JP2017095839A - Laminate manufacturing method and manufacturing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method to improve stability of spinning by an electrospinning mechanism.SOLUTION: An electrospinning mechanism 1 comprises: a container 3, which stores a raw material liquid 2 containing a raw material resin, which is a raw material of fiber, and a solvent that melts the raw material resin; a discharge body 5, which discharges the raw material liquid 2 toward a principal surface on one side of a sheet; a pipe 6, which feeds the raw material liquid 2 to the discharge body 5 from the container 3; and a voltage application device 7, which applies voltage on the discharge body 5. A laminate manufacturing method uses the electrospinning mechanism and comprises: an application process to apply voltage on the discharge body 5 along with the raw material liquid 2 inside the discharge body 5 using the voltage application device 7; and an accumulation process to discharge the charged raw material liquid 2 from the discharge body 5 toward the principal surface of the sheet to generate the fiber containing the raw material resin and accumulate the fiber on the principal surface of the sheet. The container 3 is surrounded by an insulation member 8, which has a lower insulation plate 8a covering the bottom part of the container 3 and an insulation wall 3b covering the lateral face of the container.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method and an apparatus for producing a laminate using an electrospinning mechanism.

  An electrospinning method is known as a method of laminating a nonwoven fabric containing ultrafine fibers on a base sheet (Patent Documents 1 and 2). In the electrospinning method, a raw material liquid containing a resin that is a raw material of a fiber is supplied to an emitter to which a high voltage is applied, and the raw material liquid is charged positively, for example, and a sheet-like target is grounded or negatively charged. Then, the fiber is formed by spraying the raw material liquid from the nozzle toward the target. The formed fiber is deposited on the target to obtain a laminate of the fiber and the target.

JP 2008-179916 A JP 2009-35839 A

  The container for storing the raw material liquid and the emitter are connected by a pipe. The raw material liquid is supplied from the container to the emitter through the pipe. That is, the raw material liquid is continuous inside the emitter, pipe and container. Therefore, the raw material liquid in the container has the same potential as the raw material liquid charged in the discharge body. Therefore, the container for storing the charged raw material liquid is also charged. When the container is positively charged, when discharged from the container, the potential of the raw material liquid in the emitter is lowered and the voltage is lowered. As a result, the electrospinning stability is impaired. The same applies when the container is negatively charged.

  One aspect of the present invention is a container that stores a raw material resin that is a raw material for fibers and a raw material liquid that contains a solvent that dissolves the raw material resin, and an emitter that discharges the raw material liquid toward one main surface of the sheet. A method of producing a laminate using an electrospinning mechanism comprising: a pipe for supplying the raw material liquid from the container to the emitter; and a voltage applying device for applying a voltage to the emitter. An application step of applying a voltage to the raw material liquid inside the emitter together with the emitter using the voltage application device, and the charged raw material liquid from the emitter toward the main surface of the sheet And a deposition step of depositing the fibers on the main surface of the sheet to form the fibers containing the raw material resin, and the container includes a lower insulating plate that covers the bottom of the container; Insulation covering the side of the container If, surrounded by an insulating member comprising a method for producing a laminate.

  Another aspect of the present invention is a container that stores a raw material resin that is a raw material of a fiber and a solvent that dissolves the raw material resin, and a discharge that discharges the raw material liquid toward one main surface of the sheet. A laminate manufacturing apparatus comprising: an electrospinning mechanism comprising: a body; a pipe for supplying the raw material liquid from the container to the emitter; and a voltage applying device for applying a voltage to the emitter. The present invention relates to an apparatus for manufacturing a laminate, in which the container is surrounded by an insulating member that includes a lower insulating plate that covers the bottom of the container and an insulating wall that covers a side surface of the container.

  According to the present invention, the spinning stability by the electrospinning mechanism is improved.

It is a figure which shows typically the principal part of the electrospinning mechanism which concerns on one Embodiment of this invention. It is a figure which shows typically the discharge body which concerns on one Embodiment of this invention.

  The method for manufacturing a laminate according to the present invention includes a container that stores a raw material resin that is a raw material for fibers and a solvent that dissolves the raw material resin, and a discharge that discharges the raw material liquid toward one main surface of the sheet. A method of manufacturing a laminate using an electrospinning mechanism comprising a body, a pipe for supplying a raw material liquid from a container to a discharge body, and a voltage application device for applying a voltage to the discharge body, And applying the voltage to the raw material liquid inside the emitter together with the emitter, and discharging the charged raw material liquid from the emitter toward the main surface of the sheet to produce a fiber containing the raw material resin And depositing the fibers on the main surface of the sheet. At this time, the container is surrounded by an insulating member including a lower insulating plate that covers the bottom of the container and an insulating wall that covers the side surface of the container. As a result, the container is unlikely to receive an external load (particularly contact with a conductor) that promotes discharge from the container, and discharge from the container is suppressed. As a result, the voltage of the electrospinning mechanism is stabilized and the spinning stability is improved.

  The insulating wall preferably covers the side surface of the container with an interval. Since the space is formed between the insulating wall and the container, the discharge from the container can be further suppressed. When the insulating wall is sufficiently thick, the insulating wall and the container may be in contact with each other.

  The upper end of the insulating wall is preferably above the upper end of the side surface of the container, and the upper part of the container is preferably covered with an upper insulating plate. This is because the container becomes more difficult to receive an external load.

  The container and the insulating member are preferably accommodated in the tank in that the external load applied to the container can be further reduced. When the tank is made of metal, it is preferable from the viewpoint of safety to connect the tank to the ground to prevent the tank from being charged.

  The space inside the container may be communicated with the space inside the tank and outside the container. In this case, in the deposition step, the inside of the tank can be pressurized and the raw material liquid stored in the container can be sent into the pipe. Thus, the electrospinning mechanism is simplified by causing the tank to function as a high-pressure pump.

  The laminated body manufacturing apparatus according to the present invention includes a container that stores a raw material resin that is a raw material for fibers and a solvent that dissolves the raw material resin, and a discharge that discharges the raw material liquid toward one main surface of the sheet. The electrospinning mechanism includes a body, a pipe that supplies a raw material liquid from the container to the emitter, and a voltage application device that applies a voltage to the emitter. At this time, the container is surrounded by an insulating member including a lower insulating plate that covers the bottom of the container and an insulating wall that covers the side surface of the container. Thereby, a container becomes difficult to receive an external load and the discharge from a container is suppressed. As a result, the voltage of the electrospinning mechanism is stabilized and the spinning stability is improved.

  Hereinafter, an embodiment of a manufacturing method and a manufacturing apparatus according to the present invention will be described with reference to the drawings. FIG. 1 is a diagram schematically showing the main parts (mainly containers and insulating members) of the electrospinning mechanism according to the first embodiment of the present invention. FIG. 2 is a diagram schematically showing an emitter provided in the electrospinning mechanism according to the first embodiment of the present invention.

  The laminate is manufactured by a method using an electrospinning mechanism 1 as illustrated in FIG. That is, the laminate uses the voltage application device 7 to apply a voltage to the raw material liquid 2 inside the discharger 5 together with the discharger 5, and the charged raw material liquid 2 from the discharger 5 to a sheet (not shown). And producing a fiber (not shown) containing a raw material resin, and depositing the fiber on the main surface of the sheet.

[Electrospinning mechanism]
An electrospinning mechanism 1 includes a container 3 that stores a raw material resin that is a raw material of a fiber and a solvent 2 that dissolves the raw material resin, and an emitter 5 that discharges the raw material liquid 2 toward one main surface of the sheet. And a pipe 6 for supplying the raw material liquid 2 from the container 3 to the emitter 5 and a voltage applying device 7 for applying a voltage to the emitter 5.

  The container 3 is a stationary type, and is placed on a gantry or a floor (not shown). The material of the container 3 is not particularly limited as long as it has corrosion resistance to the raw material liquid. Examples of the material of the container 3 include polypropylene and polyethylene. The size is not particularly limited, and may be set as appropriate according to the manufacturing scale.

  In the application step, a voltage is applied to the emitter 5 by the voltage application device 7, and the emitter 5 is positively charged. At this time, the raw material liquid 2 accommodated in the emitter 5 is also charged to substantially the same potential. On the other hand, the target sheet is placed on a grounded support (not shown; for example, a conveyor belt or a roller). Thereby, a potential difference (for example, 20 to 200 kV) corresponding to the voltage applied by the voltage application device 7 is generated between the raw material liquid 2 inside the emitter 5 and the sheet. In this state, the deposition process is performed. That is, the raw material liquid 2 discharged from the emitter 5 toward the sheet causes an electrostatic explosion while moving in a space (generation space) between the emitter 5 and the sheet in a charged state, thereby causing a fibrous material. (Fiber) is produced. The produced fiber is deposited on the sheet, and a laminate of the sheet and the fiber is obtained. The support may be negatively charged. Alternatively, the emitter 5 may be negatively charged and the support may be grounded or positively charged.

  The raw material liquid 2 is supplied from the container 3 to the positively charged emitter 5 through the inside of the pipe 6. Therefore, the raw material liquid 2 accommodated in the emitter 5 is positively charged. The raw material liquid 2 is continuous inside the emitter 5, the pipe 6 and the container 3. Therefore, the raw material liquid 2 stored in the container 3 is positively charged and the container 3 is positively charged.

  Here, when a conductor (for example, including a person) comes into contact with the charged container 3 and is discharged from the container 3, the potential of the raw material liquid 2 in the emitter 5 is temporarily linked with this. Decline. As a result, the voltage of the electrospinning mechanism 1 temporarily decreases, and the electrospinning stability is impaired. In the present embodiment, the container 3 that stores the raw material liquid 2 is surrounded by the insulating member 8, thereby suppressing discharge from the container 3 and improving the electrospinning stability. In addition, since human contact with the container 3 is prevented, safety is also improved.

  The insulating member 8 includes a lower insulating plate 8 a that covers the bottom of the container 3, and an insulating wall 8 b that covers the side surface of the container 3. It is preferable that the insulating member 8 further includes an upper insulating plate 8 c that covers the upper portion of the container 3. This is because the container 3 becomes more difficult to receive an external load.

  The insulating wall 8b is preferably arranged at a predetermined distance d from the side surface of the container 3 so as not to contact the side surface of the container 3. Thereby, the discharge from the container 3 is further suppressed. The interval d may be appropriately set according to the potential of the container 3 so that dielectric breakdown does not occur. The distance d may not be constant with respect to all side surfaces of the container 3. If the insulating wall 8b is sufficiently thick, the insulating wall 8b and the side surface of the container 3 may be in contact with each other.

  The insulating wall 8b and the lower insulating plate 8a may be in contact or bonded, or may not be in contact. For example, when the distance d is sufficiently large so that the electric charge accumulated in the container 3 is not discharged, there may be a gap between the insulating wall 8b and the lower insulating plate 8a. The insulating wall 8b and the upper insulating plate 8c may be in contact or bonded, or may not be in contact. For example, as shown in FIG. 1, there may be a gap between the insulating wall 8b and the upper insulating plate 8c.

  The size of the lower insulating plate 8a and the upper insulating plate 8c is not particularly limited as long as the bottom or upper portion of the container 3 can be covered. The height of the insulating wall 8 b is not particularly limited, but it is preferable that the upper end of the insulating wall 8 b is above the upper end of the side surface of the container 3. This is because the container 3 becomes more difficult to receive an external load.

  The material of the insulating member 8 is not particularly limited as long as it has insulating properties. Examples of the material of the insulating member 8 include glass, various rubbers, polyolefin resin, fluororesin resin, ceramics, and the like. The thickness is not particularly limited, and may be set as appropriate according to the potential of the container 3. For example, the thickness of the lower insulating plate 8a and the upper insulating plate 8c may be 10 to 30 mm. In particular, it is preferable that the lower insulating plate 8a in contact with the container 3 is thicker. The thickness of the insulating wall 8b may be 1 to 10 mm, for example. As will be described later, when the insulating wall 8b is in the form of a single layer or a plurality of layers, the total thickness of the sheet-like insulating wall 8b may be 1 to 10 mm.

  The material of the pipe 6 is not particularly limited as long as it has corrosion resistance to the raw material liquid 2. Examples of the material of the pipe 6 include various resins, glasses, metals such as stainless steel, and the like. The diameter of the pipe 6 is not particularly limited, and may be appropriately set according to the supply amount of the raw material liquid 2 and the like. For example, the diameter of the pipe 6 may be 3 to 15 mm.

  The container 3 and the insulating member 8 are preferably accommodated in the tank 9. This is because the external load on the container 3 is further reduced. In this case, the upper insulating plate 8 c may be attached to the lid of the tank 9.

  Thus, when the container 3 and the insulating member 8 are accommodated in the tank 9, the insulating wall 8b is not required to be self-supporting. That is, an inexpensive sheet-like insulating material (insulating sheet) can be used as the material of the insulating wall 8b. That is, it is preferable that the container 3 and the insulating member 8 are accommodated in the tank 9 in terms of cost. For example, after the lower insulating plate 8a made of a plate-like insulating material is disposed in the tank 9, an insulating sheet temporarily fixed in a state of being rolled into a cylindrical shape is inserted. After the insertion, when the insulating sheet is released from temporary fixing, the cylindrical insulating sheet spreads and is arranged along the inner wall of the tank 9 to form the insulating wall 8b. At this time, the insulating sheet is rounded and temporarily fixed so as to be single or double or more. The insulating wall 8b can be arranged in the tank by such a low-cost and simple method. In this method, there may be a gap between the insulating wall 8b and the lower insulating plate 8a. However, this gap does not significantly affect the insulation property when the distance d is sufficiently secured. Finally, the container 3 is placed on the lower insulating plate 8a.

  Furthermore, it is preferable that the space in the container 3 communicates with the space in the tank 9 (outside the container). In this case, gas is supplied to the inside of the tank 9 to increase the pressure in the tank 9 so that the tank 9 functions as a high-pressure pump and the raw material liquid 2 stored in the container 3 is fed into the pipe 6. Can do. Furthermore, the tank 9 can also function as a pump for discharging the raw material liquid 2 stored in the emitter 5 from the emitter 5. Thereby, the electrospinning mechanism 1 is simplified. What is necessary is just to adjust the supply amount of the gas in the tank 9 with the gate valve 10, for example.

  The material of the tank 9 is not particularly limited. Especially, it is preferable that the tank 9 is metal from the point of intensity | strength. In particular, when the inside of the tank 9 is pressurized as described above, the tank 9 is preferably made of metal. Examples of the material of the metal tank 9 include stainless steel, iron, and aluminum alloy. When the tank 9 is made of metal, it is preferable to connect the tank 9 to the ground from the viewpoint of safety to prevent the tank 9 from being charged. The thickness (wall thickness) of the side wall of the tank 9 is not particularly limited. The thickness of the side wall of the tank 9 may be, for example, 5 to 20 mm from the viewpoint of strength.

[Emitter]
FIG. 2 schematically shows the emitter 5 according to the present embodiment. The emitter 5 is made of a conductor and has, for example, a long shape. The inside is hollow, and the raw material liquid 2 is supplied through the pipe 6. On the side of the emitter 5 facing the sheet 4, a plurality of outlets (not shown) for the raw material liquid 2 are provided. The shape of the cross section perpendicular to the longitudinal direction of the emitter 5 is not particularly limited, and may be a shape (V-type nozzle) that gradually decreases from the top to the bottom. In FIG. 2, the container 3 for storing the raw material liquid 2 and the insulating member 8 surrounding the container 3 are omitted.

  For example, the discharger 5 is installed above the discharger 5, and the second support 15 extending downward from the first support 14 parallel to the sheet 4 causes the longitudinal direction of the discharger 5 to be parallel to the main surface of the sheet 4. It is supported to become. The first support 14 may be movable so that the emitter 5 can be swung.

  The charging means for charging the emitter 5 and the sheet 4 includes a voltage applying device 7 that applies a voltage to the emitter 5, a counter electrode 13 that is installed in parallel with the conveyor belt 12 that supports the sheet 4, and It consists of The counter electrode 13 is grounded (grounded). Thereby, a potential difference corresponding to the voltage applied by the voltage application device 7 can be provided between the emitter 5 and the counter electrode 13 (sheet 4). The configuration of the charging unit is not particularly limited. For example, the sheet 4 may be negatively charged. Moreover, you may comprise the conveyor belt 12 from a conductor instead of providing the counter electrode 13. FIG.

[Raw material]
The raw material liquid 2 contains a raw material resin and a solvent. The raw material resin is a raw material of the fiber 2F, and the solvent dissolves the raw material resin (hereinafter referred to as a first solvent). From the raw material liquid 2, a fiber 2F containing a raw material resin is formed. The mixing ratio of the raw material resin and the first solvent in the raw material liquid 2 varies depending on the type of the selected raw material resin and the type of the first solvent. The ratio of the 1st solvent in the raw material liquid 2 is 60 mass% to 95 mass%, for example. The raw material liquid 2 may contain a solvent other than the first solvent for dissolving the raw material resin, various additives, and the like.

  The type of raw material resin is not particularly limited. For example, polyamide (PA), polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polyacetal (POM), polycarbonate (PC), polyetheretherketone ( PEEK), polysulfone (PSF), polyethersulfone (PES), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polyarylate (PAR), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinyl Examples of the polymer include alcohol (PVA), polyvinyl acetate (PVAc), polypropylene (PP), polyethylene terephthalate (PET), and polyurethane (PU). You may use these individually or in combination of 2 or more types. Among these, PES is preferable because it is suitable for the electrospinning method.

  What is necessary is just to select an appropriate thing as a 1st solvent according to the kind and manufacturing conditions of raw material resin. For example, 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, acetic acid Methyl, ethyl acetate, propyl acetate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, methyl chloride, ethyl chloride, methylene chloride, chloroform, o-chlorotoluene, p- Lorotoluene, 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 (DMAc), dimethyl sulfoxide, pyridine, water, etc. it can. These may be used alone or in combination of two or more. Among these, when a fiber containing PES is formed by an electrospinning method, DMAc is preferable because it is suitable for the electrospinning method and easily dissolves PES.

  The average fiber diameter of the fibers 2F formed using the electrospinning mechanism 1 is not particularly limited. According to the electrospinning mechanism 1, for example, ultrafine fibers having an average fiber diameter of 3 μm or less and further 1 μm or less can be formed. From the viewpoint of spinnability, the average fiber diameter is preferably 30 nm or more, and more preferably 50 nm or more. The spinnability of such ultrafine fibers is particularly susceptible to changes in the voltage of the electrospinning mechanism 1. Therefore, stabilizing the voltage of the electrospinning mechanism 1 is important when producing ultrafine fibers stably.

The accumulation amount (mass per unit area) of the fiber 2F is not particularly limited, and may be set as appropriate according to the application. The accumulation amount of the fiber 2F is, for example, 0.5 g / m ² or more and 10 g / m ² or less, and may be 0.9 g / m ² or more and 7 g / m ² or less.

[Sheet]
The sheet 4 is a target of the raw material liquid 2 to be injected, and is a collector that collects the fibers 2F generated using the electrospinning mechanism 1. Moreover, the sheet | seat 4 has a role as a base material which supports the accumulated fiber 2F in the obtained laminated body.

  The form and material of the sheet 4 are not particularly limited, and may be appropriately selected depending on the application. Examples of the sheet 4 include fiber structures such as resin sheets, paper sheets, woven fabrics, knitted fabrics, and nonwoven fabrics.

  Examples of the resin constituting the resin sheet include polyesters such as PP, PE, and PET. Examples of the fiber constituting the fiber structure include glass fiber, cellulose, acrylic resin, PP, polyethylene (PE), polyester (for example, PET, polybutylene terephthalate, etc.), PA, or a mixture thereof. The fiber diameter of the fiber is, for example, 0.5 μm or more and 20 μm or less, and may be 10 μm or more and 20 μm or less.

The thickness of the sheet 4 is not particularly limited, and may be set as appropriate depending on the application. The thickness of the sheet 4 is, for example, 100 μm or more and 500 μm or less. The mass per unit area of the sheet 4 is not particularly limited, and may be set as appropriate according to the application. The mass per unit area of the sheet 4 is, for example, 5 g / m ² or more and 60 g / m ² or less.

  The laminate of the present invention includes an air purifier or an air conditioner filter medium, a battery separation sheet, a fuel cell membrane, an in vitro test sheet such as a pregnancy test sheet, a medical sheet for cell culture, a dust mask, etc. It is suitable as a dust-proof cloth, dust-proof clothing, cosmetic sheet, wiping sheet for wiping off dust, and the like.

  1: electrospinning mechanism, 2: raw material liquid, 3: container, 4: sheet, 5: emitter, 6: pipe, 7: voltage application device, 8: insulating member, 8a: lower insulating plate, 8b: insulating wall, 8c: upper insulating plate, 9: tank, 10: gate valve, 12: conveyor belt, 13: counter electrode, 14: first support, 15: second support

Claims (8)

A container for storing a raw material resin containing a raw material resin as a fiber raw material and a solvent for dissolving the raw material resin;
An emitter for releasing the raw material liquid toward one main surface of the sheet;
A pipe for supplying the raw material liquid from the container to the emitter;
A method of producing a laminate using an electrospinning mechanism comprising a voltage applying device for applying a voltage to the emitter,
Applying a voltage to the raw material liquid inside the emitter together with the emitter using the voltage application device;
A discharging step of discharging the charged raw material liquid from the emitter toward the main surface of the sheet, generating the fiber containing the raw material resin, and depositing the fiber on the main surface of the sheet; , And
The manufacturing method of a laminated body with which the said container is surrounded by the insulating member provided with the lower insulating board which covers the bottom part of the said container, and the insulating wall which covers the side surface of the said container.   The manufacturing method of the laminated body of Claim 1 with which the said insulating wall has covered the side surface of the said container at intervals.   The manufacturing method of the laminated body of Claim 1 or 2 with which the upper end of the said insulating wall exists above the upper end of the said side surface of the said container.   The manufacturing method of the laminated body as described in any one of Claims 1-3 with which the said insulating member is further provided with the upper insulating board which covers the upper part of the said container.   The manufacturing method of the laminated body as described in any one of Claims 1-4 with which the said container and the said insulating member are accommodated in the tank.   The method for manufacturing a laminated body according to claim 5, wherein the tank is made of metal and connected to a ground. The space inside the container and the space outside the container are in communication with the tank,
The manufacturing method of the laminated body of Claim 5 or 6 which pressurizes the inside of the said tank and sends the said raw material liquid stored in the said container to the said pipe in the said deposition process. A container for storing a raw material resin containing a raw material resin as a fiber raw material and a solvent for dissolving the raw material resin;
An emitter for releasing the raw material liquid toward one main surface of the sheet;
A pipe for supplying the raw material liquid from the container to the emitter;
A laminate manufacturing apparatus comprising an electrospinning mechanism including a voltage applying device that applies a voltage to the emitter.
The manufacturing apparatus of a laminated body with which the said container is enclosed by the insulating member provided with the lower insulating board which covers the bottom part of the said container, and the insulating wall which covers the side surface of the said container.

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