JP2009024290A - Electrodeposion apparatus, method for producing polymer web and polymer web produced therewith - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means enabling the more simple production of a polymer web having a good orientation property and a high strength in an electrodeposition method. <P>SOLUTION: An electrodeposition apparatus for applying a voltage between a polymer liquid medium-supplying portion and a scattered polymer-receiving portion to form an electric field between both the portions, and supplying a polymer liquid medium from the polymer liquid medium-supplying portion to the scattered polymer-receiving portion to form a polymer web at least partially containing the scattered polymer on the scattered polymer-receiving portion is characterized in that the scattered polymer-receiving portion is a cylindrical electrode rotatable on a central shaft, and the apparatus further has a rotation driving means for rotating the cylindrical electrode on the central shaft. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention provides a method for producing a polymer web having orientation and high strength by an electrodeposition method (electrospinning method), a polymer web obtained by the production method, and an electro in which the production method can be carried out. It relates to a deposition device.

  An electrospinning method is known as a general method used for producing a polymer web composed of fibers having a single fiber diameter of nano-order. In this method, after preparing a polymer solution, a high voltage is applied to the polymer solution to extrude it from a die to form ultrafine fibers. In general, a polymer web having a fiber diameter of several hundreds of nanometers can be produced by this method. As a method for producing a polymer web by electrospinning, a multi-nozzle continuous production method is also known. This is a method in which a solution is supplied from a polymer solution tank to a multi-nozzle by a pump, a voltage is applied between a nozzle and an application object, and a polymer web is applied to the application object (Patent Document 1).

  Here, in recent years, this polymer web is expected to be applied to the electronics field such as electric guns for electric wires and light emitters on semiconductor substrates, the environmental field such as high performance filters, and the medical field such as wound protection materials and artificial organs. Has been. However, the polymer web obtained by the conventional method including Patent Document 1 may not have sufficient strength required for the application to be applied, and the application to the application is hindered. There is.

Therefore, Patent Document 2 discloses a method for producing a polymer web in which a polymer web formed by an electrodeposition method is stretched in one direction and fibers are rearranged in the stretch direction in order to improve the strength of the fiber sheet. It is disclosed. Specifically, the stretching process is performed at a temperature within the range of {(fiber glass transition temperature) -30} ° C. to (fiber glass transition temperature) ° C.
JP 2002-201559 A Japanese Patent Application Laid-Open No. 2005-97753

  However, when a high-strength fiber sheet is produced by the method described in Patent Document 2, it is necessary to separately perform the polymer solution discharge step and the stretching treatment step, and the stretching treatment step involves reheating. Since this is a process, there is a problem in that the production top surface is overwhelmed. Then, an object of this invention is to provide the means which has the orientation and can manufacture a high strength polymeric web more simply.

That is, according to the present invention (1), a voltage is applied between the polymer liquid medium supply unit (discharge unit 100) and the flying polymer receiving unit (collector electrode unit 110) to generate an electric field in the space between these two units. Forming and supplying the polymer liquid medium from the polymer liquid medium supply unit (discharge unit 100) toward the flying polymer receiving unit (collector electrode unit 110); In an electrodeposition apparatus for forming a polymer web containing at least part of the flying polymer on the electrode part 110),
The flying polymer receiving part (collector electrode part 110) is a cylindrical electrode (collector electrode 111) rotatable around a central axis,
The device is
An electrodeposition apparatus (Electrodeposition apparatus A) further comprising a rotation drive unit (rotation motor 112) for rotating the cylindrical electrode (collector electrode 111) about the central axis.

According to the present invention (2), the device is
The polymer liquid medium supply unit (discharge unit 100) and / or the rotation drive means (rotation motor) so that the surface linear velocity of the cylindrical electrode (collector electrode 111) is larger than the discharge rate of the polymer liquid medium. 112) is an apparatus (Electrodeposition apparatus A) according to the invention (1), further comprising a relative speed control means (relative speed control means 130) for controlling (112).

In the present invention (3), a voltage is applied between the polymer liquid medium supply unit (discharge unit 100) and the flying polymer receiving unit (collector electrode unit 110) to form an electric field in the space between these two units. By supplying the polymer liquid medium from the polymer liquid medium supply unit (discharge unit 100) toward the flying polymer receiving unit (collector electrode unit 110), the flying polymer receiving unit (collector electrode unit) 110) In the method for producing a polymer web comprising the step of forming a polymer web containing at least a part of the flying polymer as described above,
While using the cylindrical polymer electrode (collector electrode 111) that can rotate around the central axis as the flying polymer receiving portion (collector electrode portion 110),
While rotating the cylindrical electrode (collector electrode 111) around the central axis, the polymer liquid medium is directed from the polymer liquid medium supply unit (discharge unit 100) toward the cylindrical electrode (collector electrode 111). It is a method characterized by including the process to discharge.

  The present invention (4) is the method according to the invention (3), wherein in the step, the surface linear velocity of the cylindrical electrode (collector electrode 111) is made larger than the discharge velocity of the polymer liquid medium.

  The present invention (5) is the method of the invention (3) or (4), wherein the surface linear velocity of the cylindrical electrode (collector electrode 111) is 1 m / s or more.

  The present invention (6) is a polymer web produced by the method according to any one of the inventions (3) to (5).

  Here, the definition of each term in this claim and this specification is described. First, the “polymer liquid medium” is not particularly limited as long as it is a liquid medium containing a polymer, and includes any of a polymer solution, a polymer dispersion, and a polymer melt. The “flying polymer” is not particularly limited as long as it is a flying object derived from the polymer liquid medium supplied from the polymer liquid medium supply unit, and even if it is liquid or the solvent volatilizes during the flight. For example, the polymer is in a dry form. “Polymer web containing at least a part of flying polymer” means a polymer web composed only of flying polymer, or a composite of other substrate (eg, fiber, film, etc.) and flying polymer. (For example, the flying polymer adhered to another substrate) may be used.

  Advantageous Effects of Invention According to the present invention, it is possible to more easily produce a high-strength polymer web having orientation without separately performing a polymer liquid medium discharge step and a stretching treatment step. Play.

  Hereinafter, the best mode of the present invention will be described with reference to the drawings. The technical scope of the present invention is not limited to the best mode. Specifically, in the following best mode, terms are used in a limited manner such as taking a polymer solution as an example of the polymer liquid medium, but the technical scope of the present invention is limited to the limited terms. It is not something.

Device Configuration FIG. 1 is a diagram showing an embodiment of an electrodeposition device according to the best mode. Here, the electrodeposition apparatus A includes a discharge unit 100 for discharging a polymer solution toward a collector electrode 111 described later, a collector electrode unit 110 disposed at a position facing the discharge unit 100, A power supply unit 120 that applies a voltage between the discharge unit 100 and the collector electrode unit 110 (more precisely, between the nozzle electrode 101 of the discharge unit 100 and the collector electrode 111 of the collector electrode unit 110); And a relative speed control means 130 for controlling the discharge speed of the polymer solution and the surface linear speed of the collector electrode 111. Hereinafter, each component will be described in detail.

  First, a discharge unit 100 that constitutes a part of the electrodeposition apparatus A has a nozzle electrode 101 that is open so that a polymer solution can be discharged, and is in a liquid conduction relationship with the nozzle electrode 101. A liquid container 102 for holding the polymer solution to be supplied to the nozzle 101, and a pressing device (liquid ejection device) that pushes the polymer solution in the liquid container 102 and ejects the polymer solution from the opening of the nozzle electrode 101 to the outside. , Syringe pump) 103. Here, when the pressing device 103 is driven and controlled in the ejection direction, the polymer solution moves from the liquid container 102 to the nozzle electrode 101 and is ejected by a certain amount. By keeping the amount of the polymer solution ejected constant, a constant polymer web can be constructed per fixed time. Hereinafter, each element which comprises the discharge part 100 is explained in full detail.

  First, the nozzle electrode 101 has an opening as described above, has a function of discharging a polymer solution toward the collector electrode 111, is itself conductive, and is electrically connected to the power source 120. Therefore, it also has a function as an electrode. In the embodiment shown in FIG. 1, there is one nozzle electrode, but it is not always necessary to have one nozzle, and a plurality of nozzles may be provided. In FIG. 1, the nozzle electrode 101 plays the role of an electrode. However, the nozzle and the electrode do not have to be integrated, and may be used by further providing an electrode near the nozzle.

  Next, the collector electrode part 110 which constitutes a part of the electrodeposition apparatus A has a cylindrical shape and can rotate around the central axis, and a rotation motor for rotating the collector electrode 111 112. Here, as shown in FIG. 2, the collector electrode 111 holds the rotating shaft 116 penetrating the major axis direction at its center, and the rotating shaft 116 is a bearing portion of the support body 115 at both ends thereof. It is rotatably supported. Furthermore, the rotating shaft 116 of the collector electrode 111 and the rotating shaft of the rotating motor 112 are connected by an insulating joint member 114 such as a resin coupling.

  Next, the power supply unit 120 constituting a part of the electrodeposition apparatus A is a power supply that is electrically connected to the nozzle electrode 101 and the collector electrode 111 and can apply a voltage between the electrodes. Here, the power source that can be used for the power source unit 120 is not particularly limited, and examples thereof include a DC power source, a pulse power source, and an AC power source.

  Next, the relative speed control means 130 that constitutes a part of the electrodeposition apparatus A uses the collector electrode 111 so that the surface linear velocity of the collector electrode 111 is larger than the discharge speed of the polymer solution from the discharge portion 100. The relative speed control means 130 for controlling the surface linear velocity, the pressing device 103 and / or the rotary motor 112 are driven and controlled. Note that the relative speed control unit 130 can be realized by a computer including a CPU, a ROM, and a RAM, for example. In the ROM, a program for determining under what conditions the pressing device 103 and the rotary motor 112 are driven is recorded, and in the RAM, the driving conditions are determined based on the program. These parameters (for example, nozzle diameter, working liquid, collector electrode diameter, etc.) are temporarily recorded.

Manufacturing method (various conditions regarding manufacturing)
Next, a method for producing a polymer web by the electrodeposition method using the electrodeposition apparatus A according to the best mode will be described in detail.

  First, prior to carrying out this method, the liquid container 102 is filled with a polymer liquid medium, for example, a polymer solution or a polymer melt. Here, the polymer liquid medium that can be used in the apparatus according to the best mode is not particularly limited, and examples thereof include a polymer solution, a polymer dispersion, and a polymer melt. The polymer used in the polymer solution, polymer dispersion, or polymer melt is not particularly limited, but may be a general polymer such as vinyl polymer, acrylic polymer, urethane, nylon, conductive polymer, protein, etc. Natural polymers can be used, such as polyvinyl alcohol, nylon 66, polyacrylonitrile, polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyethylene oxide, cellulose, polyether urethane, polylactic acid, polycarbonate. Examples include prolactan, fibroin and collagen. Moreover, the polymer used is not limited to a single component, and two or more of the above-described polymers may be mixed and used.

  Here, when a solvent is used for the polymer liquid medium, the solvent is not particularly limited, and examples thereof include water, acetone, chloroform, ethanol, methanol, toluene, xylol, cyclohexane, dimethylformamide and the like. The solvent to be used is not limited to a single component, and two or more of the above-described solvents may be mixed and used. Furthermore, in order to improve the electrical characteristics of the polymer solution, an electrolyte such as sodium hydroxide or lithium chloride may be added to water.

  Next, in a state where a DC high voltage is applied between the nozzle electrode 101 and the collector electrode 111, the pressing device (syringe pump) 103 is operated to discharge a polymer solution or the like from the nozzle electrode 101. The released polymer solution or the like is released from the nozzle electrode 101 into an electric field generated between the nozzle electrode 101 and the collector electrode 111. When a polymer solution is used, the polymer released in the electric field flies and forms a polymer web on the rotating collector electrode 111. Thus, since the web which came from the nozzle electrode 101 adheres sequentially on the rotating collector electrode 111, the polymer web which has orientation is formed on the collector electrode 111.

  Here, when obtaining a polymer web of a desired form (shape, diameter, etc.), the nozzle diameter, the supply speed of liquid from the nozzle electrode (discharge speed), the surface linear velocity of the collector electrode, the distance between the electrodes, and the distance between the electrodes Depends on voltage, liquidity, etc. For example, by making the surface linear velocity of the collector electrode 111 faster than the flying speed of the polymer solution, it is possible to produce a polymer web having orientation in a state where tension is applied to the constructed polymer web. The rotation speed is usually in a range where the surface linear velocity is 0.1 m / min to 100 m / s. Here, from the viewpoint of obtaining a polymer web having higher strength (high breaking strength), it is preferable to rotate the collector electrode at a high speed. The nozzle diameter is preferably 0.1 to 2.0 mm. Moreover, 5-30 kV is suitable for the voltage between a discharge part and a collector electrode. Furthermore, the discharge amount of the discharged polymer liquid medium is preferably 10 μl / min to 1 ml / min.

Polymer web to be produced and its use The polymer web obtained by the apparatus according to the best mode of the present invention has high strength because the fibers are oriented, and various uses for which orientation and high strength are required, for example, It can be applied to electronics fields such as electric wires and light emitter electron guns on semiconductor substrates, environmental fields such as high performance filters, and medical fields such as wound protection materials and artificial organs.

Example 1
The electrodeposition apparatus A shown in FIG. 1 was constructed, and the electrodeposition was actually performed.
Place 0.5 ml of 5% aqueous solution of polyvinyl alcohol (MW200,000) in a discharge unit 100 (syringe pump equipped with a 1 ml glass syringe and a metal nozzle with a luer lock with an inner diameter of 0.5 mm), 75 μl per minute It adjusted so that it might discharge (discharge speed 6.5mm / s).
A collector electrode (cylinder type rotating electrode) 111 having the structure shown in FIG. 1 was rotated through a rotary motor 112 so that the cylinder surface linear velocity was 14.13 m / s.
The distance between the nozzle electrode 101 and the collector electrode 111 of the discharge unit 100 was adjusted to 180 mm, and a voltage of 15 kV was applied with the nozzle electrode 101 being positive. At this time, a current of approximately 40 to 50 μA was observed.
By driving the pressing device 103, fine fibers of polyvinyl alcohol were generated between the nozzle electrode 101 and the collector electrode 111, and the fibers adhered and deposited on the collector electrode 111.
After the pressing device 103 was driven for 10 minutes, the voltage application and the driving of the pressing device 103 were stopped, and the rotation of the collector electrode 111 was stopped. Fine fibers were deposited on the surface of the collector electrode 111.
When deposits on the collector electrode 111 were peeled off and observed with a microscope, it was observed that fine fibers were oriented and deposited in the rotational direction of the collector electrode 111. In addition, 200 fibers in the microscope field of view were arbitrarily selected and the average fiber diameter was measured to be 27 nm.

Comparative Example 1
Electrodeposition was performed under the same conditions as in Example 1 except that the collector electrode 111 was not rotated.
When the fibrous material deposit was peeled off and observed with a microscope, the fiber orientation was not observed, and the fibers were deposited randomly.
In addition, 200 fibers in the microscope were arbitrarily selected, and the average fiber diameter was measured and found to be 143 nm.

  The apparatus according to the present invention can efficiently produce a high-strength polymer web structure having orientation.

FIG. 1 shows an apparatus according to the best mode. FIG. 2 shows a side view of the collector electrode of the device according to the best mode. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100: Discharge part 101: Nozzle electrode 102: Liquid container 103: Liquid discharge apparatus 110: Collector electrode part 111: Collector electrode 112: Rotary motor 114: Insulating joint member 120: Power supply part 130: Relative speed control means

Claims (6)

A voltage is applied between the polymer liquid medium supply unit and the flying polymer receiving unit to form an electric field in the space between these two parts, and from the polymer liquid medium supplying unit to the flying polymer receiving unit In an electrodeposition apparatus for forming a polymer web containing at least part of the flying polymer on the flying polymer receiving unit by supplying the polymer liquid medium,
The flying polymer receiving portion is a cylindrical electrode that can rotate around a central axis,
The device is
The electrodeposition apparatus further comprising a rotation driving means for rotating the cylindrical electrode about the central axis. The device is
The apparatus further comprises a relative speed control means for controlling the polymer liquid medium supply unit and / or the rotation driving means so that a surface linear velocity of the cylindrical electrode is larger than a discharge speed of the polymer liquid medium. Item 1. The apparatus according to Item 1. A voltage is applied between the polymer liquid medium supply unit and the flying polymer receiving unit to form an electric field in the space between these two parts, and from the polymer liquid medium supplying unit to the flying polymer receiving unit In the method for producing a polymer web, comprising the step of forming the polymer web containing at least a part of the flying polymer on the flying polymer receiving unit by supplying the polymer liquid medium.
While using a cylindrical electrode that can rotate around the central axis as the flying polymer receiver,
A method comprising discharging the polymer liquid medium from the polymer liquid medium supply unit toward the cylindrical electrode while rotating the cylindrical electrode about the central axis.   The method according to claim 3, wherein in the step, the surface linear velocity of the cylindrical electrode is made larger than the discharge velocity of the polymer liquid medium.   The method of Claim 3 or 4 that the surface linear velocity of the said cylindrical electrode is 1 m / s or more.   A polymer web produced by the method according to claim 3.

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