本發明是關於一種含有高分子的纖維之紡絲方法，其包含從噴嘴前端讓高分子溶液噴出的步驟，是在剛噴出後之高分子溶液的周圍供給氣體並進行紡絲之紡絲方法，該氣體含有與高分子溶液的溶媒為相同的溶媒之蒸氣；並關於該紡絲方法所使用的裝置。The present invention relates to a spinning method of a fiber containing a polymer, which comprises a step of discharging a polymer solution from a tip end of a nozzle, and is a spinning method of supplying a gas around a polymer solution immediately after ejection and spinning. This gas contains a vapor of the same solvent as the solvent of the polymer solution; and an apparatus used in the spinning method.
近年來，奈米纖維所構成的薄片等的成形體，因為具有高的比表面積，作為具有習知纖維成形體所無法達成的特性之素材受到矚目。作為這種奈米纖維的製造方法(紡絲方法)，電紡法是眾所皆知的。In recent years, a molded article such as a sheet composed of a nanofiber has a high specific surface area, and has attracted attention as a material having properties which cannot be achieved by a conventional fiber molded body. As such a method for producing a nanofiber (spinning method), an electrospinning method is well known.
電紡法，是將讓聚合物溶解於溶媒而成的溶液(紡絲液)供應到紡絲液吐出噴嘴的前端，在噴嘴前端和電極(收集器)間施加高電壓，藉此在收集器上獲得纖維成形體的方法。該方法係包含：讓高分子溶解於溶媒而製造溶液(紡絲液)的步驟、將該紡絲液供應到噴嘴前端並施加高電壓的步驟、讓該紡絲液從噴嘴前端朝向電極(收集器)方向噴出的步驟、從噴出後的紡絲液讓溶媒蒸發而形成纖維成形體的步驟、作為可任意實施的步驟之讓所形成的纖維成形體之電荷消失的步驟、以及藉由讓電荷消失而使纖維成形體在收集器上累積的步驟。In the electrospinning method, a solution (spinning solution) obtained by dissolving a polymer in a solvent is supplied to a tip end of a spinning solution discharge nozzle, and a high voltage is applied between a tip end of the nozzle and an electrode (collector), thereby being on the collector. A method of obtaining a fibrous formed body. The method comprises the steps of: dissolving a polymer in a solvent to produce a solution (spinning solution), supplying the spinning solution to a tip of the nozzle and applying a high voltage, and allowing the spinning solution to pass from the nozzle tip toward the electrode (collecting The step of ejecting in the direction, evaporating the solvent from the spinning solution after the ejection to form a fiberThe step of forming the body, the step of eliminating the charge of the formed fiber body as a step which can be arbitrarily carried out, and the step of accumulating the fiber formed body on the collector by letting the electric charge disappear.
電紡法的課題在於，縱使是在紡絲液採用揮發性溶媒的情況仍能進行連續生產。關於這點，在專利文獻1揭示一種技術，是在習知技術的單管噴嘴附近，將正在生成的奈米纖維用溶媒包圍，利用溶媒流物理性地防止及/或洗淨所生成的奈米纖維往噴嘴之吸附，藉此可進行連續生產。The problem of the electrospinning method is that continuous production can be carried out even when a volatile solvent is used in the spinning dope. In this regard, Patent Document 1 discloses a technique in which a nanofiber being formed is surrounded by a solvent in the vicinity of a single-tube nozzle of the prior art, and the generated naphthalene is physically prevented and/or washed by the solvent flow. The adsorption of the rice fibers to the nozzle allows continuous production.
專利文獻1：日本特開2010-236133號公報Patent Document 1: Japanese Laid-Open Patent Publication No. 2010-236133
本發明人等查明，在電紡法中，當紡絲液的溶媒是採用揮發性溶媒的情況，在讓紡絲液從噴嘴前端噴出的步驟中，在噴嘴前端所形成的泰勒錐(Taylor cone，在噴嘴前端於紡絲時產生者，藉由對供應到噴嘴前端的液滴施加超過其表面張力的電壓，使該液滴被朝電壓方向拉伸而產生之通常呈錐狀者)產生固化，其固形物隨著時間經過而成長，此乃造成紡絲安定性的惡化、紡絲產率的降低、甚至變得無法連續生產的問題之原因。而且已知，此問題並不限定於電紡法，這是在氣體中讓高分子溶液進行紡絲之紡絲法共同的問題。The present inventors have found that in the electrospinning method, in the case where the solvent of the spinning dope is a volatile solvent, in the step of allowing the spinning solution to be ejected from the tip end of the nozzle, the Taylor cone formed at the tip end of the nozzle (Taylor cone) Producing at the tip end of the nozzle at the time of spinning, by applying a voltage exceeding the surface tension of the droplet supplied to the tip end of the nozzle, causing the droplet to be stretched in the direction of voltage to produce a generally tapered shape to cause solidification The solid matter grows with the passage of time, which is a cause of deterioration of spinning stability, reduction in spinning yield, and even failure to continuously produce. Further, it is known that this problem is not limited to the electrospinning method, which is a common problem in the spinning method in which a polymer solution is spun in a gas.
本發明的目的，是為了解決這種問題而提供一種方法及裝置，例如將電紡中之泰勒錐的固化、成長予以抑制等，將在氣體中讓高分子溶液進行紡絲之紡絲法中在噴嘴前端之紡絲液的固化予以抑制。The object of the present invention is to provide a method for solving such a problem.Further, for example, the curing and growth of the Taylor cone in electrospinning are suppressed, and the spinning of the spinning solution at the nozzle tip is suppressed in the spinning method in which the polymer solution is spun in a gas.
有鑑於上述問題，本發明人等深入研究的結果發現，作為紡絲機器之噴嘴裝置，係具備：對噴嘴供給作為纖維的原料之高分子溶液的手段、以及對該噴嘴的前端供給該高分子溶液之溶媒蒸氣的手段，一邊在該噴嘴的前端附近供給該高分子溶液之溶媒蒸氣，一邊對該噴嘴供給作為纖維的原料之高分子溶液而製造纖維，藉此將在氣體中吐出紡絲液的紡絲方法中在噴嘴前端之紡絲液的固化予以抑制，而到達本發明的完成。In view of the above-described problems, the inventors of the present invention have found that the nozzle device of the spinning machine includes means for supplying a polymer solution as a raw material of the fiber to the nozzle, and supplying the polymer to the tip end of the nozzle. In the solvent vapor of the solution, the solvent vapor of the polymer solution is supplied in the vicinity of the tip of the nozzle, and a polymer solution as a raw material of the fiber is supplied to the nozzle to produce a fiber, thereby discharging the spinning solution in the gas. In the spinning method, the solidification of the spinning solution at the tip end of the nozzle is suppressed, and the completion of the present invention is reached.
亦即，本發明為以下所說明者。That is, the present invention is as described below.
[1]一種紡絲用噴嘴裝置，係具備噴嘴、高分子溶液供給手段以及溶媒蒸氣供給手段，高分子溶液供給手段，是對噴嘴供給高分子溶液而從噴嘴前端讓高分子溶液噴出；溶媒蒸氣供給手段，是至少在剛噴出後之高分子溶液的周圍供給氣體，該氣體含有與高分子溶液的溶媒為相同的溶媒之蒸氣。[1] A nozzle device for spinning, comprising a nozzle, a polymer solution supply means, and a solvent vapor supply means, wherein the polymer solution supply means supplies a polymer solution to the nozzle to eject the polymer solution from the tip end of the nozzle; The supply means supplies a gas at least around the polymer solution immediately after the discharge, and the gas contains a vapor of the same solvent as the solvent of the polymer solution.
[2]在[1]所記載的紡絲用噴嘴裝置，其構成為，係具有：由噴嘴、即內管及包圍內管的外管所組成之雙重管構造部分，含有與高分子溶液的溶媒為相同的溶媒之蒸氣的氣體是從內管和外管之間的空間供給。[2] The spinning nozzle device according to [1], comprising a double tube structure portion composed of a nozzle, that is, an inner tube and an outer tube surrounding the inner tube, and containing a polymer solution The gas in which the solvent is the same solvent vapor is supplied from the space between the inner tube and the outer tube.
[3]一種紡絲方法，是含有高分子的纖維之紡絲方法，其包含從噴嘴前端讓高分子溶液噴出的步驟，至少在剛噴出後之高分子溶液的周圍供給氣體並進行紡絲，該氣體含有與高分子溶液的溶媒為相同的溶媒之蒸氣。[3] A spinning method comprising a method of spinning a polymer-containing fiber, comprising the step of ejecting a polymer solution from a tip end of a nozzle, and supplying a gas at least around a polymer solution immediately after the ejection, and spinning. This gas contains a vapor of the same solvent as the solvent of the polymer solution.
[4]在[3]所記載的紡絲方法，其中，所供給的氣體含有在紡絲時的條件下為氣相的物質，所供給的氣體中，與高分子溶液的溶媒為相同的溶媒之蒸氣是飽和蒸氣。[4] The spinning method according to [3], wherein the gas to be supplied contains a substance which is in a gas phase under the conditions at the time of spinning, and the solvent to be supplied is the same solvent as the solvent of the polymer solution. The vapor is a saturated vapor.
本發明的效果，是在氣體中讓高分子溶液進行紡絲之紡絲法中，將在用於吐出紡絲液之噴嘴前端的紡絲液之固化予以抑制。藉此，可減少纖維成分在噴嘴前端之堵塞及噴出不良，進而使紡絲安定性及紡絲產率提高，又能進行連續生產。The effect of the present invention is to suppress the curing of the spinning dope at the tip end of the nozzle for discharging the spinning solution in the spinning method in which the polymer solution is spun in a gas. Thereby, the clogging of the fiber component at the tip end of the nozzle and the ejection failure can be reduced, and the spinning stability and the spinning yield can be improved, and continuous production can be performed.
1‧‧‧定量供給器1‧‧‧Quantitative feeder
2‧‧‧注射器2‧‧‧Syringe
3‧‧‧連接軟管3‧‧‧Connecting hose
4‧‧‧雙重噴嘴4‧‧‧Double nozzle
5‧‧‧連接軟管5‧‧‧Connecting hose
6‧‧‧溶媒起泡瓶6‧‧‧Solvent foaming bottle
7‧‧‧控制用針閥7‧‧‧Control needle valve
8‧‧‧體積流量計8‧‧‧Volume flowmeter
9‧‧‧氣體供給部9‧‧‧Gas Supply Department
10‧‧‧原料溶液(紡絲液)之供給口10‧‧‧ Supply port of raw material solution (spinning solution)
11‧‧‧含有溶媒蒸氣的氣體之供給口11‧‧‧Supply port for gas containing solvent vapor
圖1係利用電紡法之纖維製造機器的整體圖，其採用作為本發明的噴嘴裝置的一例之雙重管噴嘴。Fig. 1 is an overall view of a fiber manufacturing machine using an electrospinning method using a double tube nozzle as an example of the nozzle device of the present invention.
圖2係作為本發明的噴嘴裝置的一例之具有雙重管構造的噴嘴裝置。Fig. 2 is a nozzle device having a double tube structure as an example of the nozzle device of the present invention.
在本發明的噴嘴裝置中，作為對噴嘴供給作為纖維的原料之高分子溶液(紡絲液)的手段可採用，作為在氣體中讓高分子溶液進行紡絲之紡絲裝置的噴嘴裝置通常使用者。此外，作為對該噴嘴的前端供給紡絲液的溶媒蒸氣之手段，雖沒有特別的限制，但較佳為在電紡法中不妨礙朝向紡絲時的紡絲方向之泰勒錐形成者，例如可採用，構成為具有作為噴嘴而被供給紡絲液的內管、及包圍內管的外管，含有紡絲液溶媒的蒸氣之氣體是從內管和外管之間的空間，朝向與從噴嘴噴出紡絲液的方向大致相同的方向供給。藉此，至少剛噴出後的高分子溶液是處於該溶媒蒸氣的氛圍下。In the nozzle device of the present invention, a means for supplying a polymer solution (spinning solution) as a raw material of the fiber to the nozzle can be employed as the gas.A nozzle device for a spinning device that spins a polymer solution is usually used by a user. Further, the means for supplying the solvent vapor of the spinning dope to the tip end of the nozzle is not particularly limited, but is preferably formed by a Taylor cone which does not hinder the spinning direction at the time of spinning in the electrospinning method. The inner tube having the spinning solution supplied as a nozzle and the outer tube surrounding the inner tube are configured, and the gas containing the spinning solution solvent is a space between the inner tube and the outer tube, and is directed toward and from the nozzle. The direction in which the spinning solution is discharged is supplied in substantially the same direction. Thereby, at least the polymer solution immediately after the ejection is in an atmosphere of the solvent vapor.
在本發明的製造方法，作為從噴嘴前端讓高分子溶液噴出的步驟，可採用在氣體中讓高分子溶液進行紡絲之紡絲方法中的通常方法。此外，作為在至少剛噴出後之高分子溶液的周圍(附近)供給含有與高分子溶液的溶媒為相同的溶媒之蒸氣的氣體之步驟，較佳為在電紡法中不致妨礙朝向紡絲時的紡絲方向之泰勒錐形成的方法，例如可採用，朝向與從噴嘴噴出紡絲液的方向大致相同的方向，在被噴出之紡絲液的周圍噴吹含有紡絲液的溶媒之氣體的方法。In the production method of the present invention, as a step of discharging the polymer solution from the tip end of the nozzle, a usual method in a spinning method in which a polymer solution is spun in a gas can be employed. Further, the step of supplying a gas containing a vapor of the same solvent as the solvent of the polymer solution to the periphery (near) of the polymer solution immediately after the discharge is preferably not hindered in the electrospinning process. The method of forming the Taylor cone in the spinning direction may be, for example, a method of blowing a gas containing a solvent of the spinning solution around the discharged spinning solution in a direction substantially the same as the direction in which the spinning solution is discharged from the nozzle. .
本發明，只要是屬於從紡絲液讓其溶媒氣化而生成纖維之紡絲技術，不管是哪個都能適用，例如適用於電紡法、濕式(solution)紡絲法、或是乾式(force)紡絲法，其中最適用於電紡法。The present invention can be applied to any spinning technique in which a solvent is vaporized from a spinning solution to form a fiber, and is applicable to, for example, an electrospinning method, a wet spinning method, or a dry type (force). Spinning method, which is most suitable for electrospinning.
作為在本發明可使用的聚合物的種類可列舉：聚偏二氟乙烯、聚偏二氟乙烯-六氟丙烯共聚物、聚丙烯腈、聚丙烯腈-甲基丙烯酸酯共聚物、聚甲基丙烯酸甲酯、聚氯乙烯、聚偏二氯乙烯-丙烯酸酯共聚物、聚乙烯、聚丙烯、尼龍12、尼龍-4,6等的尼龍系、聚芳醯胺、聚苯并咪唑、聚乙烯醇、纖維素、醋酸纖維素、醋酸纖維素丁酸酯、聚乙烯吡咯啶酮-醋酸乙烯、聚(雙-(2-(2-甲氧基-乙氧基乙氧基))膦氮烯)、聚環氧丙烷、聚乙烯亞胺、聚丁二酸乙烯、聚苯胺、聚亞乙基硫醚、聚甲醛-低聚氧乙烯、SBS共聚物、聚羥基丁酸酯、聚醋酸乙烯、聚對苯二甲酸乙二酯、聚氧化乙烯、膠原、聚乳酸、聚乙醇酸、聚D,L-乳酸-乙醇酸共聚物、聚芳酯、聚富馬酸丙二醇酯、聚己內酯等的生物分解性高分子、多肽、蛋白質等的生物聚合物、煤焦瀝青、石油瀝青等的瀝青系等之可溶解於某些溶媒的各種高分子。The type of the polymer which can be used in the present invention is exemplified by polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, and polyAcrylonitrile-methacrylate copolymer, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride-acrylate copolymer, polyethylene, polypropylene, nylon 12, nylon-4, 6, etc. , polyarylamine, polybenzimidazole, polyvinyl alcohol, cellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone-vinyl acetate, poly(bis-(2-(2-methoxy) -Ethoxyethoxy))phosphazene), polypropylene oxide, polyethyleneimine, polybutylene succinate, polyaniline, polyethylene sulfide, polyoxymethylene-oligooxyethylene, SBS Copolymer, polyhydroxybutyrate, polyvinyl acetate, polyethylene terephthalate, polyethylene oxide, collagen, polylactic acid, polyglycolic acid, poly D, L-lactic acid-glycolic acid copolymer, polyarylate Biodegradable polymers such as poly-maleic acid propylene glycol ester and polycaprolactone, biopolymers such as polypeptides and proteins, pitches such as coal tar pitch and petroleum pitch, etc., can be dissolved in various solvents. molecule.
高分子溶液的溶媒和作為溶媒蒸氣所使用的溶媒是相同的，作為可使用的溶媒種類，例如可列舉：丙酮、氯仿、乙醇、2-丙醇、甲醇、甲苯、四氫呋喃、水、苯、苯甲醇、1,4-二噁烷、1-丙醇、四氯化碳、環己烷、環己酮、二氯甲烷、酚、吡啶、三氯乙烷、醋酸、N,N-二甲基甲醯胺、二甲亞碸、N,N-二甲基乙醯胺、1-甲基-2-吡咯酮、碳酸伸乙酯、碳酸丙烯酯、碳酸二甲酯、乙腈、N-甲基嗎啉-N-氧化物、碳酸丁烯酯、1,4-丁內酯、碳酸二乙酯、乙醚、1,2-二甲氧乙烷、1,3-二甲基-2-咪唑啶酮、1,3-二草酸酯、碳酸甲乙酯、甲酸甲酯、3-甲基噁唑啶-2-酮、丙酸甲酯、2-甲基四氫呋喃、環丁碸、以及選自這些溶媒群之2種以上的混合溶媒。The solvent of the polymer solution is the same as the solvent used as the solvent vapor. Examples of the solvent that can be used include acetone, chloroform, ethanol, 2-propanol, methanol, toluene, tetrahydrofuran, water, benzene, and benzene. Methanol, 1,4-dioxane, 1-propanol, carbon tetrachloride, cyclohexane, cyclohexanone, dichloromethane, phenol, pyridine, trichloroethane, acetic acid, N,N-dimethyl Formamide, dimethyl hydrazine, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, ethyl carbonate, propylene carbonate, dimethyl carbonate, acetonitrile, N-methyl Morpholine-N-oxide, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, diethyl ether, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinium Ketone, 1,3-dioxalate, ethyl methyl carbonate, methyl formate, 3-methyloxazolidine-2-one, methyl propionate, 2-methyltetrahydrofuran, cyclobutane, and selected from These onesTwo or more mixed solvents of a solvent group.
作為本發明之具有雙重管構造的噴嘴構造，噴嘴內徑較佳為0.15~1.07mm，更佳為0.34~0.84mm。成為溶媒蒸氣被噴出的部分之雙重管噴嘴的外環的內徑較佳為1.00~2.00mm，更佳為1.30~1.70mm。若噴嘴的內徑及外環的內徑在該範圍之外，在噴嘴前端容易產生固化物。As the nozzle structure having the double tube structure of the present invention, the inner diameter of the nozzle is preferably from 0.15 to 1.07 mm, more preferably from 0.34 to 0.84 mm. The inner diameter of the outer ring of the double tube nozzle which is a portion where 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 outside this range, a cured product is likely to be generated at the tip end of the nozzle.
作為高分子溶液的流量範圍，只要是可紡絲的範圍之流量即可，沒有特別的限定，較佳為設定在20ml/h以下的範圍。The flow rate range of the polymer solution is not particularly limited as long as it is a flow rate in the range of spinnability, and is preferably set to a range of 20 ml/h or less.
關於所使用的溶媒蒸氣分壓，例如可採用溶媒的飽和蒸氣壓之1/2以上的範圍，較佳為溶媒蒸氣是飽和蒸氣。若溶媒飽和蒸氣在該範圍之外，在噴嘴前端容易產生固化物。The solvent vapor partial pressure to be used may be, for example, a range of 1/2 or more of the saturated vapor pressure of the solvent, and it is preferred that the solvent vapor is saturated vapor. If the solvent saturated vapor is outside this range, a cured product is likely to be generated at the tip end of the nozzle.
作為溶媒蒸氣的氣體流量，較佳為100~1000ml/min，更佳為200~800ml/min。若氣體流量在該範圍之外，在噴嘴前端容易產生固化物。The gas flow rate as the solvent vapor is preferably from 100 to 1,000 ml/min, more preferably from 200 to 800 ml/min. If the gas flow rate is outside this range, a cured product is likely to be generated at the tip end of the nozzle.
圖1係採用本發明的噴嘴裝置之利用電紡法的纖維製造機器的整體構造圖之一例。圖2係本發明的噴嘴裝置的一例之剖面概念圖。在這些圖中，噴嘴裝置是由噴嘴及其外管所構成，噴嘴是與纖維之原料溶液供給裝置相連，外管是與該原料溶液的溶媒蒸氣之供給裝置相連，從噴嘴吐出纖維的原料溶液，從噴嘴和外管之間的空間以包圍該吐出溶液的方式噴出該原料溶液的溶媒之蒸氣。Fig. 1 is an example of an overall configuration of a fiber manufacturing machine using an electrospinning method using a nozzle device of the present invention. Fig. 2 is a cross-sectional conceptual view showing an example of a nozzle device of the present invention. In these figures, the nozzle device is composed of a nozzle and an outer tube thereof, and the nozzle is connected to the raw material solution supply device of the fiber, and the outer tube is connected to the supply means of the solvent vapor of the raw material solution, and is spit from the nozzle.The raw material solution of the fiber is discharged from the space between the nozzle and the outer tube by bubbling the solvent of the solvent of the raw material solution so as to surround the discharge solution.
將聚乳酸乙醇酸共聚物(普拉克(Purac)公司製PURASORB PDLG5010)1重量部、乙醇(和光純藥 試藥特級)1重量份、及色素D&C Violet NO.2(斯百全化學公司(Spectrum Chem.MFG.Corp))0.0042重量份予以秤重並投入試藥瓶後，使用漩渦混合器(Vortex mixer)SI0286以刻度10攪拌5分鐘。然後，添加二氯甲烷8重量份，使用漩渦混合器SI0286以刻度10攪拌1分鐘，用高黏度攪拌器SNF-01以1000rpm攪拌10分鐘，獲得均一的紡絲用高分子溶液。1 part by weight of polylactic acid glycolic acid copolymer (PURASORB PDLG5010 manufactured by Purac Co., Ltd.), 1 part by weight of ethanol (Special grade of Pharmacopoeia), and D&C Violet NO. 2 (Spectrum) Chem. MFG. Corp.) 0.0042 parts by weight was weighed and put into the reagent bottle, and stirred for 5 minutes on a scale 10 using a Vortex mixer SI0286. Then, 8 parts by weight of dichloromethane was added, and the mixture was stirred for 10 minutes on a scale 10 using a vortex mixer SI0286, and stirred at 1000 rpm for 10 minutes with a high-viscosity stirrer SNF-01 to obtain a uniform polymer solution for spinning.
使用上述獲得的紡絲溶液進行電紡。使用噴嘴內徑0.47mm、外環內徑1.45mm之雙重管噴嘴，噴嘴數為12個，各噴嘴間的節距間隔為70mm，紡絲間距離400mm，紡絲液流量4ml/h，紡絲施加電壓35kV，在此條件下進行紡絲。纖維捕集側是使用SUS304製的捕集板330mm×440mm，在捕集板施加-5kV的電壓。在紡絲時，透過封入有500ml二氯甲烷之3L玻璃製密閉容器來供給300ml/h的壓縮空氣(0.3MPa)，藉此對各噴嘴和外管間的空間供給300ml/h的飽和二氯甲烷蒸氣。在此條件下，縱使持續進行25分鐘的紡絲，在噴嘴前端也沒有產生固形物。Electrospinning was carried out using the spinning solution obtained above. A double tube nozzle with a nozzle inner diameter of 0.47 mm and an outer ring inner diameter of 1.45 mm was used. The number of nozzles was 12, the pitch between nozzles was 70 mm, the distance between spinning was 400 mm, and the flow rate of spinning solution was 4 ml/h. A voltage of 35 kV was applied, and spinning was performed under the conditions. On the fiber collecting side, a collecting plate made of SUS304 was used, 330 mm × 440 mm, and a voltage of -5 kV was applied to the collecting plate. At the time of spinning, 300 ml/h of compressed air (0.3 MPa) was supplied through a sealed container of 3 L of glass sealed with 500 ml of dichloromethane, thereby supplying 300 ml/h of saturated dichlorochloride to the space between each nozzle and the outer tube. Methane vapor. Under these conditions, longitudinalSpinning was continued for 25 minutes, and no solid matter was generated at the tip end of the nozzle.
除了紡絲時在噴嘴和外管間的空間不供給飽和二氯甲烷蒸氣以外，是以與上述實施例相同的條件進行紡絲。在此條件下，從紡絲剛開始後，在噴嘴前端就產生固形分，在開始紡絲起算40秒後，因噴嘴前端之固形分的成長而導致紡絲無法繼續進行。Spinning was carried out under the same conditions as in the above examples except that the saturated methylene chloride vapor was not supplied to the space between the nozzle and the outer tube at the time of spinning. Under these conditions, a solid content was generated at the tip end of the nozzle immediately after the start of spinning, and the spinning was not continued due to the growth of the solid portion at the tip end of the nozzle after 40 seconds from the start of spinning.
本發明適用於作為紡絲安定性及紡絲產率優異且可連續生產之紡絲方法及裝置，例如可利用於不織布的製造業。The present invention is applicable to a spinning method and apparatus which are excellent in spinning stability and spinning yield and which can be continuously produced, and can be used, for example, in a nonwoven fabric manufacturing industry.
1‧‧‧定量供給器1‧‧‧Quantitative feeder
2‧‧‧注射器2‧‧‧Syringe
3‧‧‧連接軟管3‧‧‧Connecting hose
4‧‧‧雙重噴嘴4‧‧‧Double nozzle
5‧‧‧連接軟管5‧‧‧Connecting hose
6‧‧‧溶媒起泡瓶6‧‧‧Solvent foaming bottle
7‧‧‧控制用針閥7‧‧‧Control needle valve
8‧‧‧體積流量計8‧‧‧Volume flowmeter
9‧‧‧氣體供給部9‧‧‧Gas Supply Department
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015256373 | 2015-12-28 | ||
| JP2015-256373 | 2015-12-28 |
| Publication Number | Publication Date |
|---|---|
| TW201730390Atrue TW201730390A (en) | 2017-09-01 |
| TWI707995B TWI707995B (en) | 2020-10-21 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW105143408ATWI707995B (en) | 2015-12-28 | 2016-12-27 | Spinning method and device |
| Country | Link |
|---|---|
| US (1) | US20200270771A1 (en) |
| EP (1) | EP3399077A4 (en) |
| JP (1) | JP6683737B2 (en) |
| KR (1) | KR20180098274A (en) |
| CN (1) | CN108431308A (en) |
| AU (1) | AU2016382146A1 (en) |
| BR (1) | BR112018013135A2 (en) |
| CA (1) | CA3009481A1 (en) |
| HK (1) | HK1253542A1 (en) |
| MX (1) | MX2018006927A (en) |
| RU (1) | RU2018127383A (en) |
| TW (1) | TWI707995B (en) |
| WO (1) | WO2017115876A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG11202104341VA (en)* | 2018-10-09 | 2021-05-28 | M Techx Inc | Nanofiber production apparatus and nanofiber production method |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3724672A (en)* | 1970-07-27 | 1973-04-03 | R Leonard | Asymmetric hollow fiber membranes and method of fabrication |
| DE2630055B2 (en)* | 1976-07-03 | 1978-04-27 | Bayer Ag, 5090 Leverkusen | Process for gassing the nozzle openings when extruding plastic |
| AU2705600A (en)* | 1998-10-01 | 2000-05-01 | University Of Akron, The | 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 |
| JP5131857B2 (en)* | 2009-03-31 | 2013-01-30 | 独立行政法人産業技術総合研究所 | Nanofiber manufacturing apparatus and manufacturing method by electrospinning method using double tube nozzle |
| AU2011216200B2 (en)* | 2010-02-15 | 2016-09-08 | Cornell University | Electrospinning apparatus and nanofibers produced therefrom |
| JP5673809B2 (en)* | 2012-03-14 | 2015-02-18 | 三菱レイヨン株式会社 | Hollow porous membrane production apparatus and hollow porous membrane production method |
| 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 |
| Publication number | Publication date |
|---|---|
| TWI707995B (en) | 2020-10-21 |
| KR20180098274A (en) | 2018-09-03 |
| HK1253542A1 (en) | 2019-06-21 |
| RU2018127383A (en) | 2020-01-30 |
| RU2018127383A3 (en) | 2020-01-30 |
| JPWO2017115876A1 (en) | 2018-06-14 |
| BR112018013135A2 (en) | 2018-12-11 |
| MX2018006927A (en) | 2018-08-01 |
| WO2017115876A1 (en) | 2017-07-06 |
| CN108431308A (en) | 2018-08-21 |
| EP3399077A1 (en) | 2018-11-07 |
| CA3009481A1 (en) | 2017-07-06 |
| JP6683737B2 (en) | 2020-04-22 |
| EP3399077A4 (en) | 2018-12-26 |
| AU2016382146A1 (en) | 2018-06-14 |
| US20200270771A1 (en) | 2020-08-27 |
| Publication | Publication Date | Title |
|---|---|---|
| CN102084043B (en) | Method and apparatus for manufacturing nanofiber | |
| CN101137781B (en) | Improved electroblowing web formation process | |
| CN103194805B (en) | Claw multi-nozzle electrospinning jet device with auxiliary air flow | |
| KR101816733B1 (en) | Spinning device for two-component composited nanofiber and method of manufacturing two-component composited nanofiber thereby | |
| Shahabadi et al. | Effects of process and ambient parameters on diameter and morphology of electrospun polyacrylonitrile nanofibers | |
| WO2019004353A1 (en) | Apparatus for manufacturing ultrafine fiber and method for manufacturing ultrafine fiber | |
| CN107740198A (en) | A kind of flash spinning equipment and its spinning process | |
| GB1215679A (en) | A process for the continuous production of a non-woven filamentary web in which the filaments are arranged in random manner | |
| CN106435770B (en) | Tornado electrostatic spinning nozzle | |
| TW201730390A (en) | Spinning method and spinning device | |
| CN108048943B (en) | Highly oriented porous nanofibers and method of making the same | |
| CN108330550B (en) | Non-nozzle type electrostatic spinning device and using method thereof | |
| US10138574B2 (en) | Blowing-assisted electrospinning | |
| JP4047744B2 (en) | Electrostatic spinning method and electrostatic spinning apparatus | |
| CN110241467A (en) | Inner cone angle electrospinning device and method of use thereof | |
| Pokorný et al. | Gas-assisted electrospinning and electroblowing | |
| JP2009068121A (en) | Nanofiber compounding method and apparatus | |
| JP6211613B2 (en) | Multi-zone electroblowing method | |
| US1933607A (en) | Production of textile materials | |
| JP6205517B1 (en) | Fine fiber production equipment | |
| CN203768508U (en) | Spinning nozzle device for mixture nanofibers | |
| JP2007308820A (en) | Apparatus for producing polymer fiber structure by electrostatic spinning method | |
| CN103866404A (en) | Spinning sprayer device for compound nano-fiber | |
| CN114703553B (en) | Solution jet spinning device for forming nano fibers | |
| CN221659831U (en) | A masterbatch feeding device for polylactic acid fiber production |
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |