JP2011084842A - Nanofiber film production apparatus and nanofiber film production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nanofiber film production apparatus which can accumulate nanofibers in the end portion of an electric conductive film in a state reaching up to the back side of the conductive film by a simple method in electrospinning, and to provide a nanofiber film production method. <P>SOLUTION: In the case that a target accumulation region for forming the accumulation film 30 of nanofibers 10a on a collection sheet 11 composed of an electroconductive film includes a front accumulation region C disposed on the front surface 11a side facing nozzles 5a and a back accumulation region D disposed near to the end portion 11c, produced nanofibers 10a poured down on the outside of the end portion 11c and the nozzle 5a is placed at places where the produced nanofibers 10a poured down on the outside are electrically adsorbed to the back accumulation region D. Thereby, the nanofibers 10a can be accumulated up to the back surface side in the end portion 11c of the collection sheet 11 by the simple method in the electrospinning. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a nanofiber film manufacturing apparatus and a nanofiber film manufacturing method for manufacturing a nanofiber deposited film made of a polymer material.

  An electrospinning (charge induced spinning) method is known as a method for producing a fibrous material (nanofiber) having a submicron-scale diameter. In this electrospinning method, a raw material liquid in which a polymer substance such as a resin is dispersed or dissolved in a solvent is caused to flow out into the space by a nozzle, etc. The nanofibers are generated by electrically stretching the raw material liquid by the Coulomb force that interacts with the electric charge.

  By collecting the nanofibers generated in this way with a collection sheet, a polymer web (nanofiber film) in which nanofibers made of a polymer substance are deposited in a non-woven fabric is formed (for example, patent document) 1). In the prior art example shown in this patent document, a plurality of nozzles arranged two-dimensionally facing the collection sheet are provided, and collection is performed by the plurality of nozzles while feeding the collection sheet in the horizontal direction when generating the nanofibers. An example in which a polymer solution is discharged onto a sheet is described.

JP 2008-174867 JP

  By the way, there are various uses of the nanofiber film, and depending on the use, it may be required to attach the nanofiber so as to wrap around the back side at the end of the collection sheet. For example, in the case of using a laminate in which a nanofiber deposited film is formed on a conductive film used as a collection sheet as a material for an electronic component such as a capacitor, the nanofiber is formed so as to completely cover the end of the conductive film. It is necessary to ensure electrical insulation by adhering.

  However, in the production of conventional nanofiber membranes including the examples shown in the above-mentioned patent documents, the surface to be deposited is limited to the surface facing the discharge direction of the raw material liquid exclusively on the collection sheet. There has been no disclosure of a technique in which nanofibers are wound around and deposited on the back surface side of the end face of the collector sheet. For this reason, in electrospinning, it was calculated | required that a nanofiber wraps around and adheres to the edge part of an electrically conductive film by the simple method, and ensures insulation.

  Therefore, an object of the present invention is to provide a nanofiber film manufacturing apparatus and a nanofiber film manufacturing method capable of wrapping nanofibers around the conductive film to the back side by a simple method in electrospinning and depositing the nanofibers. To do.

The nanofiber film production apparatus of the present invention is a nanofiber film production apparatus for producing a nanofiber deposited film made of a polymer material, and a discharge means for discharging a raw material solution in which the polymer material is dissolved in a solvent. A charging means for charging the raw material liquid via the discharge means; and a nanofiber formed by electrically extending the discharged raw material liquid disposed and opposed to the discharge means. A collection region that is collected by a collection sheet, and a deposition region that is a target for forming a nanofiber deposition film in the conductive film is in addition to a surface deposition region that is set on a surface side facing the ejection unit. , Including a back deposition region set in the vicinity of the end portion around the back surface at either end portion, and the discharge means is configured such that the generated nanofibers pour down outside the end portion, and In a position where the nanofibers poured down the outside it is electrically attracted to the back deposition region.

  The nanofiber film manufacturing method of the present invention is a nanofiber film manufacturing method for manufacturing a nanofiber deposited film made of a polymer material, and a raw material solution in which the polymer material is dissolved in a solvent is discharged by a discharge means. In addition, a discharging / charging step of charging the raw material liquid by a charging means, and nanofibers formed by electrically stretching the discharged and charged raw material liquid are collected by a collecting sheet made of a sheet-like conductive film. A deposition region to be a target for forming a nanofiber deposition film in the conductive film, in addition to a surface deposition region set on the surface side facing the ejection unit, A back deposition region set in the vicinity of the end portion around the back surface at the end portion, and in the discharging / charging step, the generated nanofibers are outside the end portion. The pours, the position where the and nanofibers poured down to the outer electrically attracted to the back deposition region, thereby positioning the discharge means.

  According to the present invention, in addition to the surface deposition region set on the surface side facing the ejection unit, the deposition region that is the target for forming the nanofiber deposition film in the collection sheet made of the conductive film is any of In the case of including a back deposition region set in the vicinity of the end portion around the back surface at the end portion, the generated nanofibers pour down to the outside of the end portion, and the nanofibers that pour down outside become the back deposition region. By positioning the discharge means at a position where it is electrically adsorbed, the nanofibers can be wrapped around the end of the conductive film to the back side and deposited by a simple method in electrospinning.

Structure explanatory drawing of the nanofiber membrane manufacturing apparatus of one embodiment of the present invention The block diagram which shows the structure of the control system of the nanofiber film | membrane manufacturing apparatus of one embodiment of this invention Process explanatory drawing of the nanofiber film | membrane manufacturing method (1st Example) of one embodiment of this invention Explanatory drawing of the formation process of the deposited film in the nanofiber film | membrane manufacturing method (1st Example) of one embodiment of this invention Explanatory drawing of the collection sheet and support member in the nanofiber film | membrane manufacturing method (2nd Example) of one embodiment of this invention Process explanatory drawing of the nanofiber film | membrane manufacturing method (2nd Example) of one embodiment of this invention Explanatory drawing of the collection sheet and support member in the nanofiber film | membrane manufacturing method (3rd Example) of one embodiment of this invention Process explanatory drawing of the nanofiber film | membrane manufacturing method (3rd Example) of one embodiment of this invention of one embodiment of this invention Structure explanatory drawing of the nanofiber membrane manufacturing apparatus of one embodiment of the present invention Structure explanatory drawing of the nanofiber membrane manufacturing apparatus of one embodiment of the present invention

Next, embodiments of the present invention will be described with reference to the drawings. First, the configuration of the nanofiber film manufacturing apparatus 1 will be described with reference to FIG. Referring to FIG. 1, a nanofiber film manufacturing apparatus 1 having a function of manufacturing a nanofiber deposited film made of a polymer substance includes a mechanism section 2 including a nanofiber generation section 2a and a collection section 2b. The nanofiber generator 2a has a configuration in which a plurality (here, five) of solution supply containers 5 are arranged in a row in the X direction on a flat plate-like moving plate 3 having conductivity such as a metal plate.

  A discharge nozzle 5 a having a conductive surface is attached to the lower end portion of each solution supply container 5 so as to protrude from the lower surface of the moving plate 3, and an air supply pipe 5 b is provided above the solution supply container 5. It has been incorporated tie. The solution supply container 5 stores therein a raw material liquid 10 in which a polymer material that is a raw material for nanofibers is dissolved in a solvent. The air supply pipe 5b is connected to the air supply source 8 via the open / close valve 6 and the regulator 7, and supplies air of a predetermined pressure from the air supply source 8 to the solution supply container 5 via the air supply pipe 5b. Thus, the raw material liquid 10 is discharged from the discharge nozzle 5a. Instead of using the solution supply container 5 in which the raw material liquid 10 is stored, a separate raw material liquid 10 is supplied from a solution supply pipe connected to the solution tank, and the raw material liquid 10 is discharged by an air pressure from the air supply pipe 5b. You may comprise so that it may discharge from 5a.

  At this time, the discharge of the raw material liquid 10 can be connected / disconnected by turning on / off the open / close valve 6, and the air pressure for discharging the raw material liquid 10 can be adjusted by adjusting the set pressure of the regulator 7. Can do. The solution supply container 5 provided with the discharge nozzle 5a, the air supply pipe 5b, and the air supply source 8 constitute discharge means for discharging a raw material liquid 10 in which a polymer substance is dissolved in a solvent. The discharge means is configured to include a nozzle row L in which a plurality of discharge nozzles 5a for discharging the raw material liquid 10 are arranged in a row. In addition, although the example of the discharge means provided with the several discharge nozzle 5a is shown here, the structure provided with the single discharge nozzle 5a may be sufficient depending on the film formation object.

  The moving plate 3 is electrically connected to the high voltage applying device 9, and by operating the high voltage applying device 9, a positive high voltage (+10 to 20 KV) is applied to the moving plate 3 and further conductive. A high voltage is applied to the raw material liquid 10 through the discharge nozzle 5a having a conductive surface. Accordingly, the raw material liquid 10 discharged from the discharge nozzle 5a is charged to a positive potential, and is electrically stretched by the Coulomb force that interacts with the charges in the process of being jetted downward, thereby generating the nanofiber 10a. That is, the high voltage applying device 9 is a charging unit that charges the raw material liquid 10 via the discharge nozzle 5a of the discharge unit. The discharge nozzle 5a has a nozzle diameter of 0.1 to 2 mm and a nozzle length l of 3 to 10 mm, and is arranged on the moving plate 3 with an arrangement pitch p of 5 mm at the minimum. Moreover, the high voltage applied to the moving plate 3 may be one that applies a negative high voltage (−10 to −20 KV).

  Here, as a polymer substance constituting the nanofiber 10a, polypropylene, polyethylene, polystyrene, polyethylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly-m-phenylene terephthalate, poly-p-phenylene isophthalate, Polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl chloride, polyvinylidene chloride-acrylate copolymer, polyacrylonitrile, polyacrylonitrile-methacrylate copolymer, polycarbonate, polyarylate, polyester carbonate, polyamide, aramid , Polyimide, polycaprolactone, polylactic acid, polyglycolic acid, collagen, polyhydroxybutyric acid, polyvinyl acetate Le, polypeptides and the like, and polymeric materials such as copolymers thereof can be exemplified. Moreover, the kind selected from the above may be used, and a plurality of kinds may be mixed. In addition, the above is an illustration and this invention is not limited to the said resin.

Examples of the solvent used for the raw material liquid 10 include volatile organic solvents. Specific examples are 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, benzoate Propyl acid, methyl acetate, ethyl acetate, propyl acetate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, methyl chloride, ethyl chloride, methylene chloride, chloroform, o-chloroto Ene, p-chlorotoluene, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, dichloropropane, dibromoethane, dibromopropane, methyl bromide, ethyl bromide, propyl bromide, acetic acid, Benzene, toluene, hexane, cyclohexane, cyclohexanone, cyclopentane, o-xylene, p-xylene, m-xylene, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, pyridine, water Etc. can be listed. Moreover, the kind selected from the above may be used, and a plurality of kinds may be mixed. In addition, the above is an illustration and the raw material liquid 10 used for this invention is not limited to employ | adopting the said solvent.

Further, an additive such as an aggregate or a plasticizer may be added to the raw material liquid 10. Examples of the additive include oxides, carbides, nitrides, borides, silicides, fluorides, sulfides, and the like. From the viewpoints of heat resistance and workability, oxides are preferably used. Examples of the oxide include Al ₂ O ₃ , SiO ₂ , TiO ₂ , Li ₂ O, Na ₂ O, MgO, CaO, SrO, BaO, B ₂ O ₃ , P ₂ O ₅ , SnO ₂ , ZrO ₂ , K. _{2 O, Cs 2 O, ZnO} , Sb 2 O 3, As 2 O 3, CeO 2, V 2 O 5, Cr 2 O 3, MnO, Fe 2 O 3, CoO, NiO, Y 2 O 3, Lu 2 Examples include O ₃ , Yb ₂ O ₃ , HfO ₂ , Nb ₂ O _{5 and the} like. Moreover, the kind selected from the above may be used, and a plurality of kinds may be mixed. In addition, the above is an illustration and the substance added to the raw material liquid 10 of this invention is not limited to the said additive. The mixing ratio of the solvent and the polymer material in the raw material liquid 10 varies depending on the type of the solvent and the type of the polymer material, but the amount of the polymer material is about 5 to 40%, more preferably 5 to 30%. Between is desirable.

  A nozzle reciprocating mechanism 4 is coupled to the moving plate 3. By driving the nozzle reciprocating mechanism 4, the moving plate 3 reciprocates in the Y direction (arrow a direction) together with the plurality of solution supply containers 5. Thereby, the nanofiber 10a produced | generated by the nanofiber production | generation part 2a is spread | dispersed with the reciprocation of a Y direction with respect to the surface 11a of the collection part 2b demonstrated below. The nozzle reciprocating mechanism 4 is a moving mechanism that reciprocates the discharging means having the above-described configuration in a plane parallel to the collecting surface of the collecting portion 2b. This moving mechanism reciprocates the discharge means in a direction (Y direction) orthogonal to the nozzle row L described above.

  The collection unit 2b is configured to feed the collection sheet 11 fed from the supply reel 13 by the collection reel 14 driven by the sheet feed drive mechanism 15 to send it in the X direction (arrow b). The collection sheet is sent in a state of being supported from below by a support member 12 in which an insulator such as a resin is formed into a plate shape. The surface 11a of the collection sheet 11 faces the discharge nozzle 5a of the nanofiber generator 2a, and the nanofiber 10a generated by electrically stretching the raw material liquid 10 discharged from the discharge nozzle 5a is tungsten. It is collected by the surface 11a (sheet-like collection surface) of the collection sheet 11 made of a conductive film such as a film. The collection sheet 11 is connected to the ground part 16 by a ground wire, and the charge of the collection sheet 11 charged by collecting the nanofibers 10a having a positive charge moves to the ground part 16, thereby The collection sheet 11 is gradually electrified. Instead of connecting to the grounding part 16, a negative voltage may be applied to the collection sheet 11 by a voltage application part (not shown).

The nozzle reciprocating mechanism 4, the opening / closing valve 6, the regulator 7, the high voltage applying device 9, and the sheet feeding drive mechanism 15 are controlled by the control unit 20, whereby the nanofiber film manufacturing apparatus 1 performs the nanofiber film manufacturing operation. . Here, the configuration and function of the control unit 20 will be described with reference to FIG. In FIG. 2, the control unit 20 includes a nozzle reciprocation control unit 21, a reciprocation cycle calculation unit 22, an applied high voltage control unit 23, a solution supply control unit 24, a sheet feed control unit 25, and a storage unit 26. An input unit 27 and a display unit 28 are connected to the control unit 20.

  The nozzle reciprocation controller 21 controls the reciprocation of the moving plate 3 in the Y direction by the nozzle reciprocation mechanism 4, that is, the reciprocation of the discharge nozzle 5a. The reciprocating period calculating unit 22 calculates the period in the reciprocating movement of the discharge nozzle 5 a based on data stored in the storage unit 26 in advance. The applied high voltage control unit 23 controls the voltage applied to the moving plate 3 by the high voltage applying device 9. The solution supply control unit 24 controls the open / close valve 6 and the regulator 7, thereby controlling on / off and pressure of discharge of the raw material liquid 10 from the discharge nozzle 5 a. The sheet feeding control unit 25 controls the sheet feeding driving mechanism 15, and thereby the feeding operation of the collecting sheet 11 in the collecting unit 2 b is controlled.

  The storage unit 26 stores a reciprocating stroke 26a, a reciprocating cycle 26b, an applied high voltage value 26c, a solution supply pressure 26d, and a sheet feeding speed 26e. The reciprocating stroke 26 a is data indicating the stroke of the reciprocating motion of the discharge nozzle 5 a by the nozzle reciprocating mechanism 4, and is stored for each type of the collection sheet 11 as a target. The reciprocating cycle 26 b indicates the reciprocating cycle of the discharge nozzle 5 a calculated by the reciprocating cycle calculating unit 22. The applied high voltage value 26 c is a voltage value applied to the moving plate 3 by the high voltage applying device 9, and is stored for each type of the collection sheet 11 or the raw material liquid 10 as a target.

  The solution supply pressure 26 d is an air supply pressure for discharging the raw material liquid 10, and is stored as a set value of the regulator 7 for each type of the collection sheet 11 or the raw material liquid 10 as a target. The sheet feeding speed 26e is data indicating the feeding speed of the collection sheet 11 in the collection unit 2b, and is similarly stored for each type of the collection sheet 11 and the raw material liquid 10 as a target. The input unit 27 is an input device such as a keyboard or a touch panel switch, and inputs operation command instructions and data input to the ground unit 16. The display unit 28 is a display device such as a liquid crystal panel, and displays a guidance screen and a notification screen at the time of input by the input unit 27.

  This nanofiber film manufacturing apparatus 1 is configured as described above. Next, a nanofiber film manufacturing method (first embodiment) by the nanofiber film manufacturing apparatus 1 will be described. First, referring to FIG. 3 and FIG. 4, the film forming operation employed for forming the deposited film of the nanofiber 10a on the surface 11a of the collection sheet 11 with an appropriate quality, that is, the discharge nozzle 5a is previously set. A method of forming a film while reciprocating at a set predetermined interval time will be described.

  Here, the nanofiber 10a having a charge and containing a solvent has poor quality due to film formation while the charge and solvent remain inside, that is, the density of the nanofiber 10a due to repulsion between the nanofibers 10a due to the charge. In order to prevent the deterioration and the poor solidified state due to the solvent remaining, the surface 11a of the collection sheet 11 is divided into two regions as described below, and predetermined regions set in advance in these regions. A plurality of unit deposition layers are laminated by alternately depositing the nanofibers 10a at the interval time. In this film forming operation, the control unit 20 moves the discharge means by the nozzle reciprocating mechanism 4 at a reciprocating period T based on the above-described interval time set in advance to form a deposited film with appropriate quality. Is executed by.

That is, as shown in FIG. 3A, the area in the width direction of the surface 11a, which is the collection surface of the collection sheet 11 having the width dimension B1 (Y direction dimension), is defined as the first accumulation area A1 and the second accumulation area A2. It is divided into two equally. Above each of the first deposition region A1 and the second deposition region A2, the positions of the discharge nozzles 5a for spraying the nanofibers 10a on the regions are respectively first.
The nozzle position P1 and the second nozzle position P2 are set. In the nanofiber film forming operation, the discharge nozzle 5a is reciprocated by the distance between the first nozzle position P1 and the second nozzle position P2, that is, the reciprocating stroke S, and the first deposition area A1 and the second deposition area A2 are moved. The nanofibers 10a are dispersed alternately. As will be described later, the reciprocating period T in the reciprocating movement of the discharge nozzle 5a is individually set based on the type of the target nanofiber 10a, the film formation conditions such as the applied high voltage value 26c and the solution supply pressure 26d. Is done.

  First, as shown in FIG. 3B, the discharge nozzle 5a is positioned at the first nozzle position P1, and the nanofibers 10a are dispersed from the discharge nozzle 5a to the first deposition region A1. Next, after the half period (T / 2) of the reciprocating period T has elapsed, as shown in FIG. 3C, the discharge nozzle 5a is moved to the second nozzle position P2. At this time, in the first deposition region A1, nanofibers 10a dispersed during a half cycle in FIG. 3B are deposited on the surface 11a to form a unit deposition layer 30a. Then, after each half cycle (T / 2), the discharge nozzle 5a is moved between the first nozzle position P1 and the second nozzle position P2, and alternately in the first deposition area A1 and the second deposition area A2. The nanofibers 10a are dispersed and deposited. As a result, a unit deposition layer of the nanofiber 10a is formed on the surface 11a of the collection sheet 11 for each reciprocation period T of the discharge nozzle 5a. By repeatedly performing the predetermined predetermined number of times, the deposited film 30 of the nanofiber 10a composed of a plurality of unit deposition layers (here, three unit deposition layers 30a, 30b, 30c) is formed on the surface 11a. Is formed.

  FIG. 4 shows the formation process of the deposited film in the nanofiber film formation described above. Here, after the unit deposited layer 30a is formed on the surface 11a, the next unit deposited layer 30b is formed thereon. Is shown. First, FIG. 4A shows a state in which the nanofibers 10a are deposited on the first deposition region A1, and the raw material liquid 10 discharged from the discharge nozzle 5a has a composition in which a polymer substance is dissolved in a solvent. Therefore, the nanofiber 10 a generated by electrically stretching the raw material liquid 10 is accompanied by the charge 32 together with the solvent 31. For this reason, while the nanofibers 10a are continuously dispersed in the first deposition region A1 for a half cycle and are deposited on the upper layer of the unit deposition layer 30a, the unit deposition layer 30b has a solvent 31 and a charge 32. Is accumulated.

  FIG. 4B shows a state in which the nanofibers 10a are deposited on the second deposition region A2 by moving the discharge nozzle 5a after a half cycle has elapsed. Similarly, while the nanofibers 10a are continuously applied to the second deposition region A2 and deposited on the upper layer of the unit deposition layer 30a during the half cycle, the unit deposition layer 30b includes the solvent 31 and the charge. 32 is accumulated. On the other hand, in the first deposition region A1, since the dispersion of the nanofibers 10a is suspended, the solvent 31 accumulated in the unit deposition layer 30b is evaporated and released into the atmosphere. Moreover, the electric charge 32 moves to the grounding part 16 electrically connected with the collection sheet | seat 11, and the unit deposition layer 30b will be in the state where the electric power was slowed down. Thereby, in the unit deposition layer 30b, solidification of the nanofibers 10a is promoted, and the action of repelling the nanofibers 10a disappears, so that the adhesion of the nanofibers 10a is improved and good quality characteristics are provided. A unit deposition layer 30b is formed.

FIG. 4 (c) shows a state in which the nanofibers 10a are deposited on the first deposition region A1 by moving the discharge nozzle 5a again after another half cycle has passed. In this case, the unit deposition layer 30c is formed above the unit deposition layer 30b that has already been formed. However, since the unit deposition layer 30b has already released the solvent 31 and the charge 32 as described above, Thus, there is no quality defect caused by the unit deposition layer 30c inhibiting the release of the solvent 31 and the charge 32 from the unit deposition layer 30b. Further, in the second deposition region A2, since the dispersion of the nanofibers 10a is interrupted, the solvent 31 and the charge 32 accumulated in the unit deposition layer 30b are released as described above, and the quality is good. A unit deposition layer 30b having characteristics is formed.

  That is, in the nanofiber membrane manufacturing method described above, the raw material liquid 10 in which the polymer substance is dissolved in the solvent is discharged by the discharge nozzle 5a of the discharge means, and the moving plate 3 and the discharge nozzle 5a are moved by the high voltage applying device 9. Then, the raw material liquid 10 is charged (discharge / charging process). Next, the nanofibers 10a generated by electrically stretching the discharged and charged raw material liquid 10 are collected by the surface 11a of the collection sheet 11 which is a sheet-like collection surface (collection step).

  In this collection step, the reciprocation period T based on a predetermined interval time set in advance to form the deposited film 30 with appropriate quality in a plane parallel to the surface 11a of the discharge nozzle 5a. I am trying to move with. In the present embodiment, this interval time is necessary to evaporate the solvent 31 and the slowing time required to remove the charge 32 from the unit deposition layer of the nanofiber 10a formed at each reciprocation cycle. It is set based on the solvent transpiration time, and is set so that the half period (T / 2) of the reciprocation period T is longer than the longer one of the slow current time and the solvent transpiration time. Here, the slow current time and the solvent transpiration time described above are actually film forming operations under the film forming conditions defined by the applied high voltage value 26c, the solution supply pressure 26d, etc. for each type of the target raw material liquid 10. It is determined by a so-called condition determination operation for trial and evaluating the trial result. As a specific numerical example, the above slowing time and solvent evaporation time are generally 0.5 sec. The reciprocation period T with the interval time as a half period is about 1 sec. It is possible to select the degree.

  As described above, in the first embodiment shown in FIGS. 3 and 4, the nanofibers 10a generated by electrically extending the charged raw material liquid 10 discharged and discharged by the discharge nozzle 5a of the discharge means are collected. In the collecting step of collecting by the surface 11a of the sheet 11, the discharge nozzle 5a is set in a predetermined interval time set in advance to form the deposited film 30 with appropriate quality in a plane parallel to the surface 11a. It is made to move by the reciprocation period T based on it. Thereby, normal formation of the unit deposition film which comprises the deposition film 30 is ensured, and the quality defect resulting from a residual electric charge, a solvent component, etc. can be prevented.

  Next, a nanofiber film manufacturing method (second embodiment) by the nanofiber film manufacturing apparatus 1 will be described with reference to FIGS. In the second embodiment, when a conductive film is used as a collection sheet, it is necessary to ensure electrical insulation by attaching nanofibers so as to completely cover the end of the conductive film. 1 shows a nanofiber membrane manufacturing method applied to the above.

  In FIG. 5A, the collection sheet 11 is a conductive film in which a conductive material such as tungsten is formed into a film. In addition to the surface deposition region C set in the entire range of the surface 11a facing the discharge nozzle 5a in the film forming operation, the deposition region that is the target for forming the deposition film 30 of the nanofiber 10a in the collection sheet 11 is the end region. The portion 11c includes a back deposition region D set around the back surface 11b and set in the vicinity of the end portion 11c. In this case, as shown in FIG. 5 (b), the collection unit 2 b contacts the range excluding the back accumulation region D on the back surface 11 b of the collection sheet 11 and supports the collection sheet 11. Thus, the back deposition region D is always exposed in the film forming operation.

  As in the example shown in FIG. 1, the collection sheet 11 is electrically connected to the grounding part 16 so that the electric charge that falls on the collection sheet 11 is released to the grounding part 16. Instead of grounding the collection sheet 11, a voltage application unit (not shown) that applies a voltage of the opposite polarity to the charge obtained by charging the raw material liquid 10 to the collection sheet 11 may be provided.

Next, the film formation process will be described with reference to FIG. FIG. 6A shows a fixed 1
The example in which all the required deposition areas can be covered by the dispersion | spreading range of the nanofiber 10a by the one discharge nozzle 5a is shown. In this case, the dispersion range of the nanofibers 10a by the discharge nozzle 5a covers all of the surface deposition region C of the width dimension B2, and further, the predetermined range E protrudes outward from the end portion 11c. Discharge nozzle 5a is arranged.

  Here, the predetermined range E is generated when the charged raw material liquid 10 discharged from the discharge nozzle 5a is electrically stretched, and the nanofibers 10a that pour down with the charge 32 fall outside the end portion 11c. The width is set such that a part of the width bypasses the end portion 11c and satisfies the condition for adhering and depositing on the back deposition region D by the adhering force of the charge 32. The predetermined range E is also determined by a condition determination operation for performing an experiment for each type of nanofiber 10a and each film formation condition and evaluating the deposition state.

  That is, in this second embodiment, the discharge nozzle 5a of the discharge means is such that the generated nanofibers 10a pour down to the outside of the end portion 11c of the collection sheet 11, and the nanofibers 10a that pour down to the outside are the back deposition region D. It is arrange | positioned in the position electrically adsorbed to. As a result, the deposited film 30 is formed so as to cover not only the surface deposition region C of the collection sheet 11 but also the back deposition region D of the back surface 11b so as to cover the end 11c.

  FIG. 6B is directed to a collection sheet 11 having a width dimension B2L that cannot cover a required deposition area depending on a dispersion range of the nanofibers 10a by one discharge nozzle 5a that is fixedly arranged. It shows an example of a case. In this case, the discharge nozzle 5a is reciprocated in the width direction (Y direction) of the collection sheet 11 by the nozzle reciprocating mechanism 4 without fixing the discharge nozzle 5a (see FIG. 1). That is, as shown in FIG. 6B, in a state where the discharge nozzle 5a is moved to the end portion 11c side of the collection sheet 11, the position where the predetermined range E shown in FIG. In a state where the first stroke end SE1 is moved to the opposite side of the end portion 11c, the second stroke end is set such that the remaining range of the surface deposition region C is covered by the spraying range of the nanofibers 10a by the discharge nozzle 5a. Set SE2.

  That is, in the example shown in FIG. 6B, a nozzle reciprocating mechanism that reciprocates the discharge nozzle 5 a of the discharge means in a direction (Y direction) orthogonal to the end portion 11 c in a plane parallel to the collection sheet 11. 4 adopts a configuration including. The stroke of the reciprocating motion by the nozzle reciprocating mechanism 4 is discharged to a position where the generated nanofiber 10a falls down to the outside of the end portion 11c and the nanofiber 10a poured down to the outside is electrically adsorbed to the back deposition region D. It is set so that the nozzle 5a moves.

  Instead of reciprocating the discharge nozzle 5a in the Y direction with respect to the collecting sheet 11 by the nozzle reciprocating mechanism 4, a support member 12 that supports the collecting sheet 11 is fixedly arranged by a member moving mechanism (not shown). You may make it reciprocate in the direction (Y direction) orthogonal to the edge part 11c of the collection sheet | seat 11 within the plane parallel to the discharged discharge nozzle 5a. Even in this case, the stroke of the reciprocating motion of the collection sheet 11 by the member moving mechanism is such that the generated nanofibers 10a pour down the outside of the end portion 11c and the nanofibers 10a pour down outside are electrically connected to the back deposition region D. The discharge nozzle 5 a is set so as to move relative to the collection sheet 11 at a position where it is attracted to the collection sheet 11.

That is, in the above-described nanofiber film manufacturing method (second embodiment), the raw material liquid 10 in which the polymer substance is dissolved in the solvent is discharged by the discharge nozzle 5a of the discharge means, and the moving plate is moved by the high voltage applying device 9. 3. Charge the raw material liquid 10 through the discharge nozzle 5a (discharge / charging process). Next, the nanofibers 10a generated by electrically stretching the discharged and charged raw material liquid 10 are collected by the surface 11a of the collection sheet 11 which is a sheet-like collection surface (collection step).

  In the discharging / charging step, the generated nanofibers 10a are poured down to the outside of the end portion 11c, and the discharging nozzle 5a is placed at a position where the nanofiber 10a poured into the end portion 11c is electrically adsorbed to the back deposition region D. Is located. Thereby, in the nanofiber film formation in which the deposited film of the nanofiber 10a is formed on the conductive film by electrospinning, the nanofiber 10a can be wrapped around the back surface side and deposited by a simple method, It is possible to ensure insulation at the end of the conductive film.

  Next, a nanofiber film manufacturing method (third embodiment) by the nanofiber film manufacturing apparatus 1 will be described with reference to FIGS. The third embodiment is a nanofiber that is applied when a region where nanofibers are to be deposited and a region where nanofibers are not to be deposited are mixed on the same surface of a collection sheet on which a deposited film is to be formed. It shows the film production process.

  In FIG. 7A, the collection sheet 11 is a conductive film in which a conductive material such as tungsten is formed into a film. In the collection sheet 11, the target surface 11 a of the nanofiber 10 a on which the film is formed includes a surface deposition region C that is a target for forming the deposition film 30 and a non-deposition region F that is not a target for forming the deposition film 30. It is set Te. Further, similarly to the example shown in FIG. 5 (a), in addition to the surface deposition region C set on the front surface 11a, the back deposition region set around the end portion 11c around the back surface 11b side at the end portion 11c. D is included. In this case, as illustrated in FIG. 7B, the collection unit 2 b contacts the range excluding the back accumulation region D on the back surface 11 b of the collection sheet 11 and supports the collection sheet 11. Thus, the back deposition region D is always exposed in the film forming operation.

  Prior to mounting the collection sheet 11 on the collection unit 2b, a conductor 34 such as aluminum is placed on the non-deposition region F of the surface 11a via an insulator 33 such as resin. At this time, as shown in the enlarged view in FIG. 7B, an inclined portion 33a is provided in a portion of the insulator 33 located near the boundary between the surface deposition region C and the non-deposition region F. For this reason, the end 34a of the conductor 34 placed on the insulator 33 has a form somewhat separated from the boundary with the surface deposition region C. Thereby, as will be described later, it is possible to prevent a phenomenon in which the thickness of the deposited film 30 formed in the surface deposition region C decreases near the boundary with the non-deposition region F.

  A voltage of the same polarity (for example, +1 to 5 KV) lower than the voltage (+10 to 20 KV) for charging the raw material liquid 10 is applied to the conductor 34 by the voltage application unit 35. At the same time, as in the example shown in FIG. 1, the collection sheet 11 is electrically connected to the grounding part 16, and the electric charge that falls on the collection sheet 11 is released to the grounding part 16. Instead of grounding the collection sheet 11, a voltage application unit (not shown) that applies a voltage of the opposite polarity to the charge obtained by charging the raw material liquid 10 to the collection sheet 11 may be provided.

  Next, the film formation process will be described with reference to FIG. FIG. 8A shows an example in which all necessary deposition regions can be covered by the dispersion range of the nanofibers 10a by one discharge nozzle 5a that is fixedly arranged. In this case, the dispersion range of the nanofibers 10a by the discharge nozzle 5a covers all of the surface deposition region C having the width dimension B4, and part thereof includes part of the non-deposition region F, and further from the end portion 11c to the outside. In addition, the discharge nozzle 5a is arranged so that only a predetermined range E shown in FIG. Then, a positive voltage having the same polarity as the electric charge obtained by charging the raw material liquid 10 is applied to the conductor 34 placed in the non-deposition region F via the insulator 33 by the voltage application unit 35. At this time, the collection sheet 11 is applied with ground or a negative voltage.

The nanofiber 10a generated by electrically stretching the charged raw material liquid 10 discharged from the discharge nozzle 5a falls on the surface 11a of the collection sheet 11, and a part thereof as in the example shown in FIG. Is deposited and deposited on the back deposition region D by the adhesion force of the charge 32, bypassing the end portion 11c. Then, the nanofibers 10a poured on the surface deposition region C of the surface 11a are deposited on the surface 11a in the surface deposition region C because the collection sheet 11 is grounded or a negative voltage is applied. Form.

  On the other hand, since a voltage having the same polarity as the electric charge 32 charging the nanofiber 10a is applied to the conductor 34 placed in the non-deposition region F, the conductor 34 falls on the non-deposition region F of the surface 11a. The nanofiber 10a is repelled by the conductor 34, and the deposition on the non-deposition region F is inhibited. In the exclusion action of the nanofiber 10a by the conductor 34, the end 34a of the conductor 34 is equal to the width of the inclined portion 33a provided in the vicinity of the boundary with the surface deposition region C, as shown in FIG. It is separated from the end of the surface deposition region C. Therefore, the exclusion action of the nanofibers 10a by the conductor 34 is small at the end of the surface deposition region C, and the deposited film 30 of the deposited film 30 caused by the decrease in the thickness of the deposited film 30 in the vicinity of the end of the surface deposition region C. shape defects does not occur.

  In FIG. 8B, the surface deposition region C having a width dimension B4L that cannot cover the required deposition region is set depending on the dispersion range of the nanofibers 10a by one discharge nozzle 5a that is fixedly arranged. The example in case the collection sheet | seat 11 is made into object is shown. In this case, similarly to the example shown in FIG. 6B, the discharge nozzle 5a is reciprocated in the width direction (Y direction) of the collection sheet 11 by the nozzle reciprocating mechanism 4 without fixing the discharge nozzle 5a. thereby moving (see FIG. 1). That is, as shown in FIG. 8B, in a state where the discharge nozzle 5a is moved to the end portion 11c side of the collection sheet 11, the position where the predetermined range E shown in FIG. In a state where the first stroke end SE1 is moved to the opposite side of the end portion 11c, the second stroke end is set such that the remaining range of the surface deposition region C is covered by the spraying range of the nanofibers 10a by the discharge nozzle 5a. Set SE2.

  That is, in the example shown in FIG. 8B, a nozzle reciprocating mechanism that reciprocates the discharge nozzle 5 a of the discharge means in a direction (Y direction) orthogonal to the end portion 11 c in a plane parallel to the collection sheet 11. 4 adopts a configuration including. The stroke of the reciprocating motion by the nozzle reciprocating mechanism 4 is set so that the nanofibers 10a pour into the surface deposition region C, and the generated nanofibers 10a pours outside the end portion 11c and pours outside. The discharge nozzle 5a is set to move to a position where the fiber 10a is electrically attracted to the back deposition region D.

  That is, in the above-described nanofiber film manufacturing method (third embodiment), the raw material liquid 10 in which the polymer substance is dissolved in the solvent is discharged by the discharge nozzle 5a of the discharge means, and the moving plate is moved by the high voltage applying device 9. 3. Charge the raw material liquid 10 through the discharge nozzle 5a (discharge / charging process). Next, the nanofibers 10a generated by electrically stretching the discharged and charged raw material liquid 10 are collected by the surface 11a of the collection sheet 11 which is a sheet-like collection surface (collection step).

  In the collection sheet 11, the surface 11 a that is the target surface of the nanofiber film formation includes a surface deposition region C that is a target for forming the deposition film 30 and a non-deposition region F that is not a target for forming the deposition film 30. The surface deposition region C is grounded, or a voltage opposite to the charge obtained by charging the raw material liquid 10 is applied to the surface deposition region C, and the same polarity as the charge obtained by charging the raw material solution 10 to the non-deposition region F. The voltage is applied. Thereby, in the nanofiber film formation which forms the deposited film of the nanofiber 10a in a electrically conductive film by electrospinning, the presence or absence of nanofiber deposition can be switched by a simple method.

  In each example of the above-described embodiment, an example in which the collection sheet 11 is moved in the collection unit 2b and the nanofibers 10a are continuously sprayed and deposited on the surface 11a from the discharge nozzle 5a is shown. However, the deposited film may be formed by spraying the nanofibers 10a for a predetermined time on the collection sheet 11 in a stationary state.

  In addition, the configuration of the nanofiber membrane manufacturing apparatus to be applied in the present invention is not limited to the configuration of the nanofiber membrane manufacturing apparatus 1 shown in FIG. 1, but various modifications as shown below. it is possible to apply the present invention to. The nanofiber membrane manufacturing apparatus 1A shown in FIG. 9 has an upward convex shape on the support member that supports the collection sheet 11 from below, with the collection unit 2b constituting the mechanism unit 2 in the nanofiber membrane production apparatus 1 shown in FIG. The support member 112 having the support surface 112a is used.

  Then, the collection sheet 11 fed out from the supply reel 13 and taken up by the collection reel 14 is pressed from above by the pressing rollers 17A and 17B disposed at both ends of the supporting member 112, and is made to follow the supporting surface 112a. I am doing so. Thereby, it is possible to cancel the upward warping deformation of the collection sheet 11 caused by preliminarily giving an upward convex warpage deformation to the collection sheet 11 to be formed with the nanofiber film and depositing the nanofibers 10a on the surface 11a. it can.

  Furthermore, the nanofiber film manufacturing apparatus 1B shown in FIG. 10 is configured to move the nanofiber generating unit 2a constituting the mechanism unit 2 in the nanofiber film manufacturing apparatus 1 shown in FIG. A configuration in which a triangular column-shaped nozzle head 50 having a plurality of (here, five) ejection holes 50a is mounted on the lower surface is used. The solution pipe 51 coupled to the nozzle head 50 is connected to a solution supply unit 53 via a pump 52, and the raw material liquid 10 is supplied to the nozzle head 50 by driving the pump 52.

  In this state, by supplying air for solution discharge into the nozzle head 50 through the air supply pipe 5b, the raw material liquid 10 is discharged from the discharge holes 50a, and the nanofibers 10a are similarly generated. By adopting such a method, in the configuration provided with a plurality of discharge holes 50a, the air pressure acting on each discharge hole 50a can be made uniform, and the discharge state of the raw material liquid 10 from the discharge holes 50a Can be eliminated. Instead of directly providing the discharge hole 50a in the nozzle head 50, a discharge nozzle having a shape protruding downward may be provided.

  The nanofiber film manufacturing apparatus and the nanofiber film manufacturing method of the present invention have the effect that nanofibers can be wrapped around and deposited on the back side of the conductive film by a simple method in electrospinning. The present invention can be used in the field of producing nanofiber deposited films made of molecular substances.

DESCRIPTION OF SYMBOLS 1,1A, 1B Nanofiber membrane manufacturing apparatus 2 Mechanism part 2a Nanofiber production | generation part 2b Collection part 5 Solution supply container 5a Discharge nozzle 9 High voltage application apparatus 10 Raw material liquid 10a Nanofiber 11 Collection sheet 11a Front surface 11b Back surface 12 Support Member 16 Grounding portion 30 Deposition film 30a, 30b, 30c Unit deposition layer 31 Solvent 32 Charge C Surface deposition region D Back deposition region F Non-deposition region

Claims (6)

A nanofiber film manufacturing apparatus for manufacturing a nanofiber deposited film made of a polymer material,
Discharging means for discharging a raw material liquid in which the polymer substance is dissolved in a solvent, charging means for charging the raw material liquid via the discharging means, and the raw material liquid disposed and discharged opposite to the discharging means And a collection part that collects nanofibers generated by electrically stretching by a collection sheet made of a conductive film,
In addition to the surface deposition region set on the surface side facing the discharge means, the deposition region that is the target for forming the nanofiber deposition film on the collection sheet goes around to the back side at either end. Including the back deposition area set in the vicinity of this end,
The nanofiber, wherein the discharging means is located at a position where the generated nanofibers pour down to the outside of the end and the nanofibers poured out of the end are electrically adsorbed to the back deposition region. Membrane manufacturing equipment.   The collection unit includes a support member that abuts and supports the back surface of the collection sheet in a range excluding the back accumulation region, and further, a grounding unit for grounding the collection sheet or the raw material liquid on the collection sheet The apparatus for producing a nanofiber film according to claim 1, further comprising a voltage application unit that applies a voltage having a polarity opposite to the charge obtained by charging the electrode.   A moving mechanism for reciprocating the discharge means in a direction perpendicular to the end portion in a plane parallel to the collection sheet, and the stroke of the reciprocation by the moving mechanism is generated by the discharge means. The nanofiber is poured to the outside of the end portion, and the nanofiber poured to the outside is set so as to be movable to a position where it is electrically adsorbed to the back deposition region. The nanofiber film manufacturing apparatus according to any one of the above.   A member moving mechanism that reciprocates the support member in a direction perpendicular to the end in a plane parallel to the collection sheet, and the discharge means generates the stroke of the reciprocating motion by the member moving mechanism. 3. The set nanofiber is set so as to be relatively movable to a position where the nanofiber poured onto the outside of the end portion and the nanofiber poured onto the outside are electrically adsorbed to the back deposition region. nanofiber film manufacturing apparatus according to.   The nanofiber film manufacturing apparatus according to any one of claims 1 to 4, wherein the discharge means includes a nozzle row in which a plurality of discharge nozzles for discharging the raw material liquid are arranged in a row. A nanofiber film manufacturing method for manufacturing a nanofiber deposited film made of a polymer material,
A discharging and charging step of discharging the raw material liquid in which the polymer substance is dissolved in a solvent is discharged by the discharging means, and charging the raw material liquid by the charging means, and the discharged and charged raw material liquid is electrically stretched. A collecting step of collecting the produced nanofibers by a collecting sheet made of a sheet-like conductive film,
In addition to the surface deposition region set on the front surface facing the ejection means, the deposition region that is the target for forming the nanofiber deposition film in the conductive film wraps around the back surface at either end. Including a back deposition area set near this edge,
In the discharging / charging step, the discharging means is positioned at a position where the generated nanofibers pour down to the outside of the end portion and the nanofibers pouring out of the outside are electrically adsorbed to the back deposition region. A method for producing a nanofiber film, comprising:

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