WO2015020129A1 - ナノファイバ製造装置、ナノファイバの製造方法及びナノファイバ成型体 - Google Patents
ナノファイバ製造装置、ナノファイバの製造方法及びナノファイバ成型体 Download PDFInfo
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- WO2015020129A1 WO2015020129A1 PCT/JP2014/070820 JP2014070820W WO2015020129A1 WO 2015020129 A1 WO2015020129 A1 WO 2015020129A1 JP 2014070820 W JP2014070820 W JP 2014070820W WO 2015020129 A1 WO2015020129 A1 WO 2015020129A1
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- nozzle
- electrode
- raw material
- manufacturing apparatus
- nanofiber
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0018—Pullulan, i.e. (alpha-1,4)(alpha-1,6)-D-glucan; Derivatives thereof
-
- 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
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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- 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
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
Definitions
- the present invention relates to a nanofiber manufacturing apparatus, a nanofiber manufacturing method, and a nanofiber molded body.
- the electrospinning method is attracting attention as a technology that can relatively easily manufacture a nano-sized diameter fiber (hereinafter referred to as nanofiber) without using mechanical force or heat.
- a solution of a substance that is a raw material for nanofibers is filled in a syringe, a needle-like nozzle attached to the syringe, and a collection electrode facing the needle-like nozzle
- the operation of discharging the solution from the tip of the nozzle is performed under the condition that a high DC voltage is applied during the period.
- the discharged solution is stretched by Coulomb force, the solvent is instantly evaporated, and nanofibers are formed while the raw material is solidified.
- the nanofibers are deposited on the surface of the collecting electrode.
- Patent Document 1 In order to increase the productivity of nanofiber manufacturing, in Patent Document 1, a metal ball having a small diameter, a metal spinning nozzle arranged with a small distance between the metal ball and the nozzle opening, and a metal ball A plurality of units composed of high-speed air flow injection nozzles for injecting high-speed air flow so as to be orthogonal to the path between the nozzle and the spinning nozzle opening are arranged in parallel, and a high voltage is applied between the metal sphere and the spinning nozzle to form nanofiber A nanofiber manufacturing method is disclosed in which nanofibers scattered from a plurality of units are collected and collected by a nanofiber collecting section.
- Patent Document 2 a raw material liquid injection nozzle grounded through two selectable rectifiers, a derivative in which an insulating layer made of a dielectric and a conductor layer made of a conductor are arranged on an electrode, and an alternating current is applied to the derivative.
- a nanofiber manufacturing apparatus including an alternating current power source to be applied is disclosed.
- nanofibers having opposite charging polarities are alternately manufactured to prevent the atmosphere from being charged to one polarity. This makes it possible to provide a simple device configuration for insulation treatment and safety measures, preventing charging of nearby members and facilitating collection of nanofibers.
- Patent Document 3 discloses a nanofiber manufacturing apparatus having an outflow body in which a large number of outflow holes are provided on the side surface of a conductive cylinder having a diameter of 10 mm to 300 mm instead of the raw material liquid injection nozzle. Then, a voltage is applied between the effluent and an electrode provided with an insulator layer on the surface facing the effluent to form a nanofiber, and two collecting electrodes (attracting electrodes) having opposite polarity potentials. ) Attracts nanofibers and collects them on the material to be deposited.
- the thin insulator layer with a thickness of 0.2 mm can prevent the nanofiber from adhering to the electrode, and can change the charged state of the nanofiber and efficiently use the two collecting electrodes (attracting electrodes). Can collect.
- Patent Document 4 also proposes a technique in which the raw material liquid injection nozzle is made of resin instead of metal. This makes it possible to control the solidification of the raw material liquid at the nozzle, simplifying the nozzle cleaning operation and preventing discharge from the nozzle. At this time, instead of the metal nozzle, the electrode of any shape is placed in the raw material liquid storage container or in the transport path between the storage container and the nozzle, thereby charging the raw material liquid.
- the productivity of nanofibers is fundamentally determined by the amount of raw material liquid injected from one raw material liquid injection nozzle per unit time. That is, even if a large amount of raw material liquid is supplied to the raw material liquid injection nozzle per unit time, it is necessary to be able to perform normal and stable spinning. In the nanofiber manufacturing apparatus using the electrospinning method, this is realized by increasing the charge amount of the raw material liquid to be injected. However, in terms of increasing the charge amount of the raw material liquid, the techniques described in the above-mentioned documents are not sufficient, and it is not easy to obtain nanofibers with satisfactory productivity.
- an object of the present invention is to provide a nanofiber manufacturing apparatus that can eliminate the disadvantages of the above-described conventional technology.
- the present invention comprises a raw material injection means comprising a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode; A nanofiber production apparatus comprising a collection means for collecting nanofibers, The voltage generating means generates a voltage so that the nozzle becomes an anode and the electrode becomes a cathode, The electrode has a substantially entire surface facing the nozzle covered with a coating with a dielectric exposed on the surface, The present invention provides a nanofiber manufacturing apparatus in which the dielectric exposed on the surface has a thickness of 0.8 mm or more.
- the present invention also includes a raw material injection means including a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode; A nanofiber production apparatus comprising a collection means for collecting nanofibers, The voltage generating means generates a voltage so that the nozzle becomes an anode and the electrode becomes a cathode, Provided is a nanofiber manufacturing apparatus in which substantially the entire outer surface of the nozzle is covered with a coating body with a dielectric exposed on the surface, and the coating body extends beyond the tip of the nozzle. .
- the present invention also includes a raw material injection means including a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode; A nanofiber production apparatus comprising a collection means for collecting nanofibers, The voltage generating means generates a voltage so that the nozzle becomes a cathode and the electrode becomes an anode, It is an object of the present invention to provide a nanofiber manufacturing apparatus in which substantially the entire outer surface of the nozzle is covered with a coating with a dielectric exposed on the surface.
- the present invention also includes a raw material injection means including a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode; A nanofiber production apparatus comprising a collection means for collecting nanofibers, The voltage generating means generates a voltage so that the nozzle becomes a cathode and the electrode becomes an anode, The electrode has a substantially entire surface facing the nozzle covered with a coating with a dielectric exposed on the surface, The present invention provides a nanofiber manufacturing apparatus in which the dielectric exposed on the surface has a thickness of 0.8 mm or more.
- the present invention provides a raw material injection means comprising a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode; A nanofiber production apparatus comprising a collection means for collecting nanofibers,
- the present invention provides a nanofiber manufacturing apparatus in which the collecting means has a collecting electrode, and substantially the entire surface of the collecting electrode is covered with a coating with a dielectric exposed.
- the present invention provides a nanofiber manufacturing method for manufacturing nanofibers using the nanofiber manufacturing apparatus.
- the present invention provides a nanofiber molded body comprising nanofibers manufactured using the nanofiber manufacturing apparatus.
- the amount of charge of the raw material liquid used for the production of nanofibers can be made higher than before, and as a result, the productivity of nanofibers can be increased more than before and the space can be saved.
- An electrospinning apparatus that can be achieved and a nanofiber manufacturing apparatus using the same are provided.
- FIG.1 (a) is a side view in one Embodiment of the nanofiber manufacturing apparatus of this invention
- FIG.1 (b) is a front view in Fig.1 (a).
- FIG. 2 is a cross-sectional view showing an example of a nozzle structure in the manufacturing apparatus shown in FIG.
- FIG. 3 is an exploded perspective view showing another embodiment of the nanofiber manufacturing apparatus of the present invention.
- FIG. 4 is a schematic diagram showing a cross-sectional structure of the nanofiber manufacturing apparatus shown in FIG. Fig.5 (a) is a side view which shows the cross section of another embodiment of the nanofiber manufacturing apparatus of this invention
- FIG.5 (b) is a top view in Fig.5 (a).
- FIG. 6 is a side view showing a cross section of another embodiment of the nanofiber manufacturing apparatus shown in FIG. Fig.7 (a) is a side view in further another embodiment of the nanofiber manufacturing apparatus of this invention, FIG.7 (b) is a front view in Fig.7 (a).
- Fig.8 (a) is a side view in further another embodiment of the nanofiber manufacturing apparatus of this invention, FIG.8 (b) is a front view in Fig.8 (a).
- FIG. 9 is a partially cutaway perspective view showing the airflow ejecting means in FIG.
- FIG. 10 is a schematic view showing a cross-sectional structure in still another embodiment of the nanofiber manufacturing apparatus of the present invention.
- FIG. 11 is a schematic diagram showing an exploded perspective view of a main part of the nanofiber manufacturing apparatus shown in FIG.
- FIG. 12A is a front view of the airflow ejecting means in the nanofiber manufacturing apparatus shown in FIG. 9, and
- FIG. 12B is a cross-sectional view of the airflow ejecting means along the longitudinal direction of the nozzle.
- FIG. 13 is a front view showing still another embodiment of the electrospinning apparatus of the present invention.
- FIG. 14 is a schematic diagram showing a cross-sectional structure of the electrospinning apparatus shown in FIG.
- FIG. 15 is an exploded perspective view of the electrospinning apparatus shown in FIG.
- FIG. 16 is a schematic view (corresponding to FIG. 13) showing a cross-sectional structure of another embodiment of the electrospinning apparatus.
- FIG. 17 is a schematic view showing a nanofiber manufacturing apparatus provided with the electrospinning apparatus shown in FIG.
- FIG. 18 is a schematic diagram illustrating the structure of the nozzle in a cross-sectional view.
- FIG. 19 is a diagram showing the relationship between the thickness of the covering in the nanofiber manufacturing apparatus shown in FIG. 1 and the leakage current flowing between the nozzle and the electrode.
- 20 (a) is a schematic diagram showing an apparatus for measuring the charge amount of the raw material liquid in the manufacturing apparatus shown in FIG. 1, and FIG. 20 (b) is in the manufacturing apparatus shown in FIG. 3, FIG. 4 and FIG. It is a schematic diagram which shows the apparatus which measures the charge amount of a raw material liquid.
- FIG. 20 is a schematic diagram showing an apparatus for measuring the charge amount of the raw material liquid in the manufacturing apparatus shown in FIG. 1, and FIG. 20 (b) is in the manufacturing apparatus shown in FIG. 3, FIG. 4 and FIG. It is a schematic diagram which shows the apparatus which measures the charge amount of a raw material liquid.
- FIG. 21A is a scanning electron micrograph of a nanofiber manufactured by the nanofiber manufacturing apparatus according to one embodiment of the present invention
- FIG. 21B is a nanofiber manufacturing apparatus not according to the present invention. It is a scanning electron micrograph of the manufactured nanofiber.
- FIG. 22 is a scanning electron micrograph of a nanofiber manufactured by the nanofiber manufacturing apparatus according to another embodiment of the present invention.
- FIG. 23A is a scanning electron microscope image of the nanofiber obtained in Example 17, and FIG. 23B is an enlarged image of FIG.
- FIG. 24A is a scanning electron microscope image of the nanofiber obtained in Comparative Example 12, and FIG. 24B is an enlarged image of FIG.
- FIG. 1 (a) shows a side view of an embodiment of the nanofiber manufacturing apparatus of the present invention.
- FIG.1 (b) is a front view in Fig.1 (a).
- the nanofiber manufacturing apparatus 10 of the present embodiment basically employs a jet ESD method in which ESD (Electro-Spray Deposition) and high-speed jet airflow (jet) are combined.
- the manufacturing apparatus 10 includes a raw material injection unit 11 for injecting a raw material liquid for producing nanofibers.
- the raw material injection unit 11 includes a liquid feeding unit 12 and a nozzle 13.
- the nozzle 13 is erected at the tip of the liquid feeding unit 12.
- the nozzle 13 is open at the vertical upper end, and the raw material liquid can be injected through the opening.
- the nozzle 13 is made of a conductive material such as metal and has conductivity.
- the liquid feeding section 12 can inject the raw material liquid from the nozzle 13 in an amount determined per unit time.
- the nozzle 13 is composed of a needle-like straight pipe.
- a raw material liquid can be circulated in the nozzle 13.
- the lower limit of the inner diameter of the nozzle 13 is preferably set to 200 ⁇ m or more, more preferably 300 ⁇ m or more.
- the upper limit is preferably set to 3000 ⁇ m or less, more preferably 2000 ⁇ m or less.
- the inner diameter of the nozzle 13 is preferably set to, for example, 200 ⁇ m or more and 3000 ⁇ m or less, more preferably 300 ⁇ m or more and 2000 ⁇ m or less.
- the lower limit of the outer diameter of the nozzle 13 is preferably set to 300 ⁇ m or more, more preferably 400 ⁇ m or more.
- the upper limit value can be set to preferably 4000 ⁇ m or less, and more preferably 3000 ⁇ m or less.
- the outer diameter of the nozzle 13 is, for example, preferably set to 300 ⁇ m or more and 4000 ⁇ m or less, more preferably 400 ⁇ m or more and 3000 ⁇ m or less.
- the electrode 14 is disposed at a position separated from the nozzle 13. Specifically, the electrode 14 is disposed facing the opening of the nozzle 13 at a position immediately above the opening of the nozzle 13.
- the electrode 14 is plate-shaped and has two flat portions and four side portions. One of these two flat portions (the lower surface in the figure) faces the nozzle 13.
- the direction in which the nozzle 13 extends and the plane portion of the electrode 14 are substantially orthogonal.
- the electrode 14 is made of metal or the like and has conductivity.
- the distance (shortest distance) between the tip of the nozzle 13 and the electrode 14 is preferably set to 20 mm or more, particularly 30 mm or more.
- the upper limit value of the distance between the tip of the nozzle 13 and the electrode 14 is preferably set to 100 mm or less, particularly 50 mm or less. If it is wider than this, the electric field formed between the nozzle 13 and the electrode 14 becomes weak, and a high charge amount cannot be obtained.
- the distance between the two is preferably set to 20 mm or more and 100 mm or less, and more preferably set to 30 mm or more and 50 mm or less.
- a DC voltage is applied between the nozzle 13 made of a conductive material and the electrode 14 by the voltage generating means 101 via the earth 102 and the metal conductor 103.
- the nozzle 13 is grounded as shown in FIG.
- a negative voltage is applied to the electrode 14. Therefore, the electrode 14 becomes a cathode and the nozzle 13 becomes an anode, and a voltage is generated between the electrode 14 and the nozzle 13 to form an electric field.
- a positive voltage may be applied to the nozzle 13 and the electrode 14 may be grounded instead of applying the voltage shown in FIG. .
- the voltage generated by the voltage generating means 101 is changed to a DC voltage as long as the electrode 14 is kept at the cathode and the nozzle 13 is kept at the anode, that is, as long as the nozzle 13 is kept at a higher potential than the cathode 14. It may be a fluctuating voltage in which a voltage is superimposed. From the viewpoint of keeping the charge amount of the raw material liquid constant and producing nanofibers of uniform thickness, the voltage is preferably a DC voltage.
- the voltage generating means 101 a known device such as a high voltage power supply device can be used.
- the potential difference applied between the electrode 14 and the nozzle 13 is preferably 1 kV or more, particularly 10 kV or more from the viewpoint that the raw material liquid can be sufficiently charged.
- this potential difference is preferably 100 kV or less, particularly 50 kV or less, from the viewpoint of preventing discharge between the nozzle 13 and the electrode 14.
- it is preferably 1 kV to 100 kV, particularly preferably 10 kV to 50 kV.
- the voltage applied by the voltage generating means 101 is a variable voltage
- the time average of the potential difference generated between the electrode 14 and the nozzle 13 is preferably within the above range.
- the manufacturing apparatus 10 further includes an air flow injection means 15.
- the air flow ejecting means 15 can eject a primary high-speed air flow.
- the airflow ejecting means 15 is disposed at a position where an airflow can be ejected between the nozzle 13 and the electrode 14.
- the nanofiber formed from the raw material liquid is positively charged and tends to extend from the nozzle 13 serving as the anode toward the electrode 14 serving as the cathode.
- the airflow ejected from the airflow ejecting means 15 changes the traveling direction of the nanofibers and conveys the nanofibers in a direction (the right direction in the drawing of FIG. 1 (a)) while stretching the nanofibers. It contributes to that.
- the air flow ejected from the air flow ejecting means 15 for example, one dried by a dryer or the like to a humidity of 30% RH or less can be used.
- the air flow is preferably maintained at a constant temperature so that the state of the manufactured nanofibers is maintained constant.
- the flow rate of the air flow is preferably 200 m / sec or more, particularly 250 m / sec or more, for example. If it is slower than this, it becomes difficult to change the traveling direction of the nanofiber to the direction in which the collecting means is present against the electric field between the nozzle 13 and the electrode 14.
- the upper limit of the flow rate is preferably 600 m / sec or less, and particularly preferably 530 m / sec or less.
- the flow rate is preferably 200 m / sec or more and 600 m / sec or less, and particularly preferably 250 m / sec or more and 530 m / sec or less.
- the manufacturing apparatus 10 also includes a second air flow injection means 16.
- the second airflow injection means 16 injects a secondary high-speed airflow that is an airflow slower than the primary high-speed airflow over a wide range so as to include the primary high-speed airflow from the airflow injection means 15. Is.
- a collecting means for collecting the nanofibers is disposed at a position facing the air flow ejecting means 15 and the second air flow ejecting means 16.
- a collecting electrode (not shown) can be arranged as part of the collecting means.
- the collection electrode can be a flat plate made of a conductive material such as metal.
- the plate surface of the collecting electrode and the air flow injection direction are substantially orthogonal.
- the collecting electrode can be coated on the substantially entire surface with a covering with a dielectric exposed, more preferably on the entire surface.
- the substantially entire surface means a surface occupying an area of 90% or more of the total surface area of the surface.
- the entire surface means a surface that occupies 100% of the total surface area of the surface.
- a lower (negative) potential is applied to the collecting electrode than the nozzle 13 serving as the anode.
- a lower (negative) potential is applied to the electrode 14 which is a cathode.
- the lower limit of the distance (shortest distance) between the collecting electrode (electrode surface) and the tip of the nozzle 13 is preferably 100 mm or more, and more preferably 500 mm or more. By doing so, the nanofiber can be sufficiently solidified before reaching the collecting electrode.
- the upper limit is preferably 3000 mm or less, more preferably 1000 mm or less. By doing so, the force of electrical attraction by the collection electrode is increased, and the collection rate of the nanofiber is improved. For example, it is preferably 100 mm or more and 3000 mm or less, and more preferably 500 mm or more and 1000 mm or less.
- a collector in which nanofibers are collected between the collection electrode and the nozzle 13 so as to be adjacent to the collection electrode.
- insulators such as a film, a mesh, a nonwoven fabric, and paper, can be used, for example.
- air exhaust means (not shown) that exhausts the injected air flow is disposed so as to face the air flow injection means 15 and the second air flow injection means 16. You can also.
- the air exhaust means is preferably arranged on the back side (the side farther from the nozzle 13) than the collection electrode described above.
- a known device such as a suction box can be used.
- the surface facing the nozzle 13 in the plane portion constituting the plate-like electrode 14 (the electrode 14 in the figure).
- the bottom surface) is covered with a covering 17 having a dielectric exposed on the surface.
- the covering 17 is made of a single kind of dielectric.
- substantially the entire surface of the electrode facing the nozzle is covered with a covering with a dielectric exposed. More preferably, the entire surface facing the nozzle is coated with a coating with a dielectric exposed on the surface.
- the surface facing the nozzle is the surface of the electrode that can face from the tip of the nozzle (opening through which the raw material liquid is jetted).
- the substantially entire surface means a surface occupying an area of 90% or more of the total surface area of the surface, and the entire surface means a surface occupying an area of 100% of the total surface area of the surface.
- a covered body with a dielectric exposed on the surface is a covered body in which substantially the entire surface (area of 90% or more) is made of only a dielectric. As will be described later, it is preferable that the entire surface of the covering (100% area) is composed only of a dielectric.
- the covering is preferably a covering in which a dielectric is exposed on the surface and no conductor such as metal is present on the surface.
- a typical example is a covering made up of a single type of dielectric, but the covering may be a composite of multiple types of dielectrics, or the surface may be made up of only a dielectric.
- it may be a composite containing metal particles, an air layer, or the like inside (a portion not exposed on the surface).
- an air layer may exist at a part of the joint between the electrode and the covering, but it is preferable that the electrode and the covering are in close contact from the viewpoint of strengthening the bonding between the electrode and the covering.
- the covering 17 In the electrode 14 shown in FIG. 1, only the surface facing the nozzle 13 is covered with the covering 17. In addition to this, a part of the surface not facing the nozzle 13 is also covered with a dielectric exposed on the surface. It is preferably covered with the body 17. Furthermore, it is preferable that the entire surface that does not face the nozzle 13 is covered with a covering 17 having a dielectric exposed on the surface.
- the surface that does not face the nozzle is the surface of the electrode that cannot be faced from the tip of the nozzle (opening through which the raw material liquid is sprayed). More specifically, it is the surface of the electrode surface excluding the surface facing the nozzle.
- the present inventors can remarkably increase the charge amount of the raw material liquid sprayed from the nozzle 13 by covering the surface of the electrode 14 facing the nozzle 13 with the covering. I found.
- the mechanism is expected as follows.
- the cation in the raw material liquid is attracted to the electrode 14 (cathode) side by the electric field formed between the electrode 14 and the nozzle 13, and the anion in the raw material liquid is the nozzle. 13 (anode) is attracted to the inner surface.
- the raw material liquid injected toward the electrode 14 contains a large amount of cations, and the raw material liquid is positively charged.
- the discharge between the electrode 14 and the nozzle 13 is suppressed, and the applied voltage between the electrode 14 and the nozzle 13 is increased or the distance is reduced. Is possible. Thereby, the electric field between the electrode 14 and the nozzle 13 is strengthened, and the charge amount of the raw material liquid can be increased. Furthermore, since the electrode 14 (cathode) and the nozzle 13 (anode) can be regarded as a capacitor sandwiching air, inserting a dielectric between the electrodes increases the capacitance of the capacitor, and as a result, the charge amount of the raw material liquid The effect of increasing can also be expected.
- the current (leakage current) flowing between the electrode 14 and the nozzle 13 is reduced, and the effect of reducing the power consumption when manufacturing the nanofiber can be expected.
- the covering 17 not only the surface of the electrode 14 that faces the nozzle 13 but also the surface that does not face the nozzle 13 is covered with the covering 17 so that the effect is further enhanced. This is because not a few electrons are emitted to the atmosphere from the surface not facing the nozzle 13. From the viewpoint of increasing the charge amount of the raw material liquid, it is preferable to cover all surfaces of the electrode 14 with the covering body 17.
- Patent Document 2 described in the section of the background art, an insulating layer made of a dielectric material is provided on the surface of the application electrode facing the ejecting means for the purpose of reducing the risk of electric shock due to the human body contacting the application electrode.
- a nanofiber manufacturing apparatus in which is arranged is disclosed.
- a conductor layer (conductive layer) made of a conductor is further arranged on the surface of the insulating layer. That is, a covering with a conductor layer exposed on the surface is used. From such a conductor layer, electrons are likely to be emitted to the atmosphere, and it is considered that the effect of the present invention in which the emission of electrons is suppressed by using a covering with a dielectric exposed on the surface cannot be expected.
- the covering of the present invention has the entire surface (100% area) made of only a dielectric, that is, the dielectric is exposed on the surface, and a conductor such as metal is not on the surface. It is preferable that the coating body is present.
- Dielectric materials used for the covering 17 include ceramic materials such as insulating materials such as mica, alumina, zirconia, and barium titanate, bakelite (phenol resin), nylon (polyamide), vinyl chloride resin, polystyrene, polyester, and polypropylene. And resin materials such as polytetrafluoroethylene and polyphenylene sulfide. Among these, it is preferable to use at least one insulating material selected from alumina, bakelite, nylon, and vinyl chloride resin, and it is particularly preferable to use nylon. As the nylon, various polyamides such as 6 nylon and 66 nylon can be used. Moreover, a commercial item can also be used as nylon. As such a commercial item, MC nylon (trademark) is mentioned, for example.
- the dielectric used for the covering 17 can contain an antistatic agent.
- an antistatic agent By containing an antistatic agent, when the charged raw material liquid, nanofiber, or the like adheres to the covering 17, the charging of the covering 17 can be reduced.
- known commercially available products can be used. For example, Perectron (Sanyo Chemical Industry Co., Ltd.), Electro Stripper (Kao Corporation), Electro Master (Kao Corporation), Riquemar (RIKEN Vitamin ( Co., Ltd.), Riquet Master (RIKEN Vitamin Co., Ltd.) and the like can be used.
- the covering body 17 preferably covers the electrode 14 with a uniform thickness.
- the thickness of the dielectric exposed on the surface constituting the covering body 17 is preferably 0.8 mm or more, particularly 2 mm or more, particularly 8 mm or more. By doing so, it is possible to sufficiently suppress the emission of electrons from the electrode and to increase the charge amount of the raw material liquid. If it is thinner than this, the emission of electrons from the electrode 14 cannot be sufficiently suppressed, and the charge amount of the raw material liquid may not be increased.
- the said thickness points out the thickness of the coating body 17 (equal to the thickness of the coating body 17), when the coating body 17 is comprised from the single type or multiple types of dielectric material.
- the covering 17 when the covering 17 is a composite containing metal particles or an air layer in the interior (portion not exposed to the surface), it indicates the thickness of the dielectric existing between the surface and the metal or air
- the upper limit value of the thickness of the covering 17 is preferably 25 mm or less, particularly 20 mm or less, particularly 15 mm or less.
- the covering 17 is composed of a single kind or a plurality of kinds of dielectrics, for example, the thickness of the covering 17 is preferably 0.8 mm to 25 mm, particularly 2 mm to 20 mm, particularly 8 mm to 15 mm.
- Patent Document 3 described in the background section above discloses a nanofiber manufacturing apparatus in which a thin insulator layer is provided on the surface of an electrode.
- the nanofiber manufacturing apparatus is different from the present invention in that it uses an outflow body in which a large number of outflow holes are provided on the side surface of a conductive cylinder having a diameter of 10 mm to 300 mm, not a raw material liquid injection nozzle.
- An electrode having a thin insulating layer provided on the surface facing the outflow body is provided.
- the purpose of the insulator layer is to prevent the nanofiber from adhering to the electrode and to change the charged state of the nanofiber.
- a thin insulator layer having a thickness of 0.2 mm is used. ing.
- Such a thin insulator layer used in Patent Document 3 cannot sufficiently suppress the emission of electrons from the electrode, and the effect of the present invention cannot be expected.
- the amount of charge of the raw material liquid can also be increased by covering the surface with a coating with a dielectric exposed.
- the outer surface of the nozzle 13 is covered with a covering body 107.
- the covering 107 extends beyond the tip 13 a of the nozzle 13.
- the extending portion 107 a of the covering body 107 has a cylindrical shape surrounding the nozzle 13 and has a hollow portion. This hollow portion communicates with the inside of the nozzle 13.
- the outer surface of the nozzle 13 is the inner surface of the nozzle 13 in contact with the raw material liquid flowing through the nozzle 13, the surface of the tip 13 a of the nozzle 13 to which the raw material liquid is injected, and the nozzle 13 on the opposite side. It is the surface excluding the end surface.
- the covering 107 is composed of a single type or a plurality of types of dielectrics. By covering substantially the entire outer surface of the nozzle 13 with the covering 107 having a dielectric exposed, the number of electrons flying from the electrode 14 and flowing into the nozzle 13 can be suppressed. As a result, the discharge between the electrode 14 and the nozzle 13 is less likely to occur, and the applied voltage between the electrode 14 and the nozzle 13 can be increased and the distance can be reduced.
- the electric field between the electrode 14 and the nozzle 13 can be strengthened to increase the charge amount of the raw material liquid.
- the length of the extended portion 107a of the covering 107 is preferably 1 mm or more, and more preferably 10 mm or more. If it is shorter than this, the effect of extending the covering 107 is reduced.
- the upper limit value is preferably 15 mm or less, and more preferably 12 mm or less. If it is longer than this, the raw material liquid sprayed from the tip of the covering 107 and made into a fiber shape is likely to adhere to the electrode 14 or the covering 17.
- the length of the extended portion 107a is preferably 1 mm to 15 mm, particularly preferably 10 mm to 12 mm. By forming the extended portion 107a of this length, it is possible to suppress the discharge between the electrode 14 and the nozzle 13 and effectively increase the charge amount of the raw material liquid.
- the same dielectric as that that forms the covering 17 that covers the electrode 14 can be used.
- the dielectric can contain the same antistatic agent as used in the covering 17.
- the thickness of the covering 107 that covers the nozzle 13 can be the same as the thickness of the covering 17 that covers the electrode 14.
- the amount of charge of the raw material liquid can be increased also by covering substantially the entire surface of the collecting electrode, which is a part of the collecting means, with a covering with a dielectric exposed on the surface.
- the collecting electrode (not shown) is given a lower (negative) potential than the nozzle 13 serving as the anode in order to attract positively charged nanofibers. Therefore, electrons are also emitted from the surface of the collecting electrode to the atmosphere, and the electrons fly to the nozzle 13. This flying of electrons can be suppressed by covering substantially the entire surface of the collecting electrode with a covering having a dielectric exposed on the surface.
- the charge amount of the raw material liquid can be increased.
- the dielectric constituting the covering that covers the collecting electrode the same dielectric as that constituting the covering 17 that covers the electrode 14 can be used.
- the dielectric can contain the same antistatic agent as used in the covering 17. Further, it is preferable that the covering body covers the collecting electrode with a uniform thickness from the viewpoint of stabilizing the electric field between the electrode and the nozzle.
- the thickness of the dielectric exposed on the surface constituting the covering is 0.8 mm or more, particularly 2 mm or more, particularly 8 mm or more. By doing so, it is possible to sufficiently suppress the emission of electrons from the electrode and to increase the charge amount of the raw material liquid. If it is thinner than this, the emission of electrons from the collecting electrode cannot be sufficiently suppressed, and the charge amount of the raw material liquid cannot be increased.
- the upper limit of the thickness of the covering is not particularly limited, but the upper limit of the thickness is preferably 25 mm or less, particularly 20 mm or less, particularly 15 mm or less from the economical viewpoint of reducing the amount of material used.
- the covering is composed of a single kind or a plurality of kinds of dielectrics, for example, the thickness of the covering is preferably 0.8 mm or more and 25 mm or less, particularly 2 mm or more and 20 mm or less, and particularly preferably 8 mm or more and 15 mm or less.
- the covering of the collecting electrode with the covering and the covering of the electrode 14 with the covering 17 and / or the covering of the nozzle 13 with the covering 107 can be combined.
- the raw material liquid is sprayed from the tip of the nozzle 13 in a state where an electric field is generated between the electrode 14 and the nozzle 13. Since cations in the raw material liquid are attracted to the electrode 14 (cathode) side by the electric field, the raw material liquid ejected from the nozzle 13 toward the electrode 14 contains a large amount of cations, and the raw material liquid is positively charged. . As described above, the charge amount per unit mass of the raw material liquid becomes extremely high due to the electrode 14 being covered with the covering 17. The liquid surface of the raw material liquid sprayed in a charged state is deformed into a conical shape by the action of an electric field.
- the raw material liquid is drawn toward the electrode 14 all at once.
- the air flow is injected from the air flow injection means 15 toward the injected raw material liquid, thereby changing the traveling direction of the raw material liquid and directing the raw material liquid toward the collector (not shown).
- the fiber is thinned to nano-size by the self-repulsion chain of the charge of the raw material liquid, and at the same time, the volatilization of the solvent, the solidification of the polymer, and the like proceed to produce the nanofiber.
- the produced nanofibers are attracted by the electric field generated by the collecting electrode (not shown) on the airflow ejected from the airflow ejecting means 15 and the second airflow ejecting means 16, and the airflow ejecting means. 15 is deposited on the surface of the collector disposed at a position facing 15.
- a lower (negative) potential is applied to the collector electrode than the nozzle 13 serving as the anode.
- a lower (negative) potential is applied than the electrode 14 which is a cathode.
- the nanofiber manufacturing method described above since the amount of charge of the raw material liquid sprayed from the tip of the nozzle 13 is extremely high, the force for attracting the raw material liquid toward the electrode 14 becomes large. Therefore, even if a larger amount of raw material liquid (per unit time) than before is ejected from the nozzle 13, it becomes possible to produce nanofibers as thin as the conventional one. In addition, even if the discharge amount of the raw material liquid is increased, defects or the like are hardly generated in the obtained nanofiber.
- the defect referred to here is, for example, a material liquid droplet solidified as it is, or a bead-like material formed by solidifying a raw material liquid droplet without being sufficiently stretched.
- FIG. 3 and 4 show another embodiment of the manufacturing apparatus of the present invention.
- the manufacturing apparatus 18 of the present embodiment includes an electrode 19 and a raw material liquid injection nozzle 20.
- the electrode 19 has a concave spherical shape as a whole, and particularly has a substantially bowl shape.
- a concave curved surface R is provided on the inner surface.
- the electrode 19 having the concave curved surface R has a planar flange portion 19a at the position of the opening end.
- the inner surface of the electrode 19 is a concave curved surface R, the outer surface of the electrode 19 does not need to have a substantially bowl shape, and may have another shape.
- the electrode 19 is made of a conductive material and is generally made of metal.
- the electrode 19 is fixed to a base 30 made of an electrically insulating material. Further, the electrode 19 is connected to a DC high voltage power source 40 as voltage generating means as shown in FIG. 4, and a negative voltage is applied thereto.
- the opening end is circular.
- This circle may be a perfect circle or an ellipse.
- the open end of the concave curved surface R is preferably a perfect circle.
- the concave curved surface R is a curved surface at any position.
- the curved surface referred to here is (a) a curved surface that does not have a flat surface portion at all, or (b) a shape that can be regarded as a concave curved surface as a whole by connecting a plurality of segments having a flat surface portion.
- one of the three axes orthogonal to each other is connected to a plurality of annular segments having a belt-like portion with no curvature, and has a shape that can be regarded as a concave curved surface as a whole.
- a concave curved surface R is formed by connecting segments having flat portions of the same or different sizes, which are rectangular with a vertical and horizontal length of about 0.5 to 5 mm. It is preferable.
- it is preferable to form the concave curved surface R by connecting annular segments made of a plurality of flat cylinders having different radii and heights of 0.001 to 5 mm.
- the X-axis and Y-axis including the cross section of the cylinder have a curvature, and Z is the height direction of the cylinder.
- the axis has no curvature.
- the distance (shortest distance) between the tip 20a of the nozzle 20 and the concave curved surface R can be made the same as the distance (shortest distance) between the tip of the nozzle 13 and the electrode 14 in the manufacturing apparatus 10.
- the concave curved surface R has a value such that the normal line at an arbitrary position passes through the tip of the nozzle 20 or the vicinity thereof. In this respect, it is particularly preferable that the concave curved surface R has the same shape as the inner surface of the true spherical shell.
- the bottom of the concave curved surface R is open, and the nozzle assembly 21 is attached to the opening.
- the nozzle assembly 21 includes the nozzle 20 described above and a support portion 22 that supports the nozzle 20.
- the nozzle 20 is made of a conductive material, and is generally made of metal.
- the support portion 22 is made of an electrically insulating material. Therefore, the electrode 19 and the nozzle 20 described above are electrically insulated by the support portion 22.
- the nozzle 20 is grounded.
- the tip 20 a of the nozzle 20 is exposed in the electrode 19 having a concave curved surface R.
- the nozzle 20 passes through the support portion 22, and the rear end 20 b of the nozzle 20 is exposed on the back side of the electrode 19 (that is, the side opposite to the concave curved surface R).
- the nozzle 20 does not necessarily have to pass through the support portion 22, and the rear end 20 b of the nozzle 20 may be positioned in the middle of the raw material liquid supply through hole provided in the support portion 22.
- the through hole for supplying the raw material liquid provided in the rear end 20b of the nozzle 20 or the support portion 22 is connected to a supply source (not shown) of the raw material liquid.
- the nozzle assembly 21 constitutes a raw material injection means together with a raw material supply source.
- an airflow injection means 23 including a through hole is provided in the vicinity of the base of the nozzle 20 in the nozzle assembly 21.
- the airflow ejection means 23 is formed along the direction in which the nozzle 20 extends. Further, the airflow ejecting means 23 is formed so as to be able to eject an airflow toward the tip 20a of the nozzle 20.
- two airflow ejection means 23 are provided so as to surround the nozzle 20.
- the airflow ejecting means 23 is formed at a symmetrical position with the nozzle 20 in between.
- the air flow injection means 23 comprising a through hole has an opening on the rear end side connected to an air flow supply source (not shown). By supplying air from this supply source, air is ejected from the periphery of the nozzle 20. The jetted air is discharged from the tip 20a of the nozzle 20 and the raw material liquid elongated by the action of an electric field is applied to a collecting electrode (not shown) disposed at a position facing the airflow ejecting means 23. Transport toward. 3 and 4 show a state in which two airflow ejecting means 23 are provided, the number of airflow ejecting means 23 is not limited to this, but one or three or more. It may be.
- the shape (cross-sectional shape) of the through-hole forming the air flow injection means is not limited to a circle, but may be a rectangle, an ellipse, a double ring, a triangle, a honeycomb, or the like. From the viewpoint of obtaining a uniform air flow, an annular through hole surrounding the nozzle is desirable.
- the entire surface of the surface of the electrode 19 that is a cathode and the surface that faces the nozzle 20 and the surface that does not face the nozzle 20 are covered with a dielectric exposed on the surface.
- a body 207 is arranged.
- the electrode 19 and the covering 207 are in direct contact.
- the covering body 207 has a hollow convex portion 207a having a shape complementary to the electrode 19 made of the concave curved surface R.
- the top of the convex portion 207a is open, and the nozzle assembly 21 is fitted into the opening.
- the convex portion 207 a covers the surface of the electrode 19 that faces the nozzle 20.
- the covering 207 has a flange portion 207b extending in the horizontal direction from the open end of the hollow convex portion 207a.
- the flange portion 207b covers a part of the surface of the electrode 19 that does not face the nozzle 20 (flange portion 19a). In a state where the covering body 207 is fitted to the concave curved surface R of the electrode 19, the electrode 19 and the covering body 207 are fixed by a predetermined joining member.
- the joining member is made of a dielectric. By doing so, electricity does not flow to the joining member itself, it is possible to suppress the electric lines of force generated from the joined portion of the electrode 19 and the cover 207, and the electric field between the electrode 19 and the nozzle 20 can be suppressed. Disturbance can be prevented.
- the covering 207 can be easily replaced when the type of the covering 207 covering the electrode 19 is changed. Easy to use.
- an adhesive can be used as the joining member.
- a screw can be used as described later.
- the adhesive for example, an epoxy resin adhesive or an external tape can be used.
- a removable adhesive such as a denture stabilizer
- the covering 207 can be easily detached from the electrode 19, and the maintainability of the manufacturing apparatus 18 is improved.
- the screw may be made of the same or different kind of dielectric material as the cover 207 or made of wood.
- the electrode 19 and the cover 207 are bonded to each other by a bonding member made of these materials, so that an air layer is hardly generated between them, and the electric field between the electrode 19 and the nozzle 20 can be stabilized.
- a bolt 207 d as a joining member is passed through a through hole 207 c formed in the flange portion 207 b, and the bolt 207 d is screw holes provided in the flange portion 19 a of the electrode 19.
- the electrode 19 and the covering 207 are fixed by screwing into 19b.
- a hole (counterbore hole) having a size larger than the head of the bolt 207d is formed in the through hole 207c.
- the head of the bolt 207 d does not protrude from the surface of the covering 207 and is positioned inside the covering 207.
- the electric field between the electrode 19 and the nozzle 20 can be stabilized. If the electrode 19 and the cover 207 are fixed by inserting bolts from the back side of the electrode 19, it is not necessary to form a counterbore on the surface side of the cover 207, so that the electric field is further stabilized. Can do.
- the bolt 207d is preferably made of a dielectric from the viewpoint of stabilizing the electric field between the electrode 19 and the nozzle 20, and specifically, polyetheretherketone, polyphenylene sulfide, glass fiber reinforced polyamide MXD6, Examples include polycarbonate, polypropylene, ceramic, Teflon (registered trademark), polyvinylidene fluoride, non-thermoplastic polyimide resin, and hard polyvinyl chloride.
- the same dielectric as that constituting the covering 17 covering the electrode 14 can be used. And it is easy to use a molded body obtained by melt-molding various thermoplastic resins.
- the dielectric can contain the same antistatic agent as used in the covering 17. Further, the thickness of the covering 207 covering the electrode 19 can be the same as the thickness of the covering 17 covering the electrode 14.
- the charge amount of the raw material liquid can be increased by the action of the covering 207, as in the manufacturing apparatus 10 of the embodiment described above.
- the electrode 19 has a concave spherical shape, the increase in the charge amount of the raw material liquid becomes more remarkable.
- the area of the nozzle 20 is preferably small, and in particular, the length of the nozzle 20 (the distance between the front end 20a and the rear end 20b of the nozzle 20) is preferably short. Specifically, the length of the nozzle 20 is preferably 50 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less. Further, by making the electrode 19 concave spherical as in this embodiment, the volume of the electrode can be reduced as compared with the case where a planar electrode is used, and thus the manufacturing apparatus 18 can be reduced in size.
- the nozzle 20 extends in the center of a circle defined by the opening end of the concave surface R of the electrode 19 or the vicinity of the center and the center of the opening provided at the bottom of the concave surface R. Or the vicinity of the center thereof.
- the plane including the circle defined by the open end of the concave curved surface R and the direction in which the nozzle 20 extends are orthogonal.
- the tip 20 a of the nozzle 20 is located in or near the plane including the circle defined by the open end of the concave surface R of the electrode 19.
- the nozzle 20 is preferably arranged so as to be located inside the concave curved surface R with respect to the plane. Specifically, it is preferable to dispose 1 to 10 mm inside the plane.
- the concave curved surface R of the electrode 19 has a substantially hemispherical shape of a true spherical shell.
- the tip 20a of the nozzle 20 is preferably located in a plane including a circle defined by the open end of the concave curved surface R.
- the tip 20a of the nozzle 20 is preferably disposed within a radius of 10 mm from the center of the circle defined by the open end, more preferably within a radius of 5 mm, and is disposed at the center of the circle. More preferably.
- the electrode 19 may cover all the surfaces that do not face the nozzle 20 with a covering with a dielectric exposed on the surface.
- the outer surface of the electrode 19 (the surface opposite to the concave curved surface R) and the end surface of the flange portion 19a may be covered with a covering.
- substantially the entire outer surface of the nozzle 20 is the surface. It is also possible to increase the charge amount of the raw material liquid by coating with a cover with a dielectric exposed.
- the configuration shown in FIG. 2 described above can be employed.
- substantially the entire surface of the collecting electrode which is a part of the collecting means, may be covered with a covering with a dielectric exposed on the surface.
- FIG. 5 shows still another embodiment of the production apparatus of the present invention.
- FIG. 5B shows a top view of the manufacturing apparatus 310 in the present embodiment.
- FIG. 5A is a side view of the A-A ′ section in FIG. 5B as viewed from below.
- the manufacturing apparatus 310 basically has the plate-like electrode 14 of the manufacturing apparatus 10 shown in FIGS. 1 and 2 replaced with a concave spherical electrode 314.
- the manufacturing apparatus 310 includes a raw material injection unit 11 for injecting a raw material liquid for producing nanofibers.
- the raw material injection unit 11 includes a liquid feeding unit 12 and a nozzle 13.
- a concave spherical electrode 314 is disposed at a position directly above the opening of the nozzle 13 with its inner surface facing downward.
- the nozzle 13 and the electrode 314 are made of metal or the like and have conductivity.
- a DC voltage is applied between the nozzle 13 and the electrode 314 by a DC high-voltage power supply 101 which is a voltage generating means via a ground 102 and a metal conductor 103.
- the nozzle 13 is grounded as shown in FIG. 5A and becomes an anode.
- the electrode 314 has a concave spherical shape as a whole, and particularly has a substantially bowl shape.
- the concave surface R is provided in the inner surface, and it has the flat flange part 314a in the position of the opening end.
- the electrode 314 has an opening 320 for disposing the airflow ejecting means 15 at the positions of two opposing side surfaces, an airflow ejected from the airflow ejecting means 15 and a fiber material ejected from the nozzle 13.
- An opening 321 for passing the liquid is provided.
- the inner surface of the electrode 314 is a concave curved surface R, the outer surface of the electrode 314 does not need to be substantially bowl-shaped, and may have another shape.
- the manufacturing apparatus 310 includes an air flow injection unit 15.
- the airflow ejecting means 15 is disposed at a position where an airflow can be ejected between the nozzle 13 and the electrode 314 through the opening 320 provided in the electrode 314.
- the generated fiber is positively charged and extends from the nozzle 13 serving as the anode toward the electrode 314 serving as the cathode, but the air flow ejected from the air flow ejecting means 15 changes the traveling direction of the fiber. Then, it is conveyed through the opening 321 in a direction in which the collecting means is present (downward direction in FIG. 5B).
- the entire surface of the concave curved surface R and the surface of a part of the flange portion 314a of the surface of the electrode 314 serving as the cathode are covered with the covering 307 with the exposed dielectric. ing. Since the tip of the nozzle 13 is located outside the concave curved surface R, the concave curved surface R and a part of the surface of the flange portion 314 a face the nozzle 13. The thickness of the covering 307 is substantially constant, and the electrode 314 and the covering 307 are in direct contact.
- the electrode 314 and the cover 307 are fixed by bolting bolts to through-holes formed in the flange portion 314a of the electrode 314 and the flange portion of the cover 307 in the same manner as the electrode 19 and the cover 207 shown in FIG. Is done.
- the same dielectric as that constituting the covering 17 of the manufacturing apparatus 10 shown in FIG. 1 can be used. And it is easy to use a molded body obtained by melt-molding various thermoplastic resins.
- the dielectric can contain the same antistatic agent as used in the covering 17.
- the thickness of the covering 307 covering the electrode 314 can be the same as the thickness of the covering 17 covering the electrode 14. Even when the manufacturing apparatus 310 of the present embodiment is used, the charge amount of the raw material liquid can be increased by the action of the covering 307 as in the manufacturing apparatus 10 and the manufacturing apparatus 18 of the above-described embodiment.
- the length of the nozzle 13 is preferably 50 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less.
- the distance (shortest distance) between the tip of the nozzle 13 and the concave curved surface R can be made the same as the distance (shortest distance) between the tip of the nozzle 13 and the electrode 14 in the manufacturing apparatus 10.
- the position of the tip of the nozzle 13 is preferably located at or near the center of the concave curved surface R of the electrode 314. Specifically, it is preferable to arrange at a position within 10 mm from the center of the concave curved surface R. As a result, the electric field at the tip of the nozzle 13 becomes stronger, and the amount of charge of the raw material liquid increases. From this viewpoint, it is particularly preferable that the concave curved surface R of the electrode 314 has a substantially hemispherical shape of a true spherical shell.
- the electrode 314 is arranged so that a plane including a circle defined by the open end of the concave curved surface R is substantially orthogonal to the direction in which the nozzle 13 extends.
- the electrode 314 may be disposed so that the plane and the direction in which the nozzle 13 extends intersect at an angle other than 90 degrees.
- the electrode 314 may cover a part or all of the surface that does not face the nozzle 13 with a cover with a dielectric exposed on the surface.
- the outer surface of the electrode 314 (the surface opposite to the concave curved surface R) and the end surface of the flange portion 314a may be covered with a covering.
- a coating having a dielectric exposed on the entire surface of the outer surface of the nozzle 13 is provided.
- the charge amount of the raw material liquid can also be increased by covering with the body.
- the configuration shown in FIG. 2 described above can be employed.
- substantially the entire surface of the collecting electrode which is a part of the collecting means, may be covered with a covering with a dielectric exposed on the surface.
- FIG. 7 shows still another embodiment of the manufacturing apparatus of the present invention.
- FIG. 7A shows a side view of the manufacturing apparatus 410 in the present embodiment.
- FIG.7 (b) is a front view in Fig.7 (a).
- the manufacturing apparatus 410 basically uses a covering 107 that covers the nozzle 13 instead of the covering 17 that covers the electrode 14 in the manufacturing apparatus 10 shown in FIGS. 1 and 2, and The polarity of the voltage generating means 101 is reversed.
- the production apparatus 410 includes raw material injection means 11 for injecting a raw material liquid for producing nanofibers.
- the raw material injection unit 11 includes a liquid feeding unit 12 and a nozzle 13.
- a plate-like electrode 14 is disposed at a position immediately above the opening of the nozzle 13 so as to face the opening of the nozzle 13.
- the nozzle 13 and the electrode 14 are made of metal or the like and have conductivity.
- a direct current voltage is applied between the nozzle 13 and the electrode 14 by a direct current high voltage power supply 401 serving as a voltage generating means via a ground 102 and a metal conductor 103.
- the nozzle 13 is grounded as shown in FIG. 7B and becomes a cathode.
- a positive voltage is applied to the electrode 14 to become an anode.
- the manufacturing apparatus 410 includes an air flow injection unit 15. As will be described later, the nanofiber formed from the raw material liquid is negatively charged, and tries to extend from the nozzle 13 serving as the cathode toward the electrode 14 serving as the anode.
- the airflow ejected from the airflow ejecting means 15 changes the traveling direction of the nanofibers and transports the nanofibers in a direction (the right direction in FIG. 7A) of the collecting means and stretches the nanofibers. It contributes to that.
- the manufacturing apparatus 410 includes the same second airflow ejecting means 16 as the manufacturing apparatus 10, a collecting means (collecting electrode and collecting body) for collecting nanofibers, and an air exhausting means.
- a higher (positive) potential is applied to the collecting electrode than the nozzle 13 serving as the cathode.
- the above is the basic structure of the manufacturing apparatus 410 of the present embodiment.
- substantially the entire outer surface of the nozzle 13 is covered with the covering 107 having a dielectric exposed on the surface.
- the covering 107 extends beyond the tip 13a of the nozzle 13 as shown in FIG.
- the charge amount of the raw material liquid sprayed from the nozzle 13 can be remarkably increased.
- the mechanism is considered as follows.
- the anion in the raw material liquid is attracted to the electrode 14 (anode) side by the electric field formed between the electrode 14 and the nozzle 13, and the cation in the raw material liquid is the nozzle. 13 (cathode) is attracted to the inner surface.
- the raw material liquid injected toward the electrode 14 contains a large amount of anions, and the raw material liquid is negatively charged.
- the charging ability at the nozzle 13 can be prevented from being lowered, and the charge amount of the raw material liquid is increased. Furthermore, since the number of electrons flying from the nozzle 13 to the electrode 14 is reduced, the discharge between the electrode 14 and the nozzle 13 is suppressed, and the applied voltage between the electrode 14 and the nozzle 13 is increased or the distance is reduced. Is possible. Thereby, the electric field between the electrode 14 and the nozzle 13 is strengthened, and the charge amount of the raw material liquid can be increased.
- the current (leakage current) flowing between the electrode 14 and the nozzle 13 is reduced, and the effect of reducing the power consumption at the time of manufacturing the nanofiber can be expected.
- the preferred range of the length of the extending portion of the covering 107 that extends beyond the tip of the nozzle 13 is as described in the embodiment using the manufacturing apparatus 10.
- the surface of the electrode 14 faces the nozzle 13.
- the amount of charge of the raw material liquid can also be increased by covering substantially the entire surface to be covered with a covering having a dielectric exposed on the surface.
- the number of electrons flying from the nozzle 13 and flowing into the electrode 14 can be suppressed by covering the electrode 14 with a coating with a dielectric exposed on the surface. As a result, the discharge between the electrode 14 and the nozzle 13 is less likely to occur, and the applied voltage between the electrode 14 and the nozzle 13 can be increased and the distance can be reduced.
- the electric field between the electrode 14 and the nozzle 13 is strengthened, and the charge amount of the raw material liquid can be increased.
- the current (leakage current) flowing between the electrode 14 and the nozzle 13 is reduced, and an effect of reducing power consumption at the time of manufacturing the nanofiber can be expected.
- the entire surface (90% or more area) facing the nozzle 13 with a covering, and in particular, the entire surface facing the nozzle 13 (100%).
- the area is preferably covered with a covering. If the area of the uncoated surface is large, electrons flow into the electrode 14 from there, and the discharge and leakage current cannot be effectively suppressed. Further, not only the surface of the electrode 14 that faces the nozzle 13 but also the surface that does not face the nozzle 13 is covered with a covering to further enhance the effect. This is because not a few electrons flow into the surface that does not face the nozzle 13. From the viewpoint of increasing the charge amount of the raw material liquid and reducing the power consumption during the production of nanofibers, it is preferable to cover all surfaces of the electrode 14 with a covering.
- substantially the entire surface of the collecting electrode which is a part of the collecting means, may be covered with a covering with a dielectric exposed on the surface.
- the collecting electrode is given a higher (positive) potential than the nozzle 13 which is a cathode in order to attract negatively charged nanofibers. For this reason, the electrons emitted from the nozzle 13 also fly to the collecting electrode.
- By covering substantially the entire surface of the collection electrode with a coating with a dielectric exposed it is possible to prevent electrons flying from the nozzle 13 from flowing into the collection electrode. As a result, the current (leakage current) flowing between the collection electrode and the nozzle 13 is reduced, and the effect of reducing the power consumption during nanofiber production can be expected.
- FIG. 8 shows still another embodiment of the present invention.
- FIG. 8A shows a side view of the manufacturing apparatus 510 in the present embodiment.
- FIG. 8B is a front view in FIG.
- the manufacturing apparatus 510 of this embodiment basically has the same structure as the manufacturing apparatuses 10 and 410 shown in FIGS. 1 and 7.
- the manufacturing apparatus 510 of the present embodiment is different from the manufacturing apparatuses 10 and 410 shown in FIGS. 1 and 7 in the structure of the air flow injection means. 1 and FIG. 7 employs two airflow ejection means, whereas the production apparatus 510 of the present embodiment employs a single airflow ejection means 15A. Yes.
- FIG. 9 shows a partially broken perspective view of the air flow injection means 15A in the manufacturing apparatus 510 shown in FIG.
- the airflow ejecting means 15A has a plurality of openings 151A through which airflow is ejected on the front surface thereof.
- the air flow ejecting means 15A has an air supply pipe 152A connected to the back surface thereof.
- the air flow injection means 15A has a manifold structure, and an air pool space, that is, a manifold 153A is formed therein. By forming the manifold 153A, it is possible to uniformly inject an air flow from the opening 151A.
- an air flow can flow through the space between the electrode 14 and the nozzle 13 without a gap, and the raw material liquid discharged from the nozzle 13 can be effectively prevented from being attracted to and attached to the electrode 14. Further, the charge amount of the raw material liquid can be increased by applying a higher voltage.
- the air flow ejecting means 15A is made of a dielectric. By doing so, the disturbance of the electric field between the electrode 14 and the nozzle 13 can be prevented.
- the dielectric material various materials similar to the dielectric covering the electrode 14 can be used. In particular, it is preferable to use the same material as that used for covering the electrode 14 in terms of preventing disturbance of the electric field between the electrode 14 and the nozzle 13.
- the air flow injection means 15 ⁇ / b> A is arranged so that the opening 151 ⁇ / b> A faces the space between the electrode 14 and the nozzle 13.
- an air flow can flow through the space between the electrode 14 and the nozzle 13 without any gap, and the raw material liquid discharged from the nozzle 13 is effectively prevented from being attracted to and attached to the electrode 14.
- the charge amount of the raw material liquid can be increased by applying a higher voltage.
- the opening 151A formed on the front surface of the airflow ejecting means 15A communicates the manifold 153A and the external space.
- the arrangement of the opening 151A can be freely set and is not limited.
- the openings 151 ⁇ / b> A are arranged in a staggered pattern so that the rows of openings extending in the horizontal direction H are arranged in multiple rows (three rows in FIG. 9) along the vertical direction V. Can do.
- the opening 151A By arranging the opening 151A in this way, an air flow can flow through the space between the electrode 14 and the nozzle 13 without any gap, and the raw material liquid discharged from the nozzle 13 is attracted to and attached to the electrode 14. This can be effectively prevented. Further, the charge amount of the raw material liquid can be increased by applying a higher voltage.
- the opening 151A may be a space formed by a narrow gap, for example, or may be a substantially columnar space. Therefore, the shape of the opening 151A that is open on the front surface of the airflow ejecting means 15A may be a narrow line, or a circle or ellipse, and a polygon such as a triangle or a rectangle. A circular shape is preferable from the viewpoint of workability. Since the opening 151A has these shapes, an air flow can flow through the space between the electrode 14 and the nozzle 13 without a gap, and the raw material liquid discharged from the nozzle 13 is attracted to the electrode and adheres to it. Can be prevented. Further, the charge amount of the solution can be increased by applying a higher voltage. Furthermore, the consumption of air can be suppressed.
- the minimum value of the width is preferably 0.1 mm or more, and more preferably 0.3 mm or more. By doing so, the air flow can be injected while suppressing the pressure loss.
- the maximum width is preferably 1.5 mm or less, and more preferably 1.2 mm or less. By doing so, it is possible to secure a sufficient flow rate of the air flow for blowing the raw material liquid discharged from the nozzle 13 to the collecting means, and spinning becomes possible. Moreover, the consumption of air can be suppressed. From the same point, 0.1 mm to 1.5 mm is preferable, and 0.3 mm to 1.2 mm is more preferable.
- the minimum value of the diameter is preferably 0.1 mm or more, and 0.3 mm or more for the same reason as described above.
- the maximum value of the diameter is preferably 1.5 mm or less, and more preferably 1.2 mm or less.
- the diameter is preferably from 0.1 mm to 1.5 mm, and more preferably from 0.3 mm to 1.2 mm.
- the minimum value of the pitch may be 3 mm or more. Preferably, it is 5 mm or more. By doing in this way, it can prevent that the number of opening part 151A increases too much, and can suppress the processing cost of 15 A of airflow injection means.
- the maximum value of the pitch is preferably 15 mm or less, and more preferably 12 mm or less. By doing in this way, it becomes hard to produce a clearance gap between the airflows injected from each opening part 151A, and it can prevent that the raw material liquid discharged from the nozzle 13 adheres to the electrode 14 in a wide angle.
- FIG. 10 shows still another embodiment of the present invention.
- the manufacturing apparatus 610 of the present embodiment basically has the same structure as the manufacturing apparatus 18 shown in FIGS.
- the manufacturing apparatus 610 of the present embodiment is different from the manufacturing apparatus 18 shown in FIGS. 3 and 4 in the structure of the air flow ejecting means.
- an air flow ejection means 23 including a through hole is provided in the vicinity of the base portion of the nozzle 20 in the nozzle assembly 21.
- a manifold member 24 as an air flow injection unit is attached to the tip of the nozzle assembly 21.
- the manifold member 24 has a substantially cylindrical shape.
- a nozzle tip region 210 including the nozzle 20 is inserted into the substantially cylindrical inner space.
- the substantially cylindrical manifold member 24 has a large number of airflow injection ports 241 on the front surface 242a of the two annular surfaces 242a and 242b. It is open.
- the airflow injection port 241 extends in the same direction as the height direction of the substantially cylinder.
- the manifold member 24 is formed with an air reservoir space, that is, a manifold 243, which is open on an annular back surface 242b located on the opposite side to the front surface 242a.
- the manifold 243 is a space made of a torus. As shown in FIG. 12B, the manifold 243 communicates with the air flow injection port 241 described above. As shown in FIG. 10, when the manifold member 24 is attached to the tip of the nozzle assembly 21, the through hole formed in the nozzle assembly 21 and the manifold 243 communicate with each other.
- the air flow injection port 241 provided on the front surface 242a of the manifold member 24 is centered on the nozzle 20 so as to surround the nozzle 20 when the opening of the electrode 19 is viewed from the front.
- the minimum radius of the pitch circle is preferably 6 mm or more, and more preferably 7.5 mm or more. By doing so, an air flow without a gap can be generated around the nozzle 20 without interfering with the nozzle 20.
- the maximum radius of the pitch circle is preferably 15 mm or less, and more preferably 12.5 mm or less. By doing so, it is possible to effectively suppress the backflow of the air flow at the tip of the nozzle 20 and to enable spinning. From the same point, the radius of the pitch circle is preferably 6 mm or more and 15 mm or less, and more preferably 7.5 mm or more and 12.5 mm or less.
- the minimum value of the angle which the adjacent airflow injection port 241 and the center of the nozzle 20 make is 5 degrees or more, and is 8 degrees or more. It is more preferable. By doing so, an air flow without a gap can be created around the nozzle 20, and the processing cost can be reduced.
- the maximum value of the angle is preferably 60 ° or less, and more preferably 30 ° or less. By doing so, an air flow can flow through the space between the electrode 19 and the nozzle 20 without any gap, and the raw material liquid discharged from the nozzle 20 is effectively prevented from being attracted and attached to the electrode. Can do. Further, the charge amount of the raw material liquid can be increased by applying a higher voltage. From the same viewpoint, the angle is preferably 5 ° to 60 °, and more preferably 8 ° to 30 °.
- the airflow injection port 241 includes a substantially columnar space, for example, a substantially cylindrical space.
- the minimum value of the diameter is preferably 0.1 mm or more, more preferably 0.3 mm or more, and the maximum value of the diameter is preferably 1.5 mm or less, 1.2 mm or less. It is more preferable that Specifically, the diameter is preferably from 0.1 mm to 1.5 mm, and more preferably from 0.3 mm to 1.2 mm. By doing so, the air flow can be injected while suppressing the pressure loss. Further, it is possible to secure a sufficient flow rate of air flow for blowing the raw material liquid discharged from the nozzle 20 to the collecting means, and spinning becomes possible. Furthermore, the consumption of air can be suppressed.
- an air flow can be injected in the same direction as the direction in which the nozzle 20 extends.
- FIG. 13 shows a front view of still another embodiment of the electrospinning apparatus of the present invention.
- FIG. 14 is a schematic diagram showing a cross-sectional structure of the electrospinning apparatus shown in FIG.
- An electrospinning apparatus 701 shown in FIG. 13 includes an electrode 710 and a raw material liquid discharge nozzle 720.
- the electrode 710 has a cylindrical shape as a whole, and is provided with a cylindrical concave curved surface 711 on its inner surface. As long as the inner surface of the electrode 710 is a cylindrical concave curved surface 711, the overall shape does not need to be a cylindrical shape, and may be another shape.
- the cylindrical concave curved surface 711 is made of a conductive material and is generally made of metal.
- the electrode 710 is connected to a DC high voltage power source 740 as shown in FIGS.
- the opening end is circular.
- This circle may be a perfect circle or an ellipse.
- the open end of the cylindrical concave curved surface 711 is preferably a perfect circle.
- the cylindrical concave curved surface 711 is a curved surface at any position.
- the curved surface referred to here is (a) a curved surface that does not have a flat surface portion at all, or (b) as shown in FIG. Whether the shape can be regarded as a curved surface 711 or not.
- the vertical and horizontal lengths are each independently a rectangle of about 0.5 to 150 mm, and the segments G having the same or different plane portions P are joined together to form a concave It is preferable to form a curved surface 711.
- the normal line at an arbitrary position of the concave curved surface 711 is the tip of the nozzle 720 or its tip.
- the cylindrical concave curved surface 711 preferably has a curved surface shape passing through the vicinity. From this viewpoint, it is particularly preferable that the cylindrical concave curved surface 711 has the same shape as a perfect circle when viewed in a cross section perpendicular to the axial direction.
- the electrode 710 has a cylindrical shape as a whole, for example, a metal pipe cut, a cylindrical metal block with a through hole, and a semi-cylindrical electrode stacked into a cylinder A flat plate may be bent into a cylindrical shape. This is preferable because it can be easily processed and manufactured at low cost.
- the shape of the inner surface of the cross section perpendicular to the axial direction of the electrode 710 may be elliptical, and there may be fine irregularities formed when the flat plate is bent on the inner surface, but a perfect circle is preferable. This is preferable in that the amount of charge can be increased by concentrating the electric field on the nozzle tip 720a.
- the end of the joint is formed. Although it is not necessary to join all, it is preferable that there is no gap in the joint. This is preferable in that the amount of charge can be increased by concentrating the electric field on the nozzle tip 720a.
- the eccentricity of the circle or ellipse is preferably 0 or more and less than 0.6, and preferably 0 or more and less than 0.3. More preferably, it is more preferably a perfect circle with an eccentricity of 0. This is preferable in that the amount of charge can be increased by concentrating the electric field on the nozzle tip 720a.
- the length of the electrode 710 in the longitudinal direction is preferably 10 mm or more, more preferably 20 mm or more, and further preferably 30 mm or more.
- the electric field formed between the nozzle tip 720a and the electrode 710 becomes strong, and a high charge amount can be obtained.
- the upper limit it is preferably 150 mm or less, more preferably 80 mm or less, and even more preferably 60 mm or less.
- the length of the electrode 710 in the longitudinal direction is preferably 10 mm or more and 150 mm or less, more preferably 20 mm or more and 150 mm or less, further preferably 20 mm or more and 80 mm or less, and 30 mm or more and 80 mm or less. Is still more preferable, and it is still more preferable that it is 30 mm or more and 60 mm or less.
- the value of the radius is preferably 10 mm or more, more preferably 20 mm or more, and 30 mm or more. Is more preferable.
- the raw material liquid that is ejected from the nozzle tip 720 a and is in the form of a fiber becomes difficult to adhere to the electrode 710.
- the upper limit it is preferably 200 mm or less, more preferably 100 mm or less, and even more preferably 50 mm or less.
- the value of the radius of the cylindrical concave curved surface 711 in the electrode 710 is preferably 10 mm or more and 200 mm or less, more preferably 20 mm or more and 100 mm or less, and further preferably 30 mm or more and 50 mm or less.
- the electric field can be efficiently concentrated on the tip 720a of the nozzle 720, and the charge amount can be increased.
- the radius here refers to a distance between the nozzle 720 and the electrode 710 in a cross section perpendicular to the axial direction of the electrode 710.
- one end of the cylindrical concave curved surface 711 is open, and a nozzle assembly 721 is attached to the opening.
- the nozzle assembly 721 includes the nozzle 720 described above and a support portion 722 that supports the nozzle 720.
- the electrode 710 and the nozzle 720 are electrically insulated by the support portion 722.
- the tip 720a of the nozzle 720 is exposed in a cylindrical electrode 710.
- the rear end 720b of the nozzle 720 is exposed opposite to the opening side of the electrode 710.
- the rear end 720b of the nozzle 720 is connected to a raw material liquid supply source (not shown).
- the nozzle 720 is grounded as shown in FIG. On the other hand, since a negative voltage is applied to the electrode 710, an electric field is generated between the electrode 710 and the nozzle 720. Instead of applying the voltage shown in FIG. 14, a positive voltage may be applied to the nozzle 720 and the electrode 710 may be grounded.
- charging is performed using the principle of electrostatic induction as in the previous embodiments.
- electrostatic induction when a positively charged object (charged body) is brought close to a stable conductor, for example, a negative charge moves to a part of the conductor close to the charged body, and conversely, a positive charge is charged. The phenomenon of becoming an electrostatic conductor away from the body. If a positively charged portion of the conductor is grounded while the charged body is kept close to the conductor, the positive charge is electrically neutralized and the conductor becomes a charged body having a negative charge. In the embodiment shown in FIGS.
- the nozzle 720 is a charged body having a positive charge. Therefore, when the raw material liquid flows through the positively charged nozzle 720, a positive charge is supplied from the nozzle 720, and the raw material liquid is positively charged.
- the charge amount of the raw material liquid can be increased by the action of the dielectric 730 as will be described later.
- the increase in the charge amount of the raw material liquid becomes more remarkable.
- the exposed area of the nozzle 720 is preferably small, and in particular, the exposed length of the nozzle 720 (the distance between the support portion 722 and the tip 720a of the nozzle 720) is preferably short. Specifically, the exposed length of the nozzle 720 is preferably 50 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less.
- the electrode 710 a cylindrical concave curved surface 711 as in this embodiment, the volume of the electrode can be reduced as compared with the case of using a planar electrode, and thus the electrospinning apparatus 701 can be downsized. Can do.
- the electrospinning device described in Patent Document 3 described above there is no moving part, so there is an advantage that the device is not complicated.
- the nozzle 720 extends in a circle defined by the opening end of the cylindrical concave curved surface 711 of the electrode 710. It is preferable that the tip 720a of the nozzle 720 is located in a plane including a circle defined by the open end. In this case, the tip 720a of the nozzle 720 is preferably disposed within a radius of 10 mm from the center of the circle defined by the open end, more preferably within a radius of 5 mm, and is disposed at the center of the circle. More preferably.
- the tip 720a of the nozzle 720 is disposed in the vicinity of the center of a circle in a cross section perpendicular to the axial direction of the cylindrical electrode 710, and the tip 720a is formed in the cylinder in the axial direction. It is preferable to arrange in the space. In particular, when viewed along the axial direction of the cylindrical electrode 710, the tip 720 a of the nozzle 720 is disposed in a column space formed inside the cylinder, and the raw material liquid out of the two ends of the electrode 710 It is preferable to arrange between the end of the discharge side and the center of the shaft.
- the tip 720a of the nozzle 720 is disposed so as to be inside the plane defined by the opening end of the cylindrical concave curved surface 711 of the electrode 710 and in the vicinity of the plane.
- the vicinity means the inside of a distance of r / 5 from the center of the circle, where r is the radius of the circle defined by the open end of the cylindrical concave curved surface 711 of the electrode 710.
- r is the radius of the circle defined by the open end of the cylindrical concave curved surface 711 of the electrode 710.
- it is preferably located 1 mm or more and 20 mm or less inside the plane, more preferably 1 mm or more and 15 mm or less, and even more preferably 1 mm or more and 10 mm or less.
- the spinning solution can be easily discharged forward from the opening end of the cylindrical electrode.
- the raw material liquid discharged from the tip 720a of the nozzle 720 is hardly attracted to the cylindrical concave curved surface 711 of the electrode 710, and the concave curved surface 711 is not easily contaminated by the raw material liquid.
- the amount of charge can be increased by concentrating the electric field on the tip 720a of the nozzle 720.
- the nozzle 720 extends in the center of the circle defined by the opening end of the cylindrical concave curved surface 711 of the electrode 710, or in the vicinity of the center, and the other opening of the cylindrical concave curved surface 711. It is preferably arranged so as to pass through the center of the circle defined by the end or near the center. In particular, it is preferable that the plane including the circle defined by the open end of the cylindrical concave curved surface 711 and the direction in which the nozzle 720 extends are orthogonal. By disposing the nozzle 720 in this way, electric charges are further concentrated on the tip 720a of the nozzle 720. From this viewpoint, it is particularly preferable that the cylindrical concave curved surface 711 of the electrode 710 has a perfect circle shape.
- the nozzle 720 is preferably arranged so that the extending direction thereof passes through the inside of the virtual circle and the bottommost portion 711a of the cylindrical concave curved surface 711.
- the nozzle 720 extends in the inside of the virtual circle having a radius of r / 10 and in the cylindrical concave curved surface 711. It is preferable to be disposed so as to pass through the bottom 711a.
- the nozzle 720 is arranged so that the extending direction thereof passes through the center of a circle defined by the open end of the cylindrical concave curved surface 711 of the electrode 710 and the bottommost portion 711a of the concave curved surface 711.
- the form which is made is mentioned. This is preferable in that the amount of charge can be increased by concentrating the electric field on the tip 720a of the nozzle 720.
- the area of the metal portion (conductor portion) exposed in the electrode 710 of the nozzle 720 is reduced, and the area of the inner surface of the electrode 710 is increased.
- the charge density at the tip 720a of the nozzle 720 is increased.
- the lower limit of the ratio of the area of the inner surface of the electrode 710 to the area of the metal portion (conductor portion) exposed in the electrode 710 of the nozzle 720 is preferably 30 or more, and 100 or more. Is more preferable.
- the upper limit it is preferably 90000 or less, and more preferably 5000 or less.
- the area of the metal portion (conductor portion) exposed in the electrode 710 of the nozzle 720 refers to the area of the side surface of the nozzle 720 and does not include the area of the inner wall of the nozzle 720.
- the area of the inner surface of the electrode 710 does not include the area of the opening to which the nozzle assembly 721 is attached.
- the lower limit of the value of the area of the inner surface of the electrode 710 is preferably 500 mm 2 or more, and more preferably 1000 mm 2 or more.
- the upper limit is preferably 2000 ⁇ 10 2 mm 2 or less, and more preferably 4000 ⁇ 10 1 mm 2 or less.
- it is preferably 500 mm 2 or more and 2000 ⁇ 10 2 mm 2 or less, more preferably 1000 mm 2 or more and 4000 ⁇ 10 1 mm 2 or less.
- Area of exposed metal in the electrode 710 (conductor portion) of the nozzle 720 preferably has a lower limit value is 2 mm 2 or more, more preferably 5 mm 2 or more.
- it is preferably 1000 mm 2 or less, and more preferably 100 mm 2 or less.
- it is preferably 2 mm 2 or more and 1000 mm 2 or less, more preferably 5 mm 2 or more and 100 mm 2 or less.
- an air flow ejection portion 723 including a through hole is provided in the vicinity of the support portion 722 of the nozzle 720 in the nozzle assembly 721.
- the airflow ejection part 723 is formed along the direction in which the nozzle 720 extends.
- a plurality of air flow ejection portions 723 are provided so as to surround the nozzle 720.
- Each airflow ejection part 723 is formed at a symmetrical position with the nozzle 720 interposed therebetween.
- the above is the basic structure of the electrospinning apparatus 701 of the present embodiment.
- the inner surface of the electrode 710 is covered with a dielectric 730.
- the dielectric 730 is composed of a single type or a plurality of types of dielectrics.
- substantially the entire surface of the electrode facing the nozzle is covered with a dielectric. More preferably, the entire surface facing the nozzle is covered with a dielectric.
- the surface facing the nozzle is the surface of the electrode that can face from the tip of the nozzle (opening through which the raw material liquid is jetted).
- the substantially entire surface means a surface occupying an area of 90% or more of the total surface area of the surface, and the entire surface means a surface occupying an area of 100% of the total surface area of the surface.
- the dielectric almost the entire surface (area of 90% or more) is composed only of the dielectric. It is preferable that the entire surface of the dielectric (100% area) is composed only of the dielectric. That is, the dielectric of the present invention preferably has no surface of a conductor such as a metal.
- a typical example is a dielectric composed of a single type of dielectric, but the dielectric may be a composite of a plurality of types of dielectrics or the surface may be composed of only a dielectric.
- the dielectric may be a composite containing metal particles or layers, air layers, or the like inside (portions not exposed on the surface).
- an air layer may exist at a part of the junction between the electrode and the dielectric, but it is preferable that the electrode and the dielectric are in close contact from the viewpoint of strengthening the junction between the electrode and the dielectric.
- the surface facing the nozzle 720 is covered with the dielectric 730.
- a part of the surface not facing the nozzle 720 is also covered with the dielectric 730.
- the entire surface not facing the nozzle 720 is covered with the dielectric 730.
- the surface that does not face the nozzle is the surface of the electrode that cannot be faced from the tip 720a of the nozzle (opening through which the raw material liquid is injected). More specifically, it is the surface of the electrode surface excluding the surface facing the nozzle.
- the dielectric 730 and the electrode 710 can have a fitting structure.
- the dielectric 730 shown in the figure includes a cylindrical portion 731 that fits into the concave curved surface 711 of the cylindrical electrode 710, and a flange portion 732 that protrudes horizontally from the upper end of the cylindrical portion 731.
- the flange portion 732 covers one open end surface 712 of the electrode 710.
- the electrode 710 and the dielectric 730 are fixed by a predetermined bonding member.
- the joining member is preferably made of a dielectric.
- an adhesive can be used as in the joining member used in the above-described embodiment.
- the screw 733 can also be used.
- the screw 733 may be made of the same kind or different kind of dielectric material as the dielectric material 730 or wood.
- a screw 733 as a joining member is passed through a through hole 734 formed in the flange portion 732, and the screw 733 is a screw provided on one open end surface 712 of the cylindrical electrode 710. The electrode 710 and the dielectric 730 are fixed by screwing into the hole 713.
- a hole (counterbore hole) having a size larger than the head of the screw 733 is formed in the through-hole 734. Accordingly, in a state where the electrode 710 and the dielectric 730 are fixed, the head of the bolt 733 does not protrude from the surface of the flange portion 732 of the dielectric 730 and is positioned inside the flange portion 732.
- the raw material liquid is discharged from the tip 720a of the nozzle 720 in a state where an electric field is generated between the electrode 710 and the nozzle 720.
- the raw material liquid is charged by electrostatic induction until it is discharged from the nozzle 720, and is discharged in a charged state. Since charges are concentrated on the tip 720a of the nozzle 720, the charge amount per unit mass of the raw material liquid becomes extremely high.
- the surface of the raw material liquid discharged in a charged state is deformed into a conical shape by the action of an electric field.
- the raw material liquid is drawn toward the electrode 710 all at once.
- the air flow is ejected from the air flow ejecting portion 723 toward the discharged raw material liquid, so that the fiber is thinned to the nano size by the self-repulsive chain of the raw material liquid.
- the specific surface area increases and the solvent evaporates.
- nanofibers generated by drying are randomly deposited on the surface of a collector (not shown) disposed at a position facing the nozzle 720.
- a nanofiber collecting electrode (not shown) is disposed so as to face the tip 720a of the nozzle 720, and adjacent to the collecting electrode.
- a collecting body may be disposed between the collecting electrode and the nozzle 720.
- the collecting electrode can be grounded or a negative voltage can be applied to the collecting electrode.
- FIG. 17 shows an example of a nanofiber manufacturing apparatus 750 using the electrospinning apparatus 701 of the present embodiment.
- a plurality of electrospinning apparatuses 701 shown in FIGS. 13 and 14 are arranged.
- Each electrospinning device 701 is fixed to a plate-like base 745.
- Each electrospinning device 701 is two-dimensionally arranged over the plane direction of the plate surface of the base 745.
- each electrospinning apparatus 701 is arranged so that the nozzles 720 face in the same direction (upward in FIG. 17).
- a negative DC voltage is applied to the electrode 710, and the nozzle 720 is grounded.
- a nanofiber collecting electrode 751 is disposed so as to face the tip 720a of the nozzle 720.
- the collection electrode 751 is a flat plate made of a conductor such as metal.
- the plate surface of the collecting electrode 751 and the direction in which the nozzle 720 extends are substantially orthogonal.
- the collecting electrode can be coated on the substantially entire surface with a dielectric, and more preferably on the entire surface.
- the substantially entire surface means a surface occupying an area of 90% or more of the total surface area of the surface.
- the entire surface means a surface that occupies 100% of the total surface area of the surface.
- a lower (negative) potential is applied to the collecting electrode than the nozzle 720 that is an anode. In order to make the attraction more efficient, it is preferable to apply a lower (negative) potential than the electrode 711 which is a cathode.
- the lower limit of the distance between the collecting electrode 751 and the tip 720a of the nozzle 720 is preferably 100 mm or more, and more preferably 500 mm or more.
- the upper limit is preferably 3000 mm or less, more preferably 1000 mm or less. For example, it is preferably 100 mm or more and 3000 mm or less, and more preferably 500 mm or more and 1000 mm or less.
- a collector 752 for collecting nanofibers is disposed between the collection electrode 751 and the nozzle 720 so as to be adjacent to the collection electrode 751.
- the collection body 752 has a long band shape, and is drawn out from a roll-shaped raw fabric 752a.
- the drawn collection body 752 is conveyed in the direction indicated by the arrow A in FIG. 17, passes over the nozzle 720 so as to face the nozzle 720, and is wound around the winder 752b.
- the collector 752 for example, a film, a mesh, a nonwoven fabric, paper, or the like can be used.
- the collector 752 is first fed out and conveyed in the direction indicated by the arrow A. Further, a negative DC voltage is applied to the electrode 710 and the nozzle 720 and the collecting electrode 751 are grounded. Under these conditions, the raw material liquid is discharged from the tip 720a of the nozzle 720 while the air flow is ejected from the air flow ejection portion 723 provided in the electrospinning apparatus 701. Nanofibers are generated from the discharged raw material liquid, and the nanofibers are continuously deposited on the surface of the traveling collector 752. Since a plurality of electrospinning apparatuses 701 are arranged in the manufacturing apparatus 750, a large amount of nanofibers can be manufactured.
- the discharged raw material liquid has an extremely high charge amount, even if the discharge amount of the raw material liquid is increased as compared with the prior art, nanofibers having the same thickness as the conventional one can be manufactured. This also makes it possible to produce a large amount of nanofibers.
- a solution in which a polymer compound capable of forming a fiber is dissolved or dispersed in a solvent or a melt obtained by heating and melting a polymer compound can be used.
- the electrospinning method using a polymer solution as a raw material liquid is sometimes called a solution method, and the method using a polymer melt is sometimes called a melting method.
- the solution or melt can be appropriately mixed with inorganic particles, organic particles, plant extracts, surfactants, oil agents, electrolytes for adjusting ion concentration, and the like.
- Polymer compounds for producing nanofibers are generally polypropylene, polyethylene, polystyrene, polyvinyl alcohol, polyurethane, polyethylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly-m-phenylene terephthalate, poly-p-phenylene isofura.
- Tate polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl chloride, polyvinylidene chloride-acrylate copolymer, polyacrylonitrile, polyacrylonitrile-methacrylate copolymer, polycarbonate, polyarylate, polyester carbonate, nylon , Aramid, polycaprolactone, polylactic acid, polyglycolic acid, collagen, polyhydroxy Acid, polyvinyl acetate, polypeptides and the like.
- the polymer compound to be used is not limited to one type, and any plurality of types can be used in combination from the exemplified polymer compounds.
- the solvent includes water, methanol, ethanol, 1-propanol, 2-propanol, hexafluoroisopropanol, tetraethylene glycol, triethylene glycol, Dibenzyl alcohol, 1,3-dioxolane, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-hexyl ketone, methyl-n-propyl ketone, diisopropyl ketone, diisobutyl ketone, acetone, hexafluoroacetone, phenol, Formic acid, methyl formate, ethyl formate, propyl formate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl acetate, ethyl acetate, propyl acetate
- the following natural and synthetic polymers having high solubility in water include pullulan, hyaluronic acid, chondroitin sulfate, poly- ⁇ -glutamic acid, modified corn starch, ⁇ -glucan, glucooligosaccharide, heparin, keratosulfuric acid and other mucopolysaccharides, cellulose, pectin, xylan, lignin, glucomannan.
- Galacturonic acid psyllium seed gum, tamarind seed gum, gum arabic, tragacanth gum, soy water-soluble polysaccharide, alginic acid, carrageenan, laminaran, agar (agarose), fucoidan, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and the like.
- the synthetic polymer include partially saponified polyvinyl alcohol, low saponified polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, and sodium polyacrylate. These polymer compounds can be used alone or in combination of two or more.
- natural polymers such as pullulan and synthetic polymers such as partially saponified polyvinyl alcohol, low saponified polyvinyl alcohol, polyvinyl pyrrolidone and polyethylene oxide should be used. Is preferred.
- polyvinyl alcohol that can be insolubilized after formation of nanofibers
- partially saponified polyvinyl alcohol that can be crosslinked after formation of nanofibers in combination with a crosslinking agent
- poly (N-propanoylethyleneimine ) Oxazoline-modified silicones such as graft-dimethylsiloxane / ⁇ -aminopropylmethylsiloxane copolymer
- acrylic resin such as twein (main component of corn protein), polyester, polylactic acid (PLA), polyacrylonitrile resin, polymethacrylic acid resin, etc.
- High molecular compounds such as polystyrene resin, polyvinyl butyral resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyurethane resin, polyamide resin, polyimide resin, and polyamideimide resin are also used. It is possible. These polymer compounds can be used alone or in combination of two or more.
- the nanofibers manufactured by the manufacturing apparatus of each of the above embodiments are generally 10 nm or more and 3000 nm or less, particularly 10 nm or more and 1000 nm or less, when the thickness is expressed by a circle equivalent diameter.
- the thickness of the nanofiber can be measured, for example, by observation with a scanning electron microscope (SEM).
- the nanofiber manufactured using the nanofiber manufacturing apparatus of the present invention can be used for various purposes as a nanofiber molded body in which it is integrated.
- Examples of the shape of the molded body include a sheet, a cotton-like body, and a thread-like body.
- the nanofiber molded body may be used by laminating with other sheets or containing various liquids, fine particles, fibers and the like.
- the nanofiber sheet is suitably used as a sheet attached to human skin, teeth, gums and the like for non-medical purposes such as medical purposes and cosmetic purposes. Further, it is also suitably used as a high-performance filter with high dust collection and low-pressure loss, a battery separator that can be used at a high current density, a cell culture substrate having a high pore structure, and the like.
- the nanofiber cotton-like body is suitably used as a soundproofing material or a heat insulating material.
- the nozzle 13 may be a curved pipe having a curvature.
- the concave curved surface R of the electrode 19 is preferably the shape of the inner surface of the hemispherical spherical shell, but instead, for example, the shape of the inner surface of the spherical shell of the spherical crown It is good.
- the nozzle 20 is arranged at the bottom of the concave curved surface R, but the nozzle 20 may be arranged at other positions.
- the nozzle 720 is arranged at one opening end of the cylindrical shape, but the nozzle 720 may be arranged at other positions.
- the nozzle 13 (20, 720) is divided into a plurality of sections S in the cross-sectional view as shown in FIG. 18, and the raw material liquid is circulated in each section. Good. By doing so, the contact area between the raw material liquid and the inner wall of the nozzle is increased, and the raw material liquid can be more easily charged.
- the above-described inner diameter of the nozzle refers to the inner diameter in each section. The shape and inner diameter of each section may be the same or different.
- the technical elements of one embodiment may be replaced with the technical elements of another embodiment within a range that does not impair the advantageous effects achieved by the present invention.
- the airflow injection means 15A shown in FIG. 8 may be adopted.
- the present invention further discloses the following nanofiber manufacturing apparatus.
- Raw material injection means comprising a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode;
- a nanofiber production apparatus comprising a collection means for collecting nanofibers, The voltage generating means generates a voltage so that the nozzle becomes an anode and the electrode becomes a cathode, The electrode is covered with a coating with a dielectric exposed on substantially the entire surface facing the nozzle, A nanofiber manufacturing apparatus, wherein the dielectric exposed on the surface has a thickness of 0.8 mm or more.
- ⁇ 2> The nanofiber manufacturing apparatus according to ⁇ 1>, wherein a part or all of the surface of the electrode that does not face the nozzle is coated with a coating with a dielectric exposed on the surface.
- Raw material injection means comprising a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode; A nanofiber production apparatus comprising a collection means for collecting nanofibers, The voltage generating means generates a voltage so that the nozzle becomes an anode and the electrode becomes a cathode, An apparatus for producing nanofibers, wherein the outer surface of the nozzle is substantially entirely covered with a cover having a dielectric exposed on the surface, and the cover extends beyond the tip of the nozzle.
- Raw material injection means comprising a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode; A nanofiber production apparatus comprising a collection means for collecting nanofibers, The voltage generating means generates a voltage so that the nozzle becomes a cathode and the electrode becomes an anode, An apparatus for producing nanofibers, wherein a substantially entire outer surface of the nozzle is covered with a coating with a dielectric exposed on the surface.
- ⁇ 7> The nanofiber manufacturing apparatus according to ⁇ 5> or ⁇ 6>, wherein the electrode has a substantially entire surface facing the nozzle covered with a coating with a dielectric exposed on the surface.
- ⁇ 8> The nanofiber manufacturing apparatus according to ⁇ 7>, wherein a part or all of the surface of the electrode that does not face the nozzle is covered with a coating with a dielectric exposed on the surface.
- Raw material injection means comprising a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode; A nanofiber production apparatus comprising a collection means for collecting nanofibers, The voltage generating means generates a voltage so that the nozzle becomes a cathode and the electrode becomes an anode, The electrode is covered with a coating with a dielectric exposed on substantially the entire surface facing the nozzle, A nanofiber manufacturing apparatus, wherein the dielectric exposed on the surface has a thickness of 0.8 mm or more.
- ⁇ 10> The nanofiber manufacturing apparatus according to ⁇ 9>, wherein a part or all of the surface of the electrode that does not face the nozzle is coated with a coating with a dielectric exposed on the surface.
- Raw material injection means comprising a conductive nozzle for injecting a raw material liquid for producing nanofibers, An electrode spaced apart from the nozzle; Voltage generating means for generating a voltage between the nozzle and the electrode; An airflow ejecting means arranged to be able to eject an airflow between the nozzle and the electrode;
- a nanofiber production apparatus comprising a collection means for collecting nanofibers, An apparatus for producing nanofibers, wherein the collecting means has a collecting electrode, and substantially the entire surface of the collecting electrode is coated with a coating with a dielectric exposed on the surface thereof.
- ⁇ 13> The nanofiber manufacturing apparatus according to any one of ⁇ 2> to ⁇ 8> or ⁇ 10> to ⁇ 12>, wherein a thickness of the dielectric exposed on the surface is 0.8 mm or more.
- ⁇ 14> The nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 13>, wherein the dielectric exposed on the surface has a thickness of 8 mm or more.
- the thickness of the dielectric exposed on the surface constituting the covering is preferably 0.8 mm or more, particularly preferably 2 mm or more, particularly preferably 8 mm or more, and the upper limit of the thickness of the covering is 25 mm or less, particularly 20 mm or less, In particular, it is preferably 15 mm or less, and when the covering is composed of a single kind or a plurality of kinds of dielectrics, for example, the thickness of the covering is 0.8 mm or more and 25 mm or less, particularly 2 mm or more and 20 mm or less, especially 8 mm or more and 15 mm.
- the nanofiber production apparatus according to any one of ⁇ 1> to ⁇ 14> which is preferably as follows.
- ⁇ 16> The nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 15>, wherein the electrode is plate-shaped.
- the airflow ejecting means is disposed at a position where an airflow can be ejected between the nozzle and the electrode,
- the nanofiber formed from the raw material solution tries to extend from the nozzle toward the electrode, Any one of ⁇ 1> to ⁇ 16>, in which the airflow ejected from the airflow ejecting means changes the traveling direction of the nanofiber, conveys the nanofiber in a certain direction, and stretches the nanofiber.
- the nanofiber manufacturing apparatus described in 1. ⁇ 18> The nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 15>, wherein the electrode has a concave spherical shape.
- the concave curved surface of the electrode is a curved surface that does not have a flat portion at all, or a shape that can be regarded as a concave curved surface as a whole by connecting a plurality of segments having a flat portion, or three axes that are orthogonal to each other ⁇ 18>
- the concave surface of the electrode is a nanofiber manufacturing apparatus according to ⁇ 18> or ⁇ 19>, wherein a normal line at an arbitrary position has a value passing through the tip of the nozzle or the vicinity thereof.
- the direction in which the nozzle extends is the center of a circle defined by the opening end of the concave surface of the electrode, or the vicinity of the center and the center of the opening provided at the bottom of the concave surface, or the center thereof.
- the nozzle is arranged so that the plane including the circle defined by the open end of the concave surface and the extending direction of the nozzle are orthogonal to each other ⁇ 18
- the nanofiber manufacturing apparatus according to any one of> to ⁇ 20>.
- the nozzle is arranged so that the tip of the nozzle is located in a plane including a circle defined by the opening end of the concave curved surface of the electrode, or located inside the concave curved surface from the plane ⁇
- the nanofiber manufacturing apparatus according to any one of 18> to ⁇ 21>.
- the air flow ejecting means is formed along the direction in which the nozzle extends, and is formed so that an air flow can be ejected toward the tip of the nozzle. When viewed from the open end side of the electrode, a plurality of the air flow ejection means are provided so as to surround the nozzle, The air flow ejecting means is formed at a symmetrical position across the nozzle.
- the nanofiber device according to any one of ⁇ 18> to ⁇ 22>.
- ⁇ 24> The nanofiber manufacturing apparatus according to ⁇ 22>, wherein the nozzle is disposed so that a tip of the nozzle is positioned 1 to 10 mm inside the plane.
- ⁇ 25> The nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 15>, wherein the electrode has a cylindrical shape.
- the electrode has a substantially cylindrical inner surface, and a nozzle tip is disposed in the vicinity of the center in a cross section perpendicular to the axial direction. In the axial direction, the nozzle tip is disposed in a column space formed inside the cylinder ⁇ 25. > The nanofiber manufacturing apparatus described in>.
- ⁇ 27> The nanofiber manufacturing apparatus according to ⁇ 25> or ⁇ 26>, wherein the eccentricity of a circle or an ellipse in a cross section perpendicular to the axial direction of the electrode is 0 or more and less than 0.6, preferably a perfect circle with an eccentricity of 0 .
- a radius defined by a distance between the nozzle and the electrode in a cross section perpendicular to the axial direction of the electrode is 20 mm or more and 100 mm or less, and preferably 30 mm or more and 50 mm or less ⁇ 25> to ⁇ 27>.
- the nanofiber manufacturing apparatus according to any one of the above.
- ⁇ 29> The nanofiber manufacturing apparatus according to any one of ⁇ 25> to ⁇ 28>, wherein the cylindrical electrode has an axial length of 20 mm to 150 mm, preferably 30 mm to 80 mm.
- the electrode has a substantially cylindrical inner surface, the tip of the nozzle is located in a plane including a circle defined by the open end of the substantially cylinder, and the tip is a circle defined by the open end.
- the nanofiber manufacturing apparatus ⁇ 31> according to any one of ⁇ 25> to ⁇ 29>, which is located within 10 mm from the center of When viewed along the axial direction of the cylindrical electrode, the tip of the nozzle is disposed in a columnar space formed inside the cylinder, and of the two ends of the electrode, the raw material liquid discharge side ⁇ 25> thru
- the air flow ejecting means is formed along the direction in which the nozzle extends, and is formed so that an air flow can be ejected toward the tip of the nozzle.
- a plurality of the air flow ejection means are provided so as to surround the nozzle.
- the electrospinning apparatus according to any one of ⁇ 25> to ⁇ 32>, wherein the electrode is entirely covered with a dielectric.
- the thickness of the dielectric is 0.8 mm or more, more preferably 2 mm or more, particularly preferably 8 mm or more, 25 mm or less, more preferably 20 mm or less, particularly preferably 15 mm or less, and 0.8 mm or more and 25 mm or less.
- the electrospinning apparatus according to any one of ⁇ 25> to ⁇ 33>, more preferably 2 mm to 20 mm, particularly preferably 8 mm to 15 mm.
- ⁇ 35> The electric field according to any one of ⁇ 25> to ⁇ 34>, wherein a tip of the nozzle is disposed on an inner side of 1 mm or more and 10 mm or less with respect to a plane defined by a cylindrical opening end on a concave curved surface of the electrode. Spinning device.
- ⁇ 36> The nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 35>, wherein the dielectric is at least one selected from alumina, bakelite, nylon, and vinyl chloride resin.
- ⁇ 37> The nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 36>, wherein the dielectric is nylon.
- the distance between the tip of the nozzle and the electrode is preferably set to 20 mm or more, particularly 30 mm or more, and the upper limit is preferably set to 100 mm or less, particularly 50 mm or less.
- the distance between the two is 20 mm or more.
- the nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 37>, preferably set to 100 mm or less, and more preferably set to 30 mm or more and 50 mm or less.
- the flow velocity of the air flow is 200 m / sec or more, particularly preferably 250 m / sec or more, preferably 600 m / sec or less, particularly preferably 530 m / sec or less, and 200 m / sec or more and 600 m / sec or less.
- the nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 38>, which is particularly preferably 250 m / sec or more and 530 m / sec or less.
- the extending portion of the covering extending beyond the tip of the nozzle has a hollow portion in a cylindrical shape surrounding the nozzle, and the hollow portion communicates with the inside of the nozzle ⁇
- the length of the extended portion of the covering of the nozzle is preferably 1 mm or more, more preferably 10 mm or more, and the upper limit is preferably 15 mm or less, more preferably 12 mm or less.
- the lower limit of the outer diameter of the nozzle can be preferably set to 300 ⁇ m or more, more preferably 400 ⁇ m or more, and the upper limit can be set to preferably 4000 ⁇ m or less, more preferably 3000 ⁇ m or less.
- the length of the nozzle is preferably 50 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less, the nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 42> .
- the electrode or the nozzle is substantially entirely covered (90% or more area) with the covering, and preferably covered with the covering (100% area) ⁇ 1> to ⁇ 43>
- the nanofiber manufacturing apparatus according to any one of the above.
- the substantially entire surface (90% or more area) of the surface (of the covering) is composed only of the dielectric.
- the covering is (the The nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 44>, wherein the entire surface (100% area) of the covering body is made of only a dielectric.
- the raw material liquid is a solution in which a polymer compound capable of forming a fiber is dissolved or dispersed in a solvent, or a melt obtained by heating and melting a polymer compound. Fiber manufacturing equipment.
- ⁇ 47> The nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 46>, wherein the electrode and the covering are joined by a joining member made of a dielectric.
- ⁇ 48> The nanofiber manufacturing apparatus according to ⁇ 47>, wherein the bonding member is made of a dielectric.
- the bonding member is a screw or a wooden screw made of an adhesive or a dielectric.
- ⁇ 50> The nanofiber manufacturing apparatus according to ⁇ 49>, wherein the joining member is a screw, a screw hole is formed in the covering, and a counterbore process is performed on the screw hole.
- the airflow ejecting unit is made of a dielectric.
- the air flow ejecting means has a plurality of openings from which the air flow is ejected, and the openings are spaces formed by narrow gaps, or are substantially columnar spaces,
- the nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 51>, wherein the airflow ejecting unit is disposed so that the opening faces a space between the electrode and the nozzle.
- ⁇ 54> The nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 53>, in which an arrangement of openings formed in the airflow ejection unit can be freely set.
- the opening formed in the air flow ejecting means consists of a substantially columnar space
- the opening formed in the air flow ejecting means is arranged concentrically with the nozzle as a center when the electrode opening is viewed from the front ⁇ 1> to ⁇ 55>.
- the nanofiber manufacturing apparatus according to any one of 55>.
- the nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 56>, wherein the shape of the opening formed in the airflow ejection unit is a circle, an ellipse, a triangle, a quadrangle, or a polygon.
- the diameter range is preferably 0.1 mm or more and 1.5 mm or less, more preferably 0.3 mm or more and 1.2 mm or less ⁇ 1.
- the nanofiber manufacturing apparatus according to any one of> to ⁇ 57>.
- the pitch of the openings formed in the air flow ejecting means is preferably 3 mm or more and 15 mm or less, and more preferably 5 mm or more and 12 mm or less when the openings are arranged in a staggered pattern.
- the nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 58>.
- ⁇ 60> When the opening formed in the airflow ejecting means is arranged concentrically around the nozzle, the angle formed between the adjacent opening and the center of the nozzle is 5 ° or more and 60 ° or less.
- the nanofiber production apparatus according to any one of ⁇ 1> to ⁇ 59>, preferably 8 ° to 30 °.
- the radius of the pitch circle is preferably 6 mm or more and 15 mm or less, and 7.5 mm or more and 12.5 mm or less. It is more preferable that the nanofiber manufacturing apparatus according to any one of ⁇ 1> to ⁇ 60>.
- or ⁇ 61> The nanofiber molded object which consists of a nanofiber manufactured using the nanofiber manufacturing apparatus of any one.
- Examples 1 to 3 In order to evaluate the charge amount of the raw material liquid in the manufacturing apparatus 10 shown in FIG. 1, the charge amount of water was measured using water as a model raw material liquid. A method for measuring the charge amount will be described later. Since water does not form a fiber, it is easy to collect the charged liquid, and the charge amount can be easily measured by the method described later.
- the speed at which water was jetted from the nozzle 13 was 1 g / min, the inner diameter of the nozzle 13 was 2 mm, and the length was 50 mm.
- the area of the flat portion of the electrode 14 (the surface facing the nozzle 13) is 81 cm 2 (length 9 cm ⁇ width 9 cm), and the entire surface is a dielectric (nylon (MC nylon MCA-90-90- from MISUMI Corporation). 10), and coating bodies 17 made of bakelite (BLA-90-90-10 manufactured by MISUMI Corporation) and alumina (CEMN-90-90-10 manufactured by MISUMI Corporation), respectively.
- the thickness of each dielectric was 10 mm.
- the distance (shortest distance) between the tip of the nozzle 13 and the electrode 14 was 50 mm.
- a DC voltage ( ⁇ 20 kV, ⁇ 30 kV, ⁇ 40 kV) is applied between the electrode 14 and the nozzle 13 to measure the amount of current (hereinafter referred to as leakage current) flowing between the electrode 14 and the nozzle 13.
- leakage current was measured using an ammeter built in a high voltage generator (HAR-60R1-LF manufactured by Matsusada Precision Co., Ltd.) used as a voltage generator. In order to eliminate the influence of the raw material liquid on the leakage current, the raw material liquid was not injected.
- Comparative Example 1 This comparative example is an example in which the electrode 14 is not covered with the covering 17 made of a dielectric in the first embodiment. Except this, the same operation as in Example 1 was performed, and the same measurement was performed. The results are shown in Table 1.
- This comparative example is an example in which a covering body with a conductive layer (conductor layer) made of metal exposed on the surface is used as the covering body 17.
- an aluminum tape (SLIONTEC (registered trademark)) having a thickness of 0.2 mm was further laminated on the surface of the dielectric to form a covering.
- SIONTEC registered trademark
- An example corresponding to this comparative example can be found in the example of Patent Document 2. Otherwise, the same operation as in Example 1 was performed, and the same measurement was performed. The results are shown in Table 1.
- Example 4 Using the manufacturing apparatus 18 shown in FIGS. 3 and 4, the charge amount of water and the leakage current were measured in the same manner as in Examples 1 to 3.
- the concave curved surface R of the electrode 19 was a hemisphere having a radius of 45 mm, and the tip 20a of the nozzle 20 was placed at the center of the hemisphere. At this time, the tip 20a is located in a plane including a circle defined by the open end of the concave curved surface R.
- the extending direction of the nozzle was matched with the rotational symmetry axis of the hemisphere. Similar to FIG.
- Example 4 since the electrode 19 has a concave spherical shape, the charge amount of water is remarkably increased as compared with Comparative Examples 1 to 4 using the plate-like electrode 14.
- Example 5 In the manufacturing apparatus 10 shown in FIG. 1, the leakage current was evaluated by using a laminated body in which a plurality of polypropylene sheets having a thickness of 0.2 mm were laminated on the covering body 17.
- the structure of the manufacturing apparatus 10 was the same as in Examples 1 to 3 except that a polypropylene sheet was used for the covering 17.
- the “thickness of the dielectric exposed on the surface” is defined as the total thickness of the laminated sheets, which is the covering 17. Equal to the thickness of Therefore, the thickness of the four-layered covering 17 is 0.8 mm, and the thickness of the five-layered covering 17 is 1.0 mm.
- the entire flat portion of the electrode 14 (the surface facing the nozzle 13) was covered with the polypropylene sheet laminate, and a DC voltage of ⁇ 40 kV was applied between the electrode 14 and the nozzle 13. The amount of leakage current flowing between the electrode 14 and the nozzle 13 was measured by the same method as in Examples 1 to 3, and the presence or absence of discharge was observed. These results are shown in Table 3.
- Example 6 In the manufacturing apparatus 10 shown in FIG. 1, the leakage current and the charge amount of water were evaluated using bakelite with a thickness of 2 mm, 5 mm, 8 mm, and 10 mm for the covering 17.
- the structure of the manufacturing apparatus 10 was the same as in Examples 1 to 3, except that the thickness of the bakelite was used for the covering 17.
- the covering 17 is composed of a single type of dielectric (bakelite)
- the “thickness of the dielectric exposed on the surface” is the thickness of the dielectric (bakelite), that is, the thickness of the covering 17. Equal to thickness.
- the entire flat portion of the electrode 14 (the surface facing the nozzle 13) was covered with the bakelite, and a DC voltage of ⁇ 40 kV was applied between the electrode 14 and the nozzle 13.
- the amount of leakage current flowing between the electrode 14 and the nozzle 13 was measured by the same method as in Examples 1 to 3, and the presence or absence of discharge was observed. Further, the charge amount of water used as the model raw material liquid was measured in the same manner as in Examples 1 to 3. These results are shown in Table 4.
- the relationship between the thickness of the covering 17 (polypropylene and bakelite) and leakage current in Example 5, Comparative Example 5 and Example 6 is plotted as shown in FIG. Referring to FIG. 19, the leakage current is greatly reduced as the thickness of the covering 17 is increased from 0 mm to 0.8 mm. From this, it is understood that the emission of electrons from the electrode 14 can be effectively suppressed by setting the thickness of the covering 17 covering the electrode 14 to 0.8 mm or more. Further, when the coating is thicker than 0.8 mm and the coating thickness is 2 mm, the leakage current can be further reduced.
- Table 4 shows that when the thickness of the covering 17 is 8 mm or more, the charge amount of water measured at ⁇ 5 kV is remarkably increased, and the effect of the present invention becomes more remarkable. This is because the increase in the thickness of the dielectric increases the capacitance between the nozzle and the electrode, and significantly reduces the leakage current, thereby suppressing the flying of electrons and reducing the amount of charge. This is thought to be due to the increase. This remarkable effect cannot be obtained by the technique described in Japanese Patent Laid-Open No. 2010-59557 (Patent Document 3) in which the electrode is thinly coated with a dielectric.
- Example 7 In the manufacturing apparatus 10 shown in FIG. 1, the electrode 14 was not covered with the covering member 17, and instead, the entire outer surface of the nozzle 13 was covered with the covering member 107, and leakage current was evaluated.
- the covering 107 was made of vinyl chloride having a thickness of 2 mm, covering the entire outer surface of the nozzle 13, and extending the covering 107 beyond the tip of the nozzle 13 by 10 mm and 1 mm.
- the electrode 14 was not covered with the covering 17. Except for these, the manufacturing apparatus 10 having the same structure as in Examples 1 to 3 was used, the amount of leakage current was measured in the same manner as in Examples 1 to 3, and the presence or absence of discharge was observed. The results are shown in Table 5.
- Example 7 the covering 107 was not extended beyond the tip of the nozzle 13, and only the outer surface of the nozzle 13 or a part of the outer surface was covered with the covering 107, and the leakage current was evaluated.
- a region from the rear end (base) of the nozzle to 50 mm, 49 mm, and 25 mm was covered with a covering 107 (vinyl chloride having a thickness of 2 mm).
- Example 7 As shown in Table 5, when the applied voltage was ⁇ 40 kV, discharge was performed in all examples of Example 7 and Comparative Example 6, but when the applied voltage was ⁇ 20 kV, the length of the extended portion was 1 mm or more.
- the leakage current of a certain example 7 was significantly smaller than the leakage current of the comparative example 6 having no extension. In particular, it was found that if the extension portion is 10 mm (or more), the leakage current is maintained at 0 even when the applied voltage is ⁇ 30 kV, and discharge can be prevented. In this way, the outer surface of the nozzle is covered with a cover with a dielectric exposed on the surface, and by extending the cover beyond the tip of the nozzle, the discharge between the electrode 14 and the nozzle 13 can be suppressed. In addition, power consumption during nanofiber manufacturing due to leakage current can be suppressed.
- Example 8 In the manufacturing apparatus 10 shown in FIG. 1, the electrode 14 was covered with the covering body 17, and the entire outer surface of the nozzle 13 was covered with the covering body 107 to evaluate the leakage current.
- the covering 107 was made of vinyl chloride having a thickness of 2 mm, covering the entire outer surface of the nozzle 13, and extending the covering 107 beyond the tip of the nozzle 13 from 1 mm to 10 mm in 1 mm increments. Except for these, the manufacturing apparatus 10 having the same structure as in Example 1 was used to measure the amount of leakage current and observe the presence or absence of discharge in the same manner as in Examples 1 to 3.
- the electrode 14 is covered with a covering 17 made of MC nylon having a thickness of 10 mm. The results are shown in Table 6.
- Example 8 the covering 107 was not extended beyond the tip of the nozzle 13, and only the outer surface of the nozzle 13 or a part of the outer surface was covered with the covering 107, and the leakage current was evaluated.
- a region from the rear end (base) of the nozzle to 50 mm and 25 mm was covered with a covering 107 (vinyl chloride having a thickness of 2 mm).
- the lengths of the extended portions are written as 0 mm and ⁇ 25 mm, respectively.
- the leakage current of Example 8 in which the length of the extended portion is 1 mm or more is larger than the leakage current of Comparative Example 7 having no extended portion.
- the reduction in leakage current was significant.
- both the outer surface of the nozzle 13 and the electrode 14 are covered with a cover having a dielectric exposed on the surface, the leakage current is kept smaller and no discharge is generated.
- neutralization of the raw material liquid caused by flying electrons that is, reduction of the charge amount can be suppressed, and the discharge between the electrode 14 and the nozzle 13 can be suppressed. Power consumption can be reduced.
- the charge amount of water was measured by the following method using the apparatus shown in FIG. 20A is for Examples 1 to 3, Example 6 and Comparative Examples 1 to 4 using the manufacturing apparatus 10, and FIG. 20B is for Example 4 using the manufacturing apparatus 18. Is.
- the entire apparatus is rotated 90 degrees so that the extending direction of the nozzle 13 is horizontal.
- the entire apparatus is arranged so that the extending direction of the nozzle 20 is vertically downward.
- a -5 kV DC voltage is applied between the nozzle and the electrode with a high voltage generator (HAR-60R1-LF, manufactured by Matsusada Precision Co., Ltd.), and water is ejected from the nozzle at a rate of 1 g / min. In this state, the charged water is dripped substantially vertically downward by gravity.
- HAR-60R1-LF high voltage generator
- the dropped water droplets are received in a metal container grounded in a Faraday cage (NQ-1400 manufactured by Kasuga Denki Co., Ltd.), and the amount of water accumulated within a certain time (within a few minutes) is measured by a coulomb meter (Kasuga Denki Co., Ltd.) Measured with NK-1001, 1002).
- the mass of the accumulated water was measured with an analytical balance, and the charge amount (nC / g) per unit mass of water was determined from the ratio of the two. If the voltage applied between the nozzle and the electrode is made lower than -5 kV (the absolute value of the applied voltage is made larger than 5 kV), the charged water is scattered and water droplets cannot be collected in the metal container. As a result, all measurements were made at an applied voltage of -5 kV.
- Example 9 The nanofiber was manufactured using the manufacturing apparatus 510 shown in FIG. A 15% aqueous solution of pullulan was used as the raw material liquid. The speed at which the raw material liquid was sprayed from the nozzle 13 was 1 g / min, the inner diameter of the nozzle 13 was 2 mm, and the length was 50 mm. The area of the flat portion of the electrode 14 (surface facing the nozzle 13) was 81 cm 2 (length 9 cm ⁇ width 9 cm), and the entire surface was covered with a covering 17 made of bakelite. The thickness of the bakelite was 10 mm. An air flow having a flow rate of 100 L / min was injected from the air flow injection means 15A.
- the arrangement of the openings 151A formed on the front surface of the air flow ejecting means 15A is such that the pitch in the horizontal direction H is 10 mm, the pitch in the vertical direction V is 10 mm, and the row of openings extending in the horizontal direction H is the vertical direction V.
- photographed the obtained nanofiber with the scanning electron microscope (SEM) is shown to Fig.21 (a).
- the electrode 14 of the manufacturing apparatus 10 shown in FIG. 1 is changed to a spherical electrode (electrode having a convex spherical shape), and a nanofiber is manufactured using a manufacturing apparatus in which the electrode 14 is not covered with the covering 17. This is the result of manufacturing.
- the diameter of the spherical electrode was 25 mm, and the center of the sphere was placed directly above the tip of the nozzle 13.
- the distance (shortest distance) between the tip of the nozzle 13 and the spherical electrode was 75 mm.
- the other device structure was the same as in Example 9, and spinning was performed under the same conditions.
- photographed the obtained nanofiber with the scanning electron microscope (SEM) is shown in FIG.21 (b).
- Example 9 thin nanofibers with an average diameter of about 200 nm were obtained in Example 9 (FIG. 21 (a)), whereas in Comparative Example 8 (FIG. 21 (b)), the average diameter was about Only thick nanofibers of 500 nm were obtained. Moreover, in Example 9, the number of defects (what the raw material liquid droplets solidified as they were) was smaller than in Comparative Example 8, and a high-quality nanofiber was obtained. Since the speed of the raw material liquid injected from the nozzle 13 is the same in Example 9 and Comparative Example 8, Example 9 produces nanofibers about 6.25 times longer per unit time than Comparative Example 8. As a result, it can be seen that productivity is improved by using the manufacturing apparatus of the present configuration.
- the nanofiber having a diameter of 500 nm is faster than the raw material injection speed of 1 g / min. (Even if more than 1 g of raw material liquid is supplied to the nozzle 13 per unit time). Also from this point, it can be seen that the productivity of the manufacturing apparatus having the configuration of the present invention is improved.
- Example 10 The nanofiber was manufactured using the manufacturing apparatus 18 shown in FIGS. A 25% aqueous solution of pullulan was used as a raw material liquid. The speed at which the raw material liquid is jetted from the nozzle 20 is 1 g / min, and the speed at which the airflow is jetted from the airflow jetting means 23 is 200 L / min. A voltage of ⁇ 30 kV was applied between the nozzle 20 and the electrode 19, and spinning was performed in the same manner as in Example 4 except for the device structure other than that. The photograph which image
- SEM scanning electron microscope
- Example 10 although an aqueous solution having a high viscosity (7372.8 mPa ⁇ s) with a pullulan concentration increased to 25% was used as a raw material liquid, the average diameter was about 856 nm as shown in FIG. A high-quality nanofiber having a small size was obtained (the liquid droplet of the raw material liquid was solidified as it was).
- the charge amount of the raw material liquid is increased, and the force for attracting the raw material liquid to the electrode 19 (cathode) is improved, so that even a highly viscous solution (high concentration raw material liquid) can be spun. It is thought that it became.
- the solid content to be fiberized in the raw material liquid is increased. From this point, it can be said that the productivity of the manufacturing apparatus of the present configuration is improved.
- Examples 11 to 13 In order to evaluate the charge amount of the raw material solution in the electrospinning apparatus 701 shown in FIGS. 13 and 14, water was used as a model raw material solution, and the charge amount of water was measured. A method for measuring the charge amount will be described later. Since water does not form a fiber, it is easy to collect the charged liquid, and the charge amount can be easily measured by the method described later.
- the speed at which water was jetted from the nozzle 720 was 1 g / min, the inner diameter of the nozzle 720 was 2000 ⁇ m, and the length was 50 mm.
- the electrode 710 is a cylinder having a length of 50 mm, an inner diameter of 45 mm, and a thickness of 3 mm (carbon steel for mechanical structure S45C).
- the tip 720a of the nozzle 720 is defined by one open end of the cylindrical concave curved surface 711. It was made to lie in the plane that contains the circle. The extending direction of the nozzle was matched with the central axis of the cylinder.
- Example 11 as in FIGS. 13 and 14, the entire surface of the concave curved surface 711 of the electrode 710 was covered with a dielectric 730 (monomer cast nylon (MC901 cutting plate (blue) manufactured by Bronze Co., Ltd.)) having a thickness of 10 mm.
- MC901 cutting plate (blue) manufactured by Bronze Co., Ltd.) having a thickness of 10 mm.
- the end surface of the electrode 710 on the discharge direction side was also covered.
- Example 13 in addition to the coating of Example 12, the entire outer peripheral surface of the electrode 710 was further coated. In all examples, a DC voltage of ⁇ 5 kV was applied to the electrode 710.
- the nozzle 720 was grounded.
- Comparative Examples 9 and 10 In Comparative Example 9, the charge amount of water was measured using a manufacturing apparatus in which the dielectric 730 covering the electrode 710 of the electrospinning apparatus 701 shown in FIG. 13 was disposed at a position 15 mm away from the inner surface of the electrode 710. .
- the dielectric 730 was a cylinder having an inner diameter of 30 mm.
- Comparative Example 10 the charge amount of water was measured using a manufacturing apparatus in which the electrode 710 of the electrospinning apparatus 701 shown in FIG.
- the other measurement conditions are the same as those in Examples 11 to 13.
- a direct current voltage ( ⁇ 20 kV, ⁇ 30 kV, ⁇ 40 kV) is applied between the electrode 710 and the nozzle 720, and the amount of current flowing between the electrode 710 and the nozzle 720 (hereinafter referred to as leakage current) is measured. The presence or absence of discharge was observed.
- the leakage current was measured using an ammeter built in a high voltage generator (HAR-60R1-LF manufactured by Matsusada Precision Co., Ltd.) used as a voltage generator. In order to eliminate the influence of the raw material liquid on the leakage current, the raw material liquid was not injected.
- the entire apparatus is arranged so that the extending direction of the nozzle 720 is vertically downward.
- a -5 kV DC voltage is applied between the nozzle and the electrode with a high voltage generator (HAR-60R1-LF, manufactured by Matsusada Precision Co., Ltd.), and water is ejected from the nozzle at a rate of 1 g / min.
- the charged water is dripped substantially vertically downward by gravity.
- the dropped water droplets are received in a metal container grounded in a Faraday cage (Kasuga Denki Co., Ltd.
- Examples 14 to 16 In the electrospinning apparatus 701 shown in FIGS. 13 and 14, the amount of charge is measured when the position of the tip 720a of the nozzle 720 is arranged inward from the plane formed at the opening end of the electrode 710 with respect to the axial direction of the electrode 710. did. At the same time, the raw material liquid was used instead of water, and the contamination state of the electrode 710 and the dielectric 730 covering the electrode 710 with the raw material liquid was evaluated. Evaluation criteria will be described later. The measurement conditions are the same as when measuring Examples 11 to 13.
- Example 14 the position of the tip 720a of the nozzle 720 was set on the plane formed at the opening end of the electrode 710 in the same manner as in Examples 11 to 13.
- Example 15 the position of the tip 720a of the nozzle 720 was 16 mm inward from the plane formed at the opening end of the electrode 710.
- Example 16 the position of the tip 720a of the nozzle 720 was 32 mm inward from the plane formed at the opening end of the electrode 710.
- A There is little contamination of the electrode 710 and the dielectric 730 by the raw material liquid.
- B Contamination of the electrode 710 and the dielectric 730 with the raw material liquid is slightly observed.
- C There is much contamination of the electrode 710 and the dielectric 730 by the raw material liquid.
- Comparative Example 11 In Comparative Example 11, charging is performed when the position of the tip 720a of the nozzle 720 in the electrospinning apparatus 701 shown in FIGS. 13 and 14 is arranged outward from the plane formed at the open end of the electrode with respect to the axial direction of the electrode 710. The amount was measured. At the same time, using the raw material liquid instead of water, the contamination state of the electrode 710 and the dielectric 730 covering the electrode 710 with the raw material liquid was evaluated. The measurement conditions are the same as when measuring Examples 1 to 3.
- the raw material liquid becomes difficult to adhere to the electrode 710 and the dielectric 730, and the electrode 710 and It has been found that contamination of the dielectric 730 can be reduced.
- Example 17 Nanofibers were manufactured using an electrospinning apparatus 701 shown in FIG.
- the coating conditions for the dielectric 730 were the same as those in Example 13.
- a 15% by weight aqueous solution of pullulan was used as a raw material liquid.
- the speed at which the raw material liquid is ejected from the nozzle 720 is 1 g / min, an air flow having a flow rate of 150 L / min is ejected from the air flow ejecting means 723, a voltage of ⁇ 20 kV is applied between the nozzle 720 and the electrode 710, and the nozzle 720
- the distance from the tip 720a to the collection plate was 1200 mm.
- photographed the obtained nanofiber with the scanning electron microscope (SEM) is shown to Fig.23 (a) and FIG.23 (b).
- This comparative example is a result of manufacturing nanofibers using a manufacturing apparatus in which the electrode 710 of the electrospinning apparatus 701 shown in FIG.
- the rest of the apparatus structure was the same as in Example 17, and spinning was performed under the same conditions as in Example 17 except that the applied voltage was -10 kV.
- the voltage to be applied was set to a value at which nanofibers can be manufactured.
- photographed the obtained nanofiber with the scanning electron microscope (SEM) is shown to Fig.24 (a) and FIG.24 (b).
- Example 17 As shown in FIGS. 23 (a) and 23 (b), nanofibers with an average diameter of 305 nm were obtained in Example 17, whereas as shown in FIGS. 24 (a) and 24 (b). In Comparative Example 12, only nanofibers having an average diameter of 487 nm were obtained. In addition, Example 17 had fewer defects than those of Comparative Example 12 (the raw material liquid droplets solidified as they were), and a high-quality nanofiber was obtained. Since the speed of the raw material liquid injected from the nozzle 720 is the same in Example 17 and Comparative Example 12, assuming that the nanofibers are uniformly formed with an average diameter, Example 17 is more unit than Comparative Example 12.
- nanofibers having a length of about 2.5 times per unit time can be manufactured, and that productivity is improved by using the manufacturing apparatus having the configuration of the present invention.
- nanofibers having an average diameter of 487 nm are 1 g / min. It is possible to manufacture at a faster raw material injection speed (even if more than 1 g of raw material liquid is supplied to the nozzle 720 per unit time). Also from this point, it can be seen that the productivity of the manufacturing apparatus having the configuration of the present invention is improved.
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Abstract
Description
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陽極になり、かつ前記電極が陰極になるように電圧を発生させ、
前記電極は前記ノズルと対向する面の略全面が、表面に誘電体の露出した被覆体で被覆され、
前記表面に露出した誘電体の厚みが0.8mm以上であるナノファイバ製造装置を提供するものである。
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陽極になり、かつ前記電極が陰極になるように電圧を発生させ、
表面に誘電体の露出した被覆体によって、前記ノズルの外面の略全面が被覆されているとともに、該被覆体が該ノズルの先端を越えて延出しているナノファイバ製造装置を提供するものである。
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陰極になり、かつ前記電極が陽極になるように電圧を発生させ、
表面に誘電体の露出した被覆体によって、前記ノズルの外面の略全面が被覆されているナノファイバ製造装置を提供するものである。
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陰極になり、かつ前記電極が陽極になるように電圧を発生させ、
前記電極は前記ノズルと対向する面の略全面が、表面に誘電体の露出した被覆体で被覆され、
前記表面に露出した誘電体の厚みが0.8mm以上であるナノファイバ製造装置を提供するものである。
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記捕集手段が捕集用電極を有し、該捕集用電極の略全面が表面に誘電体の露出した被覆体で被覆されているナノファイバ製造装置を提供するものである。
本発明では、電極はノズルと対向する面の略全面が、表面に誘電体の露出した被覆体で被覆される。更に好ましくはノズルと対向する面の全面が、表面に誘電体の露出した被覆体で被覆される。ノズルと対向する面とは、ノズルの先端(原料液が噴射する開口部)から臨むことのできる電極の表面のことである。より詳細には、ノズルの先端上の各点から電極に向けて直線を引いたときに電極と最初に接する点の集合のことである。また略全面とは当該面の全表面積の90%以上の面積を占める面を意味し、全面とは当該面の全表面積の100%の面積を占める面を意味する。表面に誘電体の露出した被覆体とは、該表面の略全面(90%以上の面積)が誘電体のみで構成された被覆体のことである。後述するように、該被覆体は表面の全面(100%の面積)が誘電体のみで構成されていることが好ましい。すなわち、本発明において、被覆体は表面に誘電体が露出し、表面に金属などの導電体が非存在とした被覆体であることが好ましい。単一種の誘電体から構成された被覆体がその典型例であるが、被覆体は複数種の誘電体が積層された複合体であってもよいし、表面が誘電体のみで構成されていれば、内部(表面に露出しない部分)に金属の粒子又は空気の層等を含んだ複合体であってもよい。特に電極と被覆体の接合部の一部に空気の層が存在していてもよいが、電極と被覆体の接合を強固にする観点からは電極と被覆体は密着している方が好ましい。なお本発明では、当該被覆体の表面を更に被覆するような物体は存在しないものと想定している。仮に、当該被覆体の表面を更に被覆するような、金属等からなる導電層が存在するならば本発明の効果は低減する。
前記効果を有効に発現させるためには、ノズル13と対向する面の略全面(90%以上の面積)を被覆体17で被覆することが好ましく、特にノズル13と対向する面の全面(100%の面積)を被覆体17で被覆することが好ましい。被覆していない面の面積が大きいと、そこから電子が大気に放出され、飛来した電子によって原料液の帯電量が減少してしまう。また、電極14の表面のうちのノズル13と対向する面だけではなく、ノズル13と対向しない面をも被覆体17で被覆することによって前記効果は一層大きくなる。ノズル13と対向しない面からも少なからず電子が大気に放出されるからである。原料液の帯電量を高めるという観点からは、電極14のすべての面を被覆体17で被覆するのが好ましい。
先に背景技術の項で述べた特許文献3には、電極の表面に薄い絶縁体層を設けたナノファイバ製造装置が開示されている。当該ナノファイバ製造装置は、原料液噴射ノズルではなく、直径10mm~300mmの導電性円筒の側面に多数の流出孔を設けた流出体を用いている点でそもそも本発明とは構成が異なるが、流出体に対向する面に薄い絶縁体層を設けた電極を備えている。しかしながら絶縁体層の目的は、電極にナノファイバが付着するのを防止し、かつナノファイバの帯電状態を変化させることであり、該目的を達するために0.2mm厚の薄い絶縁体層を用いている。特許文献3で用いられているこのような薄い絶縁体層では電極からの電子の放出を十分に抑制することはできず、本発明の効果は期待できないと考えられる。
ノズル13の外面の略全面を、表面に誘電体の露出した被覆体107で被覆することによって、電極14から飛来しノズル13に流入する電子の数を抑制することができる。その結果、電極14とノズル13の間の放電が起きにくくなり、電極14とノズル13の間の印加電圧を増やすことや、距離を狭めることが可能になる。これによって電極14とノズル13の間の電界を強めて原料液の帯電量を高められる。前記効果を有効に発現させるためには、ノズル13の外面の略全面(90%以上の面積)を被覆体107で被覆することが好ましく、特にノズル13の外面の全面(100%の面積)を被覆体107で被覆することが好ましい。また被覆体107をノズル13の先端13aを越えて延出させることによって、ノズル13の先端13aに電子が飛来するのを抑制でき、原料液の帯電量を更に高めることができる。
本実施形態の製造装置においては、被覆体による捕集用電極の被覆と前述の被覆体17による電極14の被覆及び/又は被覆体107によるノズル13の被覆とを組み合わせることもできる。
ノズル20の先端20aと凹曲面Rとの間の距離(最短距離)は、製造装置10におけるノズル13の先端と電極14との間の距離(最短距離)と同様にすることができる。
前記と同様の観点から、ノズル20の先端20aは、凹曲面Rにおける開口端によって画成される円を含む平面内に位置することが好ましい。この場合、ノズル20の先端20aが、開口端によって画成される円の中心から半径10mm以内に配置されることが好ましく、半径5mm以内に配置されることがより好ましく、円の中心に配置されることが更に好ましい。
電極314は全体として凹球面形状をしており、特に略椀形をしている。そしてその内面に凹曲面Rを備え、その開口端の位置に平面状のフランジ部314aを有している。更に電極314は対向する二つの側面の位置に、空気流噴射手段15を配置するための開口320と、空気流噴射手段15から噴射された空気流及びノズル13から噴射されファイバ状になった原料液を通すための開口321を有している。なお電極314は、その内面が凹曲面Rとなっている限りにおいて、その外面の形状は略椀形になっていることを要せず、その他の形状となっていてもよい。
本実施形態の製造装置310を用いた場合にも、先に述べた実施形態の製造装置10及び製造装置18と同様に、被覆体307の作用によって原料液の帯電量を増加させることができる。しかも本実施形態の製造装置310は、製造装置18と同様に、電極314が凹球面形状をしているため、原料液の帯電量の増加が一層顕著となり、しかも製造装置を小型化することができる。このときノズル13の長さは50mm以下であることが好ましく、10mm以下であることが更に好ましく、5mm以下であることが一層好ましい。
ノズル13の開口の直上の位置に、板状の電極14がノズル13の開口に対面して配置されている。ノズル13と電極14は金属等から構成されており導電性を有している。ノズル13と電極14との間には、アース102と金属導線103を介して、電圧発生手段である直流高圧電源401によって直流電圧が印加されるようになっている。ノズル13は図7(b)に示すとおり接地され、陰極となる。これに対して電極14には正電圧が印加され、陽極となる。
前記効果を有効に発現させるためには、ノズル13の外面の略全面(90%以上の面積)を被覆体107で被覆することが好ましく、特にノズル13の外面の全面(100%の面積)を被覆体107で被覆することが好ましい。また被覆体107をノズル13の先端を越えて延出させることによって、ノズル13の先端から電子が放出されるのを抑制でき、原料液の帯電量を更に高めることができる。ノズル13の先端を越えて延出させる、被覆体107の延出部分の長さの好ましい範囲は、製造装置10を用いた実施形態で述べたとおりである。
同様の目的のために、ノズル720の先端720aは、円筒形状の電極710の軸方向に垂直の断面における円の中心近傍に配置され、該軸方向においては先端720aが円筒内部に形成される円柱空間内に配置されていることが好ましい。特に、円筒形状の電極710の軸方向に沿って見たとき、ノズル720の先端720aが、円筒内部に形成される円柱空間内に配置され、かつ電極710の2つの端部のうち、原料液の吐出側の端部から軸の中心までの間に配置されることが好ましい。具体的には、ノズル720の先端720aは、電極710の円筒形状の凹曲面711における開口端によって画成される平面の内側であって、かつ該平面の近傍に位置するように配置されることが有利である。近傍とは、電極710の円筒形状の凹曲面711における開口端によって画成される円の半径をrとしたとき、その円の中心からr/5の距離より内側である。具体的には前記平面よりも1mm以上20mm以下内側に配置することが好ましく、1mm以上15mm以下内側に配置することがより好ましく、1mm以上10mm以下内側に配置することが更に好ましい。ノズル720の先端720aの位置をこのようにすることで、紡糸液を円筒電極の開口端部より前方に排出しやすい点で好ましい。また、ノズル720の先端720aから吐出された原料液が、電極710の円筒形状の凹曲面711に引き寄せられにくくなり、該凹曲面711が該原料液によって汚染されづらくなる。また、こうすることで、ノズル720の先端720aに電界を集中させて帯電量を高められる点で好ましい。
本発明では、電極はノズルと対向する面の略全面が、誘電体で被覆される。更に好ましくはノズルと対向する面の全面が、誘電体で被覆される。ノズルと対向する面とは、ノズルの先端(原料液が噴射する開口部)から臨むことのできる電極の表面のことである。より詳細には、ノズルの先端上の各点から電極に向けて直線を引いたときに電極と最初に接する点の集合のことである。また略全面とは当該面の全表面積の90%以上の面積を占める面を意味し、全面とは当該面の全表面積の100%の面積を占める面を意味する。誘電体は、表面の略全面(90%以上の面積)が誘電体のみで構成されている。誘電体は、表面の全面(100%の面積)が誘電体のみで構成されていることが好ましい。すなわち、本発明の誘電体は、表面に金属などの導電体が非存在としたものが好ましい。単一種の誘電体から構成された誘電体がその典型例であるが、誘電体は複数種の誘電体が積層された複合体であってもよいし、表面が誘電体のみで構成されていれば、内部(表面に露出しない部分)に金属の粒子や層、あるいは空気の層等を含んだ複合体であってもよい。特に電極と誘電体の接合部の一部に空気の層が存在していてもよいが、電極と誘電体の接合を強固にする観点からは電極と誘電体は密着している方が好ましい。なお本発明では、当該誘電体の表面を更に被覆するような物体は存在しないものと想定している。仮に、当該誘電体の表面を更に被覆するような、金属等からなる導電層が存在するならば本発明の効果は低減する。
誘電体730を、電極710の凹曲面711に嵌め合わせた状態においては、所定の接合部材によって電極710と誘電体730とを固定する。
前記の接合部材は誘電体で構成されていることが好ましい。こうすることで、接合部材自身に電気が流れることがなくなり、電極710と誘電体730との接合部から発生する電気力線を抑えることが可能となり、電極710とノズル720との間の電界の乱れを防止することができる。また、接合部材によって電極710と誘電体730とを接合することで、電極710を被覆する誘電体730の種類を変更する場合に、該誘電体730を容易に取り換えることができ、電界紡糸装置701が使いやすくなる。
<1>
ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陽極になり、かつ前記電極が陰極になるように電圧を発生させ、
前記電極は前記ノズルと対向する面の略全面が表面に誘電体の露出した被覆体で被覆され、
前記表面に露出した誘電体の厚みが0.8mm以上であるナノファイバ製造装置。
電極はノズルと対向しない面の一部又はすべてが、表面に誘電体の露出した被覆体で被覆されている<1>に記載のナノファイバ製造装置。
<3>
表面に誘電体の露出した被覆体によって前記ノズルの外面の略全面が被覆されているとともに、該被覆体が該ノズルの先端を越えて延出している<1>又は<2>に記載のナノファイバ製造装置。
<4>
ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陽極になり、かつ前記電極が陰極になるように電圧を発生させ、
表面に誘電体の露出した被覆体によって、前記ノズルの外面の略全面が被覆されているとともに、該被覆体が該ノズルの先端を越えて延出しているナノファイバ製造装置。
<5>
ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陰極になり、かつ前記電極が陽極になるように電圧を発生させ、
表面に誘電体の露出した被覆体によって、前記ノズルの外面の略全面が被覆されているナノファイバ製造装置。
<6>
被覆体が前記ノズルの先端を越えて延出している<5>に記載のナノファイバ製造装置。
前記電極は前記ノズルと対向する面の略全面が、表面に誘電体の露出した被覆体で被覆されている<5>又は<6>に記載のナノファイバ製造装置。
<8>
前記電極は前記ノズルと対向しない面の一部又はすべてが、表面に誘電体の露出した被覆体で被覆されている<7>に記載のナノファイバ製造装置。
<9>
ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陰極になり、かつ前記電極が陽極になるように電圧を発生させ、
前記電極は前記ノズルと対向する面の略全面が表面に誘電体の露出した被覆体で被覆され、
前記表面に露出した誘電体の厚みが0.8mm以上であるナノファイバ製造装置。
<10>
前記電極は前記ノズルと対向しない面の一部又はすべてが、表面に誘電体の露出した被覆体で被覆されている<9>に記載のナノファイバ製造装置。
<11>
捕集手段が捕集用電極を有し、該捕集用電極の略全面が表面に誘電体の露出した被覆体で被覆されている<1>ないし<10>のいずれか1に記載のナノファイバ製造装置。
ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記捕集手段が捕集用電極を有し、該捕集用電極の略全面が表面に誘電体の露出した被覆体で被覆されているナノファイバ製造装置。
<13>
前記表面に露出した誘電体の厚みが0.8mm以上である<2>ないし<8>又は<10>ないし<12>のいずれか1に記載のナノファイバ製造装置。
<14>
前記表面に露出した誘電体の厚みが8mm以上である<1>ないし<13>のいずれか1に記載のナノファイバ製造装置。
<15>
被覆体を構成する、表面に露出した誘電体の厚みは、0.8mm以上、特に2mm以上、とりわけ8mm以上であることが好ましく、被覆体の厚みの上限値は、25mm以下、特に20mm以下、とりわけ15mm以下であることが好ましく、被覆体が単一種又は複数種の誘電体から構成されている場合、例えば被覆体の厚みは0.8mm以上25mm以下、特に2mm以上20mm以下、とりわけ8mm以上15mm以下とすることが好ましい<1>ないし<14>のいずれか1に記載のナノファイバ製造装置。
<16>
電極が板状である<1>ないし<15>のいずれか1に記載のナノファイバ製造装置。
前記空気流噴射手段は、前記ノズルと前記電極の間に空気流を噴射することが可能な位置に配置されており、
原料液から形成されたナノファイバは、前記ノズルから前記電極に向かって伸びていこうとし、
前記空気流噴射手段から噴射された空気流は前記ナノファイバの進行方向を転換させ、捕集手段のある方向に搬送するとともに、該ナノファイバを延伸させる<1>ないし<16>のいずれか1に記載のナノファイバ製造装置。
<18>
電極が凹球面形状をしている<1>ないし<15>のいずれか1に記載のナノファイバ製造装置。
<19>
前記電極における凹曲面が、平面部を全く有していない曲面であるか、平面部を有する複数のセグメントを繋ぎ合わせて全体として凹曲面とみなせる形状となっているか、又は互いに直交する三軸のうち一軸が曲率を有さない帯状部を有する複数の環状セグメントを繋ぎ合わせて全体として凹曲面とみなせる形状となっている<18>に記載のナノファイバ製造装置。
<20>
前記電極における凹曲面は、その任意の位置における法線が前記ノズルの先端又はその近傍を通るような値となっている<18>又は<19>に記載のナノファイバ製造装置。
<21>
前記ノズルの延びる方向が、前記電極の凹曲面における開口端によって画成される円の中心か、又はその中心の近傍と、該凹曲面における最底部に設けられた開口の中心か、又はその中心の近傍とを通るように配置されることが好ましく、とりわけ、凹曲面の開口端によって画成される円を含む平面と、ノズルの延びる方向とが直交するように、該ノズルを配置した<18>ないし<20>のいずれか1に記載のナノファイバ製造装置。
前記ノズルの先端が、電極の凹曲面における開口端によって画成される円を含む平面内に位置するか、又は該平面よりも該凹曲面の内側に位置するように、該ノズルを配置した<18>ないし<21>のいずれか1に記載のナノファイバ製造装置。
<23>
前記空気流噴射手段は、前記ノズルの延びる方向に沿って形成されており、該ノズルの先端の方向に向けて空気流を噴射させることが可能なように形成されており、
前記電極の開口端側から見たとき、前記空気流噴射手段は、前記ノズルを取り囲むように複数設けられており、
前記空気流噴射手段は、前記ノズルを挟んで対称な位置に形成されている。<18>ないし<22>のいずれか1に記載のナノファイバ装置。
<24>
前記ノズルの先端が、前記平面より1~10mm内側に位置するように該ノズルを配置する<22>に記載のナノファイバ製造装置。
<25>
電極が円筒形状をしている<1>ないし<15>のいずれか1に記載のナノファイバ製造装置。
<26>
前記電極は内面が略円筒形状であり、軸方向に垂直の断面における中心近傍にノズル先端が配置され、軸方向においてはノズル先端が円筒内部に形成される円柱空間内に配置されている<25>に記載のナノファイバ製造装置。
前記電極の軸方向に垂直の断面における円又は楕円の離心率は0以上0.6未満であり、好ましくは離心率0の真円である<25>又は<26>に記載のナノファイバ製造装置。
<28>
前記電極の軸方向に垂直な断面における前記ノズルと前記電極との間の距離で定義される半径は、20mm以上100mm以下であり、30mm以上50mm以下であることが好ましい<25>ないし<27>のいずれか1に記載のナノファイバ製造装置。
<29>
円筒形状をしている前記電極の軸方向の長さが20mm以上150mm以下であり、30mm以上80mm以下であることが好ましい<25>ないし<28>のいずれか1に記載のナノファイバ製造装置。
<30>
前記電極は内面が略円筒形状であり、該略円筒の開口端によって画成される円を含む平面内に前記ノズルの先端が位置し、かつ該先端は、該開口端によって画成される円の中心から10mm以内に位置する<25>ないし<29>のいずれか1に記載のナノファイバ製造装置
<31>
円筒形状の前記電極の軸方向に沿って見たとき、前記ノズルの先端が、円筒内部に形成される円柱空間内に配置され、かつ前記電極の2つの端部のうち、原料液の吐出側の端部から軸方向の中心までの間に配置されている<25>ないし<30>のいずれか1に記載のナノファイバ製造装置
前記空気流噴射手段は、前記ノズルの延びる方向に沿って形成されており、該ノズルの先端の方向に向けて空気流を噴射させることが可能なように形成されており、
前記電極の開口端側から見たとき、前記空気流噴射手段は、前記ノズルを取り囲むように複数設けられており、
前記空気流噴射手段は、前記ノズルを挟んで対称な位置に形成されている<25>ないし<31>のいずれか1に記載のナノファイバ装置。
<33>
電極は誘電体によってその全面が被覆されている<25>ないし<32>のいずれか1に記載の電界紡糸装置。
<34>
誘電体の厚みは、0.8mm以上、より好ましくは2mm以上、特に8mm以上であることが好ましく、 25mm以下、より好ましくは20mm以下、特に15mm以下であることが好ましく、0.8mm以上25mm以下、より好ましくは2mm以上20mm以下、特に8mm以上15mm以下とすることが好ましい<25>ないし<33>のいずれか1に記載の電界紡糸装置。
<35>
前記ノズルの先端が、前記電極の凹曲面における円筒形状の開口端によって画成される平面よりも1mm以上10mm以下内側に配置されている<25>ないし<34>のいずれか1に記載の電界紡糸装置。
<36>
誘電体がアルミナ、ベークライト、ナイロン、塩化ビニル樹脂の中から選ばれる少なくとも1種以上である<1>ないし<35>のいずれか1に記載のナノファイバ製造装置。
<37>
誘電体がナイロンである<1>ないし<36>のいずれか1に記載のナノファイバ製造装置。
ノズルの先端と電極との間の距離は、20mm以上、特に30mm以上に設定することが好ましく、上限値は100mm以下、特に50mm以下に設定することが好ましく、例えば両者間の距離は、20mm以上100mm以下に設定することが好ましく、30mm以上50mm以下に設定することが更に好ましい<1>ないし<37>のいずれか1に記載のナノファイバ製造装置。
<39>
空気流の流速は、200m/sec以上、特に250m/sec以上とすることが好ましく、600m/sec以下、特に530m/sec以下とすることが好ましく、200m/sec以上600m/sec以下にすることが好ましく、特に250m/sec以上530m/sec以下であることが好ましい<1>ないし<38>のいずれか1に記載のナノファイバ製造装置。
<40>
ノズルの先端を越えて延出している被覆体のうち延出部分は、ノズルを取り囲む筒状の形態をして中空部を有しており、この中空部がノズルの内部と連通している<3>、<4>又は<6>のいずれか1に記載のナノファイバ製造装置。
<41>
前記ノズルの被覆体の延出部分の長さは、1mm以上であることが好ましく、10mm以上であることが更に好ましく、上限値は、15mm以下であることが好ましく、12mm以下であることが更に好ましく、1mm以上15mm以下、特に10mm以上12mm以下であることが好ましい<3>、<4>又は<6>のいずれか1に記載のナノファイバ製造装置。
前記ノズルの外径は、その下限値を好ましくは300μm以上、更に好ましくは400μm以上に設定することができ、その上限値を好ましくは4000μm以下、更に好ましくは3000μm以下に設定することができ、例えば好ましくは300μm以上4000μm以下、更に好ましくは400μm以上3000μm以下に設定することができる、<1>ないし<41>のいずれか1に記載のナノファイバ製造装置。
<43>
前記ノズルの長さは50mm以下であることが好ましく、10mm以下であることが更に好ましく、5mm以下であることが一層好ましい、<1>ないし<42>のいずれか1に記載のナノファイバ製造装置。
<44>
前記電極又は前記ノズルは、前記被覆体で略全面(90%以上の面積)が被覆され、好ましくは前記被覆体で全面(100%の面積)が被覆されている<1>ないし<43>のいずれか1に記載のナノファイバ製造装置。
<45>
表面に誘電体の露出した前記被覆体は、(該被覆体の)該表面の略全面(90%以上の面積)が誘電体のみで構成されており、好ましくは、該被覆体は、(該被覆体の)該表面の全面(100%の面積)が誘電体のみで構成されている<1>ないし<44>のいずれか1に記載のナノファイバ製造装置。
<46>
前記原料液として、ファイバ形成の可能な高分子化合物が溶媒に溶解又は分散した溶液あるいは高分子化合物を加熱、溶融した融液を用いる、<1>ないし<45>のいずれか1に記載のナノファイバ製造装置。
前記電極と前記被覆体を、誘電体から構成される接合部材で接合した<1>ないし<46>のいずれか1に記載のナノファイバ製造装置。
<48>
前記接合部材は誘電体で構成されている<47>に記載のナノファイバ製造装置。
<49>
前記接合部材は粘着剤又は誘電体で構成されたネジ又は木製のネジである<47>又は<48>に記載のナノファイバ製造装置。
<50>
前記接合部材がネジであり、前記被覆体にネジ穴が形成されており、該ネジ穴にザグリ加工がされている<49>に記載のナノファイバ製造装置。
<51>
前記空気流噴射手段は誘電体で構成されている<1>ないし<50>のいずれか1に記載のナノファイバ製造装置。
前記空気流噴射手段は、前記空気流が噴出する複数の開口部を有し、該開口部は細幅の隙間からなる空間であるか、又は略柱状の空間であり、
前記空気流噴射手段は、前記電極と前記ノズルとの間の空間に前記開口部が臨むように配置されている<1>ないし<51>のいずれか1に記載のナノファイバ製造装置。
<53>
前記空気流噴射手段はマニホールド構造を有している<1>ないし<52>のいずれか1に記載のナノファイバ製造装置。
<54>
前記空気流噴射手段に形成された開口部の配置を自由に設定することができる<1>ないし<53>のいずれか1に記載のナノファイバ製造装置。
<55>
前記空気流噴射手段に形成された開口部は略柱状の空間からなり、
前記開口部を3列の千鳥格子状に配置して空気流の隙間を埋めるようにした<1>ないし<54>のいずれか1に記載のナノファイバ製造装置。
<56>
前記空気流噴射手段に形成された開口部は、前記電極が凹球面形状の場合は該電極の開口部を正面視したとき、前記ノズルを中心として同心円状に配置されている<1>ないし<55>のいずれか1に記載のナノファイバ製造装置。
前記空気流噴射手段に形成された開口部の形状は、円形、楕円形、三角形、四角形又は多角形である<1>ないし<56>のいずれか1に記載のナノファイバ製造装置。
<58>
前記空気流噴射手段に形成された開口部が円形の場合、直径の範囲は0.1mm以上1.5mm以下であることが好ましく、0.3mm以上1.2mm以下であることがより好ましい<1>ないし<57>のいずれか1に記載のナノファイバ製造装置。
<59>
前記空気流噴射手段に形成された開口部のピッチは、該開口部が千鳥格子状に配置されている場合、3mm以上15mm以下であることが好ましく、5mm以上12mm以下であることがより好ましい<1>ないし<58>のいずれか1に記載のナノファイバ製造装置。
<60>
前記空気流噴射手段に形成された開口部が前記ノズルを中心として同心円状に配置されている場合、隣り合う開口部と該ノズルの中心とがなす角度は、5°以上60°以下であることが好ましく、8°以上30°以下であることがより好ましい<1>ないし<59>のいずれか1に記載のナノファイバ製造装置。
<61>
前記空気流噴射手段に形成された開口部が前記ノズルを中心として同心円状に配置されている場合、ピッチ円の半径は6mm以上15mm以下であることが好ましく、7.5mm以上12.5mm以下であることがより好ましい<1>ないし<60>のいずれか1に記載のナノファイバ製造装置。
<1>ないし<61>のいずれか1に記載のナノファイバ製造装置を使用してナノファイバを製造するナノファイバ製造方法。
<63>
<1>ないし<61>のいずれか1に記載のナノファイバ製造装置を使用して製造したナノファイバからなるナノファイバ成型体。
図1に示す製造装置10における原料液の帯電量を評価するため、水をモデル原料液として用い、水の帯電量を測定した。帯電量の測定方法は後述する。水はファイバ化しないため、帯電した液の捕集が容易であり、後述の方法で簡便に帯電量を測定することができる。ノズル13から水を噴射する速度は1g/minとし、ノズル13の内径は2mm、長さは50mmとした。電極14の平面部(ノズル13と対向する面)の面積は81cm2(縦9cm×横9cm)とし、該面の全面を誘電体(ナイロン((株)ミスミ製MCナイロンMCA-90-90-10)、ベークライト((株)ミスミ製BLA-90-90-10)、アルミナ((株)ミスミ製CEMN-90-90-10))からなる被覆体17でそれぞれ被覆した。誘電体の厚みはいずれも10mmとした。ノズル13の先端と電極14との距離(最短距離)は50mmとした。
また、電極14とノズル13の間に直流電圧(-20kV、-30kV、-40kV)を印加し、電極14とノズル13の間に流れる電流(以下、漏れ電流と呼ぶ)の量を測定するとともに放電の有無を観察した。漏れ電流の測定は、電圧発生手段として用いた高電圧発生装置(松定プレシジョン(株)製のHAR-60R1-LF)に内蔵されている電流計を用いていった。なお漏れ電流に及ぼす原料液の影響を排除するため、原料液は噴射しなかった。これらの結果を表1に示す。
本比較例は、実施例1において電極14を誘電体からなる被覆体17で被覆しなかった例である。これ以外は実施例1と同様の操作を行い、同様の測定をいった。結果を表1に示す。
本比較例は、被覆体17として、表面に金属からなる導電層(導体層)の露出した被覆体を用いた例である。実施例1ないし3において、誘電体の表面に厚さ0.2mmのアルミニウムテープ(SLIONTEC(登録商標))を更に積層し、被覆体を形成した。本比較例に対応する例は特許文献2の実施例に見られる。それ以外は実施例1と同様の操作を行い、同様の測定をいった。結果を表1に示す。
また実施例1ないし3と、比較例2ないし4との対比から明らかなとおり、表面に金属からなる導電層(導体層)の露出した被覆体を用いた各比較例では、電圧の印加とともに漏れ電流が顕著に増加し、-40kVの印加では放電が発生した。また、モデル原料液として用いた水の帯電量は各実施例よりも小さくなった。
図3及び図4に示す製造装置18を用いて、実施例1ないし3と同様な方法で、水の帯電量及び漏れ電流を測定した。
電極19の凹曲面Rは半径45mmの半球とし、ノズル20の先端20aを半球の中心に設置した。このとき先端20aは凹曲面Rにおける開口端によって画成される円を含む平面内に位置する。ノズルの延びる方向は半球の回転対称軸と一致させた。図4と同様に、電極19の凹曲面Rの全面及びフランジ部19aの一部を厚み10mmの誘電体(モノマーキャストナイロン(白銅製MC901切板(青)))からなる被覆体207で被覆した。それ以外の測定条件は実施例1ないし3と同じである。これらの結果を表2に示す。
図1に示す製造装置10において、被覆体17に、厚さ0.2mmのポリプロピレンシートを複数枚、積層した積層体を用いて、漏れ電流を評価した。
被覆体17にポリプロピレンのシートを用いた以外は、製造装置10の構造は実施例1ないし3と同一とした。被覆体17には、厚さ0.2mmのポリプロピレンシートを4枚積層した積層体と、5枚積層した積層体を用いた。積層した各シートは隣接するシートと密着させた。本実施例の場合、被覆体17が単一種の誘電体(ポリプロピレン)から構成されているため、「表面に露出した誘電体の厚み」は積層したシートの総厚みとして定義され、それは被覆体17の厚みに等しい。したがって、4枚積層した被覆体17の厚みは0.8mmとなり、5枚積層した被覆体17の厚みは1.0mmとなる。
電極14の平面部(ノズル13と対向する面)の全面を前記ポリプロピレンシートの積層体で被覆し、電極14とノズル13の間に直流電圧-40kVを印加した。そして実施例1ないし3と同様の方法で、電極14とノズル13の間に流れる漏れ電流の量を測定するとともに放電の有無を観察した。これらの結果を表3に示す。
実施例5と同様の実験を、ポリプロピレンシートの積層枚数を0枚、1枚、2枚、3枚にしていった。このときの被覆体17の厚み(表面に露出した誘電体の厚み)はそれぞれ0mm、0.2mm、0.4mm、0.6mmとなる。結果を表3に示す。
図1に示す製造装置10において、被覆体17に、厚さ2mm、5mm、8mm、10mmのベークライトを用いて、漏れ電流と水の帯電量を評価した。
被覆体17に前記厚みのベークライトを用いた以外は、製造装置10の構造は実施例1ないし3と同一とした。本実施例の場合も、被覆体17が単一種の誘電体(ベークライト)から構成されているため、「表面に露出した誘電体の厚み」は誘電体(ベークライト)の厚み、すなわち被覆体17の厚みに等しい。
電極14の平面部(ノズル13と対向する面)の全面を前記ベークライトで被覆し、電極14とノズル13の間に直流電圧-40kVを印加した。そして実施例1ないし3と同様の方法で、電極14とノズル13の間に流れる漏れ電流の量を測定するとともに放電の有無を観察した。また、実施例1ないし3と同様な方法で、モデル原料液として用いた水の帯電量を測定した。これらの結果を表4に示す。
図1に示す製造装置10において、電極14を被覆体17で被覆せず、代わりに、ノズル13の外面の全面を被覆体107で被覆して、漏れ電流を評価した。
被覆体107には厚さ2mmの塩化ビニルを用い、ノズル13の外面の全面を被覆するとともに、被覆体107を、ノズル13の先端を越えて10mm及び1mm延出させた。そして電極14は被覆体17で被覆しなかった。これら以外は、実施例1ないし3と同一の構造の製造装置10を用い、実施例1ないし3と同様な方法で漏れ電流の量を測定するとともに放電の有無を観察した。結果を表5に示す。
実施例7において、ノズル13の先端を越えて被覆体107を延出させず、ノズル13の外面のみ又は外面の一部を被覆体107で被覆し、漏れ電流を評価した。
長さ50mmのノズル13の外面のうち、ノズルの後端(根元)から50mm、49mm、25mmまでの領域を被覆体107(厚さ2mmの塩化ビニル)で被覆した。便宜的にこれらを、延出部分の長さがそれぞれ0mm、-1mm、-25mmであると表記する。例えば、延出部分の長さが-25mmのとき、ノズル13の先端から25mmまでの領域は被覆体で被覆されず、ノズルが露出している。これらの被覆体を用いた以外は、実施例7と同様にして漏れ電流の量を測定するとともに放電の有無を観察した。結果を表5に示す。
図1に示す製造装置10において、電極14を被覆体17で被覆するとともに、ノズル13の外面の全面を被覆体107で被覆して、漏れ電流を評価した。被覆体107には厚さ2mmの塩化ビニルを用い、ノズル13の外面の全面を被覆するとともに、被覆体107を、ノズル13の先端を越えて1mmから10mmまで1mm刻みに延出させた。これら以外は、実施例1と同一の構造の製造装置10を用い、実施例1ないし3と同様な方法で漏れ電流の量を測定するとともに放電の有無を観察した。なお本実施例では電極14は厚さ10mmのMCナイロンからなる被覆体17で被覆されている。結果を表6に示す。
実施例8において、ノズル13の先端を越えて被覆体107を延出させず、ノズル13の外面のみ又は外面の一部を被覆体107で被覆し、漏れ電流を評価した。
長さ50mmのノズル13の外面のうち、ノズルの後端(根元)から50mm及び25mmまでの領域を被覆体107(厚さ2mmの塩化ビニル)で被覆した。便宜的にこれらを、延出部分の長さがそれぞれ0mm、-25mmであると表記する。例えば、延出部分の長さが-25mmのとき、ノズル13の先端から25mmまでの領域は被覆体で被覆されず、ノズルが露出している。これらの被覆体を用いた以外は、実施例8と同様にして漏れ電流の量を測定するとともに放電の有無を観察した。結果を表6に示す。
図8に示す製造装置510を用いてナノファイバの製造をいった。原料液としてプルラン15%水溶液を用いた。ノズル13から原料液を噴射する速度は1g/minとし、ノズル13の内径は2mm、長さは50mmとした。電極14の平面部(ノズル13と対向する面)の面積を81cm2(縦9cm×横9cm)とし、該面の全面をベークライトからなる被覆体17で被覆した。ベークライトの厚みは10mmとした。空気流噴射手段15Aから流量100L/minの空気流を噴射した。空気流噴射手段15Aの前面に形成された開口部151Aの配置は、水平方向Hのピッチが10mmで、鉛直方向Vのピッチが10mmであり、水平方向Hに延びる開口部列が、鉛直方向Vに沿って3列配置された千鳥格子状とした。各開口部は円柱状の空間からなり、その直径は1mmであった。ノズル13の先端と電極14との距離(最短距離)は40mmとし、ノズル13と電極14の間に-30kVの電圧を印加した。得られたナノファイバを走査型電子顕微鏡(SEM)で撮影した写真を図21(a)に示す。
本比較例は、図1に示す製造装置10の電極14を球状電極(凸球面形状をした電極)に変更し、かつ電極14を被覆体17で被覆していない製造装置を用いてナノファイバの製造をいった結果である。球状電極の直径は25mmとし、ノズル13の先端の鉛直直上に球の中心を配置した。ノズル13の先端と球状電極との距離(最短距離)は75mmとした。それ以外の装置構造は実施例9と同様であり、同様の条件にて紡糸をいった。得られたナノファイバを走査型電子顕微鏡(SEM)で撮影した写真を図21(b)に示す。
図3及び図4に示す製造装置18を用いてナノファイバの製造をいった。原料液としてプルラン25%水溶液を用いた。ノズル20から原料液を噴射する速度を1g/minとし、空気流噴射手段23から空気流を噴射する速度は200L/minとした。ノズル20と電極19の間に-30kVの電圧を印加し、それ以外の装置構造は実施例4と同様にして紡糸をいった。得られたナノファイバを走査型電子顕微鏡(SEM)で撮影した写真を図22に示す。
図13及び図14に示す電界紡糸装置701における原料液の帯電量を評価するため、水をモデル原料液として用い、水の帯電量を測定した。帯電量の測定方法は後述する。水はファイバ化しないため、帯電した液の捕集が容易であり、後述の方法で簡便に帯電量を測定することができる。ノズル720から水を噴射する速度は1g/minとし、ノズル720の内径は2000μm、長さは50mmとした。電極710は、長さが50mmで、内径が半径45mmで、厚み3mmの円筒(機械構造用炭素鋼S45C)とし、ノズル720の先端720aは円筒形状の凹曲面711における一方の開口端によって画成される円を含む平面内に位置するようにした。ノズルの延びる方向は円筒の中心軸と一致させた。実施例11は図13及び図14と同様に、電極710の凹曲面711の全面を厚み10mmの誘電体730(モノマーキャストナイロン(白銅(株)製MC901切板(青)))で被覆した。実施例12は電極710の吐出方向側の端面も被覆した。実施例13では、実施例12の被覆に加え、更に電極710の外周面の全面を被覆した。いずれの実施例においても、電極710に-5kVの直流電圧を印加した。ノズル720は接地した。
比較例9では、図13に示す電界紡糸装置701の電極710を被覆している誘電体730を、電極710の内面から15mm離した位置に配置した製造装置を用い、水の帯電量を測定した。誘電体730は内径が半径30mmの円筒とした。比較例10では、図13に示す電界紡糸装置701の電極710を誘電体730で被覆しない製造装置を用い、水の帯電量を測定した。それ以外の測定条件は実施例11ないし13と同じである。これらの結果を表7に示す。
図13及び図14に示す電界紡糸装置701におけるノズル720の先端720aの位置を電極710の軸方向に対して電極710の開口端に形成される平面から内側寄りへ配置したときの帯電量を測定した。同時に、水に替えて原料液を用い、該原料液による電極710及び電極710を被覆している誘電体730の汚染状態を評価した。評価基準は後述する。測定する条件は実施例11ないし13を測定したときと同様であり、(i)ノズル720と対向する内面を被覆した場合(実施例11と同様)、(ii)ノズル720と対向する内面と開口端面を被覆した場合(実施例12と同様)、及び(iii)ノズル720の内外面及び開口端面の全面を被覆した場合(実施例13と同様)の3条件で測定した。実施例14は実施例11ないし13と同様にノズル720の先端720aの位置を電極710の開口端に形成される平面上の位置とした。実施例15はノズル720の先端720aの位置を電極710の開口端に形成される平面から内側へ16mmの位置とした。実施例16はノズル720の先端720aの位置を電極710の開口端に形成される平面から内側へ32mmの位置とした。これらの結果を表9に示す。
A:原料液による電極710及び誘電体730の汚染が少ない。
B:原料液による電極710及び誘電体730の汚染がやや見られる。
C:原料液による電極710及び誘電体730の汚染が多い。
比較例11では、図13及び図14に示す電界紡糸装置701におけるノズル720の先端720aの位置を電極710の軸方向に対して電極の開口端に形成される平面から外側へ配置したときの帯電量を測定した。同時に、水に代えて原料液を用いて、該原料液による電極710及び電極710を被覆している誘電体730の汚染状態を評価した。測定する条件は実施例1ないし3を測定したときと同様であり、(i)ノズル720と対向する内面を被覆した場合(実施例11と同様)、(ii)ノズル720と対向する内面と開口端面を被覆した場合(実施例12と同様)、(iii)ノズル720の内外面及び開口端面の全面を被覆した場合(実施例13と同様)の3条件で測定した。ノズル720の先端720aの位置は電極710の開口端に形成される平面から外側へ16mmの位置とした。これらの結果を表9に示す。
また、表9に示す結果から明らかなとおり、実施例14、15及び比較例11では原料液による電極710及び誘電体730の汚染が少ないことが判る。また、実施例16では原料液による電極710及び誘電体730の汚染がやや見られることが判る。
これらの結果から、ノズル720の先端720aの位置を電極710の凹曲面の内側に配置することで、帯電量を高められることが判った。また、ノズル720の先端720aの位置を、電極710における原料液の吐出側の開口端寄りに配置することで、原料液が電極710及び誘電体730に付着しにくくなり、原料液による電極710及び誘電体730の汚染を低減できることが判った。
図13に示す電界紡糸装置701を用いてナノファイバの製造をいった。誘電体730の被覆条件は実施例13と同様とした。原料液としてプルラン15質量%水溶液を用いた。ノズル720から原料液を噴射する速度は1g/minとし、空気流噴射手段723から流量150L/minの空気流を噴出し、ノズル720と電極710の間に-20kVの電圧を印加し、ノズル720の先端720aから捕集板までの距離は1200mmとした。得られたナノファイバを走査型電子顕微鏡(SEM)で撮影した写真を図23(a)及び図23(b)に示す。
本比較例は、図13に示す電界紡糸装置701の電極710を誘電体730で被覆していない製造装置を用いてナノファイバの製造をいった結果である。それ以外の装置構造は実施例17と同様であり、印加する電圧を-10kVとした以外は実施例17と同様の条件にて紡糸をいった。印加する電圧は、ナノファイバの製造が可能である値に設定した。得られたナノファイバを走査型電子顕微鏡(SEM)で撮影した写真を図24(a)及び図24(b)に示す。
Claims (19)
- ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陽極になり、かつ前記電極が陰極になるように電圧を発生させ、
前記電極は前記ノズルと対向する面の略全面が、表面に誘電体の露出した被覆体で被覆され、
前記表面に露出した誘電体の厚みが0.8mm以上であるナノファイバ製造装置。 - 電極はノズルと対向しない面の一部又はすべてが、表面に誘電体の露出した被覆体で被覆されている請求項1に記載のナノファイバ製造装置。
- 表面に誘電体の露出した被覆体によって前記ノズルの外面の略全面が被覆されているとともに、該被覆体が該ノズルの先端を越えて延出している請求項1又は2に記載のナノファイバ製造装置。
- ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陽極になり、かつ前記電極が陰極になるように電圧を発生させ、
表面に誘電体の露出した被覆体によって、前記ノズルの外面の略全面が被覆されているとともに、該被覆体が該ノズルの先端を越えて延出しているナノファイバ製造装置。 - ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陰極になり、かつ前記電極が陽極になるように電圧を発生させ、
表面に誘電体の露出した被覆体によって、前記ノズルの外面の略全面が被覆されているナノファイバ製造装置。 - 被覆体が前記ノズルの先端を越えて延出している請求項5に記載のナノファイバ製造装置。
- 前記電極は前記ノズルと対向する面の略全面が、表面に誘電体の露出した被覆体で被覆されている請求項5又は6に記載のナノファイバ製造装置。
- 前記電極は前記ノズルと対向しない面の一部又はすべてが、表面に誘電体の露出した被覆体で被覆されている請求項7に記載のナノファイバ製造装置。
- ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記電圧発生手段は、前記ノズルが陰極になり、かつ前記電極が陽極になるように電圧を発生させ、
前記電極は前記ノズルと対向する面の略全面が、表面に誘電体の露出した被覆体で被覆され、
前記表面に露出した誘電体の厚みが0.8mm以上であるナノファイバ製造装置。 - 前記電極は前記ノズルと対向しない面の一部又はすべてが、表面に誘電体の露出した被覆体で被覆されている請求項9に記載のナノファイバ製造装置。
- 捕集手段が捕集用電極を有し、該捕集用電極の略全面が、表面に誘電体の露出した被覆体で被覆されている請求項1ないし10のいずれか一項に記載のナノファイバ製造装置。
- ナノファイバ製造用の原料液を噴射する導電性のノズルを備えた原料噴射手段と、
前記ノズルと離間して配置された電極と、
前記ノズルと前記電極の間に電圧を発生させる電圧発生手段と、
前記ノズルと前記電極の間に空気流を噴射することが可能に配置された空気流噴射手段と、
ナノファイバを捕集する捕集手段と、を備えたナノファイバ製造装置であって、
前記捕集手段が捕集用電極を有し、該捕集用電極の略全面が、表面に誘電体の露出した被覆体で被覆されているナノファイバ製造装置。 - 前記表面に露出した誘電体の厚みが0.8mm以上である請求項2ないし8又は請求項10ないし12のいずれか一項に記載のナノファイバ製造装置。
- 前記表面に露出した誘電体の厚みが8mm以上である請求項1ないし13のいずれか一項に記載のナノファイバ製造装置。
- 電極が凹球面形状をしている請求項1ないし14のいずれか一項に記載のナノファイバ製造装置。
- 電極が円筒形状をしている請求項1ないし14のいずれか一項に記載のナノファイバ製造装置。
- 誘電体がアルミナ、ベークライト、ナイロン、塩化ビニル樹脂の中から選ばれる少なくとも1種以上である請求項1ないし16のいずれか一項に記載のナノファイバ製造装置。
- 請求項1ないし17のいずれか一項に記載のナノファイバ製造装置を使用してナノファイバを製造するナノファイバ製造方法。
- 請求項1ないし17のいずれか一項に記載のナノファイバ製造装置を使用して製造したナノファイバからなるナノファイバ成型体。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016014202A (ja) * | 2014-07-02 | 2016-01-28 | 花王株式会社 | 電界紡糸装置及びそれを備えたナノファイバ製造装置 |
JP2016204816A (ja) * | 2015-04-15 | 2016-12-08 | 花王株式会社 | 電界紡糸装置 |
JP2017031517A (ja) * | 2015-07-30 | 2017-02-09 | 花王株式会社 | 電界紡糸装置 |
JP2021070906A (ja) * | 2019-10-28 | 2021-05-06 | 花王株式会社 | 繊維堆積体の製造方法、及び膜の製造方法 |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
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JP6904787B2 (ja) * | 2017-05-22 | 2021-07-21 | 花王株式会社 | 電界紡糸装置 |
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JP6882409B2 (ja) * | 2018-10-03 | 2021-06-02 | 花王株式会社 | 被膜の製造装置 |
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CA3129491A1 (en) * | 2019-02-14 | 2020-08-20 | The Uab Research Foundation | An alternating field electrode system and method for fiber generation |
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RU198693U1 (ru) * | 2020-02-11 | 2020-07-22 | Акционерное общество "МИКАРД-ЛАНА" | Игла для электрического воздействия на опухоль в теле человека или животного |
US20220042206A1 (en) * | 2020-08-05 | 2022-02-10 | Nano And Advanced Materials Institute Limited | Particle-coated fiber and method for forming the same |
KR102481109B1 (ko) * | 2020-12-07 | 2022-12-27 | (주) 로도아이 | 나노섬유 제조 장치 |
KR102484049B1 (ko) * | 2020-12-07 | 2023-01-04 | (주) 로도아이 | 나노섬유 제조 장치 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009013535A (ja) | 2007-07-05 | 2009-01-22 | Panasonic Corp | ナノファイバ製造装置、ナノファイバ製造方法 |
JP2010059557A (ja) | 2008-09-01 | 2010-03-18 | Panasonic Corp | ナノファイバ製造装置、ナノファイバ製造方法 |
JP2010189782A (ja) * | 2009-02-16 | 2010-09-02 | Panasonic Corp | ナノファイバ製造装置、ナノファイバ製造方法 |
JP2011102455A (ja) | 2009-10-15 | 2011-05-26 | Tokyo Institute Of Technology | 電界紡糸方法および電界紡糸装置 |
JP2011127234A (ja) * | 2009-12-15 | 2011-06-30 | Nanofactory Japan Co Ltd | ナノファイバー製造方法 |
JP2011140740A (ja) * | 2009-12-10 | 2011-07-21 | Panasonic Corp | ナノファイバ製造装置、および、ナノファイバ製造方法 |
JP2012107364A (ja) | 2010-11-18 | 2012-06-07 | Nanofactory Japan Co Ltd | ナノファイバー製造方法 |
WO2014057927A1 (ja) * | 2012-10-11 | 2014-04-17 | 花王株式会社 | 電界紡糸装置及びそれを備えたナノファイバ製造装置 |
JP2014111850A (ja) * | 2012-12-05 | 2014-06-19 | Mitsuhiro Takahashi | 溶融電界紡糸方式およびこれを使用して生成したナノ繊維構造体。 |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6318647B1 (en) * | 1999-08-18 | 2001-11-20 | The Procter & Gamble Company | Disposable cartridge for use in a hand-held electrostatic sprayer apparatus |
US20070031607A1 (en) * | 2000-12-19 | 2007-02-08 | Alexander Dubson | Method and apparatus for coating medical implants |
KR100406981B1 (ko) | 2000-12-22 | 2003-11-28 | 한국과학기술연구원 | 전하 유도 방사에 의한 고분자웹 제조 장치 및 그 방법 |
US6685956B2 (en) * | 2001-05-16 | 2004-02-03 | The Research Foundation At State University Of New York | Biodegradable and/or bioabsorbable fibrous articles and methods for using the articles for medical applications |
US6713011B2 (en) | 2001-05-16 | 2004-03-30 | The Research Foundation At State University Of New York | Apparatus and methods for electrospinning polymeric fibers and membranes |
US20030211135A1 (en) * | 2002-04-11 | 2003-11-13 | Greenhalgh Skott E. | Stent having electrospun covering and method |
CZ294274B6 (cs) * | 2003-09-08 | 2004-11-10 | Technická univerzita v Liberci | Způsob výroby nanovláken z polymerního roztoku elektrostatickým zvlákňováním a zařízení k provádění způsobu |
WO2005042813A1 (en) * | 2003-10-30 | 2005-05-12 | Clean Air Technology Corp. | Electrostatic spinning equipment and method of preparing nano fiber using the same |
CA2567465C (en) * | 2004-05-21 | 2011-08-09 | Craig M. Whitehouse | Charged droplet sprayers |
US7390760B1 (en) * | 2004-11-02 | 2008-06-24 | Kimberly-Clark Worldwide, Inc. | Composite nanofiber materials and methods for making same |
JP5046651B2 (ja) * | 2004-11-19 | 2012-10-10 | 帝人株式会社 | 円筒体の製造方法 |
JP2006283240A (ja) | 2005-04-01 | 2006-10-19 | Oji Paper Co Ltd | ウェブ製造装置 |
US8303874B2 (en) | 2006-03-28 | 2012-11-06 | E I Du Pont De Nemours And Company | Solution spun fiber process |
CZ299549B6 (cs) * | 2006-09-04 | 2008-08-27 | Elmarco, S. R. O. | Rotacní zvláknovací elektroda |
KR20090082376A (ko) * | 2006-11-24 | 2009-07-30 | 파나소닉 주식회사 | 나노 파이버 및 고분자 웹의 제조방법과 장치 |
JP5224704B2 (ja) | 2007-03-14 | 2013-07-03 | 株式会社メック | ナノ・ファイバ製造方法および装置 |
US8540504B2 (en) | 2007-04-20 | 2013-09-24 | National Applied Research Laboratories | Equipment for electrospinning |
TWI315358B (en) * | 2007-04-20 | 2009-10-01 | Nat Applied Res Laboratories | Electrospinning equipment and the method thereon |
KR101030824B1 (ko) | 2008-12-30 | 2011-04-22 | 주식회사 효성 | 전기방사용 절연 노즐팩 및 이를 포함하는 전기방사장치 |
JP2010180499A (ja) | 2009-02-04 | 2010-08-19 | Panasonic Corp | ナノファイバ製造装置、ナノファイバ製造方法 |
US8637109B2 (en) | 2009-12-03 | 2014-01-28 | Cook Medical Technologies Llc | Manufacturing methods for covering endoluminal prostheses |
JP5486754B2 (ja) | 2009-12-21 | 2014-05-07 | 国立大学法人東京工業大学 | 電界紡糸方法および電界紡糸装置 |
KR101166675B1 (ko) | 2010-03-24 | 2012-07-19 | 김한빛 | 방사영역에서의 온도와 습도를 조절할 수 있는 나노섬유제조용 전기방사장치 |
US8551390B2 (en) | 2010-04-12 | 2013-10-08 | The UAB Foundation | Electrospinning apparatus, methods of use, and uncompressed fibrous mesh |
JP5580670B2 (ja) | 2010-06-29 | 2014-08-27 | 花王株式会社 | ナノファイバ積層シート |
US9125811B2 (en) | 2010-06-29 | 2015-09-08 | Kao Corporation | Nanofiber laminate sheet |
JP5698509B2 (ja) * | 2010-12-06 | 2015-04-08 | トップテック・カンパニー・リミテッドTOPTEC Co., Ltd. | ナノ繊維製造装置 |
CZ304097B6 (cs) | 2012-01-19 | 2013-10-16 | Contipro Biotech S.R.O. | Zvláknovací kombinovaná tryska pro výrobu nano- a mikrovlákenných materiálu |
US20150122651A1 (en) * | 2012-03-30 | 2015-05-07 | Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. | Method and Fluidic Microsystem for Generating Droplets Dispersed in a Continuous Phase |
CN102776582A (zh) * | 2012-05-24 | 2012-11-14 | 东华大学 | 一种自动化控制的多喷头静电纺丝设备 |
-
2014
- 2014-06-09 JP JP2014118569A patent/JP5948370B2/ja active Active
- 2014-08-07 WO PCT/JP2014/070820 patent/WO2015020129A1/ja active Application Filing
- 2014-08-07 RU RU2016107138/12A patent/RU2600903C1/ru active
- 2014-08-07 US US14/910,356 patent/US10612162B2/en active Active
- 2014-08-07 CN CN201480042679.9A patent/CN105431577B/zh active Active
- 2014-08-07 KR KR1020167003209A patent/KR101715580B1/ko active IP Right Grant
- 2014-08-07 EP EP14834044.1A patent/EP3031959B1/en active Active
- 2014-08-07 BR BR112016002711-6A patent/BR112016002711B1/pt not_active IP Right Cessation
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009013535A (ja) | 2007-07-05 | 2009-01-22 | Panasonic Corp | ナノファイバ製造装置、ナノファイバ製造方法 |
JP2010059557A (ja) | 2008-09-01 | 2010-03-18 | Panasonic Corp | ナノファイバ製造装置、ナノファイバ製造方法 |
JP2010189782A (ja) * | 2009-02-16 | 2010-09-02 | Panasonic Corp | ナノファイバ製造装置、ナノファイバ製造方法 |
JP2011102455A (ja) | 2009-10-15 | 2011-05-26 | Tokyo Institute Of Technology | 電界紡糸方法および電界紡糸装置 |
JP2011140740A (ja) * | 2009-12-10 | 2011-07-21 | Panasonic Corp | ナノファイバ製造装置、および、ナノファイバ製造方法 |
JP2011127234A (ja) * | 2009-12-15 | 2011-06-30 | Nanofactory Japan Co Ltd | ナノファイバー製造方法 |
JP2012107364A (ja) | 2010-11-18 | 2012-06-07 | Nanofactory Japan Co Ltd | ナノファイバー製造方法 |
WO2014057927A1 (ja) * | 2012-10-11 | 2014-04-17 | 花王株式会社 | 電界紡糸装置及びそれを備えたナノファイバ製造装置 |
JP2014111850A (ja) * | 2012-12-05 | 2014-06-19 | Mitsuhiro Takahashi | 溶融電界紡糸方式およびこれを使用して生成したナノ繊維構造体。 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3031959A4 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016014202A (ja) * | 2014-07-02 | 2016-01-28 | 花王株式会社 | 電界紡糸装置及びそれを備えたナノファイバ製造装置 |
JP2016204816A (ja) * | 2015-04-15 | 2016-12-08 | 花王株式会社 | 電界紡糸装置 |
JP2017031517A (ja) * | 2015-07-30 | 2017-02-09 | 花王株式会社 | 電界紡糸装置 |
JP2021070906A (ja) * | 2019-10-28 | 2021-05-06 | 花王株式会社 | 繊維堆積体の製造方法、及び膜の製造方法 |
WO2021085394A1 (ja) * | 2019-10-28 | 2021-05-06 | 花王株式会社 | 繊維堆積体の製造方法、膜の製造方法及び膜の付着方法 |
US11773512B2 (en) | 2019-10-28 | 2023-10-03 | Kao Corporation | Fiber deposit production method, membrane production method, and membrane adhesion method |
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BR112016002711B1 (pt) | 2022-02-22 |
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