-spinning distance is 400 mm, the dope flow rate is 4 ml / h, and the spinning applied voltage is 35 kV. And spinning. The fiber collection side used the collection plate 330mmx440mm made from SUS304, and applied the voltage of -5kV to the collection plate. During spinning, 300 ml / h of compressed air was supplied (0.3 MPa) through a 3 L glass sealed container filled with 500 ml of dichloromethane, and 300 ml / h of this was supplied to the space between each nozzle and the outer tube. Saturated dichloromethane vapor was fed. Under these conditions, no solid matter was generated at the nozzle tip even when spinning was continued for 25 minutes.
[Comparative example]
Spinning was performed under the same conditions as in the above example except that saturated dichloromethane vapor was not supplied to the space between the nozzle and the outer tube during spinning. Under these conditions, a solid content was generated at the nozzle tip immediately after the start of spinning, and spinning could not be continued due to the solid content growth at the nozzle tip 40 seconds after the start of spinning.
本発明は、紡糸安定性や紡糸収率に優れ、また連続生産が可能な紡糸方法及び装置として有用であり、例えば不織布の製造業で利用される。 INDUSTRIAL APPLICABILITY The present invention is useful as a spinning method and apparatus that are excellent in spinning stability and spinning yield, and that can be continuously produced.
１ 定量供給器
２ シリンジ
３ 接続ホース
４ 二重ノズル
５ 接続ホース
６ 溶媒バブリング瓶
７ 制御用ニードルバルブ
８ 体積流量計
９ 気体供給部
１０ 原料溶液（ドープ液）の供給口
１１ 溶媒蒸気を含有する気体の供給口DESCRIPTION OF SYMBOLS 1
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS474010A (en) * | 1970-07-27 | 1972-02-28 | ||
| JPS536613A (en) * | 1976-07-03 | 1978-01-21 | Bayer Ag | Cleaning of spinning nozzle or hole type nozzle during extrusion of polymer melt |
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| WO2013137379A1 (en) * | 2012-03-14 | 2013-09-19 | 三菱レイヨン株式会社 | Device for producing hollow porous film and method for producing hollow porous film |
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| US6382526B1 (en) * | 1998-10-01 | 2002-05-07 | The University Of Akron | Process and apparatus for the production of nanofibers |
| RU2242546C1 (en) * | 2003-11-13 | 2004-12-20 | ФГУП ГНЦ РФ Научно-исследовательский физико-химический институт им. Л.Я. Карпова | Method for producing of thin polymer filaments |
| CN100535205C (en) * | 2006-03-06 | 2009-09-02 | 东华大学 | Gas layer propulsion electrostatic spinning apparatus and industrial application thereof |
| TWI347380B (en) * | 2008-10-02 | 2011-08-21 | Taiwan Textile Res Inst | Electro-spinning apparatus and electro-spinning method |
| AU2011216200B2 (en) * | 2010-02-15 | 2016-09-08 | Cornell University | Electrospinning apparatus and nanofibers produced therefrom |
| CN104313708B (en) * | 2014-11-20 | 2017-02-22 | 江西先材纳米纤维科技有限公司 | Method and device for producing polymer nano fibers through high-speed airflow and high-voltage static |
| CN104928768B (en) * | 2015-04-08 | 2017-05-03 | 烟台森森环保科技有限公司 | Internal and external circular air assisted electrospinning nozzle unit |
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2016
- 2016-12-26 CA CA3009481A patent/CA3009481A1/en not_active Abandoned
- 2016-12-26 EP EP16881850.8A patent/EP3399077A4/en not_active Withdrawn
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- 2016-12-26 KR KR1020187018254A patent/KR20180098274A/en not_active Application Discontinuation
- 2016-12-26 US US16/066,236 patent/US20200270771A1/en not_active Abandoned
- 2016-12-26 AU AU2016382146A patent/AU2016382146A1/en not_active Abandoned
- 2016-12-26 RU RU2018127383A patent/RU2018127383A/en not_active Application Discontinuation
- 2016-12-26 WO PCT/JP2016/089230 patent/WO2017115876A1/en active Application Filing
- 2016-12-27 TW TW105143408A patent/TWI707995B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS474010A (en) * | 1970-07-27 | 1972-02-28 | ||
| JPS536613A (en) * | 1976-07-03 | 1978-01-21 | Bayer Ag | Cleaning of spinning nozzle or hole type nozzle during extrusion of polymer melt |
| JP2010236133A (en) * | 2009-03-31 | 2010-10-21 | National Institute Of Advanced Industrial Science & Technology | Apparatus for producing nanofiber by electrospinning method using double-pipe nozzle and nanofiber production method |
| WO2013137379A1 (en) * | 2012-03-14 | 2013-09-19 | 三菱レイヨン株式会社 | Device for producing hollow porous film and method for producing hollow porous film |
Also Published As
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|---|---|
| TWI707995B (en) | 2020-10-21 |
| TW201730390A (en) | 2017-09-01 |
| KR20180098274A (en) | 2018-09-03 |
| RU2018127383A3 (en) | 2020-01-30 |
| CN108431308A (en) | 2018-08-21 |
| EP3399077A1 (en) | 2018-11-07 |
| AU2016382146A1 (en) | 2018-06-14 |
| WO2017115876A1 (en) | 2017-07-06 |
| JP6683737B2 (en) | 2020-04-22 |
| CA3009481A1 (en) | 2017-07-06 |
| BR112018013135A2 (en) | 2018-12-11 |
| EP3399077A4 (en) | 2018-12-26 |
| US20200270771A1 (en) | 2020-08-27 |
| HK1253542A1 (en) | 2019-06-21 |
| RU2018127383A (en) | 2020-01-30 |
| MX2018006927A (en) | 2018-08-01 |
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