WO2020195635A1 - Film cleaning device and method for manufacturing cleaning-completed film - Google Patents

Film cleaning device and method for manufacturing cleaning-completed film Download PDF

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Publication number
WO2020195635A1
WO2020195635A1 PCT/JP2020/009105 JP2020009105W WO2020195635A1 WO 2020195635 A1 WO2020195635 A1 WO 2020195635A1 JP 2020009105 W JP2020009105 W JP 2020009105W WO 2020195635 A1 WO2020195635 A1 WO 2020195635A1
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WO
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Prior art keywords
film
cleaning
cleaning liquid
roll
drive roll
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Application number
PCT/JP2020/009105
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French (fr)
Japanese (ja)
Inventor
石田洋規
田口貴之
増田昇三
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2020517601A priority Critical patent/JPWO2020195635A1/ja
Publication of WO2020195635A1 publication Critical patent/WO2020195635A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B11/00Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/02Cleaning by the force of jets or sprays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04Cleaning involving contact with liquid

Definitions

  • the present invention relates to a film cleaning device. Further, the present invention relates to a method for producing a washed film, in which the film is washed while being conveyed.
  • a method of transporting the film As a method of transporting the film, a method is known in which the film is held by a driven roll and tension is applied in the film traveling direction by rotating the roll to transport the film.
  • the film may slip against the drive roll, causing poor transport.
  • a solvent and an object to be cleaned tend to remain on the film, which tends to cause transport failure. This is because there are not a few objects to be cleaned in the cleaning tank, so the objects to be cleaned once removed reattach to the film, and the objects to be cleaned remain on the surface of the film taken out from the cleaning tank. is there.
  • Patent Document 1 proposes a method of removing the solution adhering to the film surface by spray-cleaning the film surface at the outlet of the cleaning tank with pure water.
  • the amount of material to be cleaned that is brought into the drive roll is reduced, the slip of the film with respect to the drive roll is improved, and the followability of the film transport speed with respect to the rotation speed of the drive roll is improved, so that the tension controllability to the film is improved. It is known to suppress the occurrence of wrinkles and meandering.
  • An object to be solved by the present invention is to provide a film cleaning apparatus that improves detergency and is less likely to cause wrinkles. Another object of the present invention is to produce a washed film having good detergency.
  • an object of the present invention is to improve the cleaning effect of the cleaning liquid from the cleaning tank lifted to the drive roll, to clean the film surface, and to perform appropriate tension control without causing wrinkles or rupture of the film.
  • An object of the present invention is to provide a cleaning device capable of increasing the transport speed.
  • the cleaning apparatus of the present invention is for cleaning a film having a drive roll (the drive roll is referred to as a first drive roll) in which the film from the cleaning tank first comes into contact with the cleaning tank and downstream of the cleaning tank.
  • a means for scraping off the cleaning liquid accompanying the film leaving the cleaning tank is provided at least on the film surface side that first comes into contact with the first drive roll immediately after passing through the cleaning tank.
  • a means for spraying the cleaning liquid onto the film is provided between the means for scraping off the cleaning liquid and the first driving roll, and is provided at least on the film surface side that first contacts the first driving roll. It is a device.
  • a film cleaning device having the following features I) to II).
  • I) It has a washing tank and a drive roll on the outlet side of the washing tank.
  • II) Between the washing tank and the driving roll, the inside of the washing tank with respect to the surface on the side where the film first contacts the driving roll (hereinafter, the surface is referred to as surface A) when viewed from the cleaning tank side.
  • a means for scraping off the cleaning liquid accompanying the surface and a means for spraying the cleaning liquid on the surface are provided in this order.
  • the drive roll of I) corresponds to the first drive roll installed downstream of the washing tank. It also intends to provide various improved aspects.
  • it is a method for producing a washed film that is washed while transporting the film. After passing through the film washing tank, the cleaning liquid accompanying the film is scraped off from the washing tank, and then the cleaning liquid is sprayed onto the film.
  • the film is passed through the washing tank in the order of the first contacting drive roll (referred to as the first drive roll), and the scraping and the spraying cause the film to come into contact with the first drive roll.
  • the first drive roll the order of the first contacting drive roll
  • the scraping and the spraying cause the film to come into contact with the first drive roll.
  • a method for producing a washed film which is performed on a film surface on the side.
  • a step of scraping off the object to be cleaned on the film surface is provided on the surface side in contact with the first drive roll, and the film is further scraped off.
  • FIG. 1 and 2 are views showing the steps used by the cleaning apparatus of the present invention for the film to be conveyed.
  • the continuously supplied film 1, the cleaning tank 2 for cleaning the film 1, the driving roll 3, and the cleaning liquid and the object to be cleaned accompanying from the inside of the cleaning tank are scraped off from the film surface.
  • It includes a roll 4 as a means, a nozzle array 5 as a means for spraying a cleaning liquid, and a drying furnace 6 for drying the film.
  • the drive roll indicates a drive roll (referred to as a first drive roll) to which the film leaving the cleaning tank 2 first contacts.
  • the film 1 runs in the direction of the arrow. After running in the cleaning liquid of the cleaning tank 2, the film 1 rises in the air while lifting the cleaning liquid 2.
  • the cleaning liquid adhering to the film 1 contains an object to be cleaned.
  • the film 1 comes into contact with the roll 4, which is a means for scraping off, and the cleaning liquid containing the object to be cleaned is scraped off. This is because the gap between the film 1 and the roll 4 gradually narrows until the film 1 approaches and comes into contact with the roll 4, so that the cleaning liquid is scraped off so as to flow downstream.
  • the traveling direction is changed by the roll 4 to reach the next roll 4.
  • the contact surfaces of the first roll 4 and the film 1 of the second roll 4 are opposite to each other. The cleaning liquid containing the object to be cleaned adhering to the film 1 is scraped off by the second roll 4.
  • the film 1 passes through the nozzle array 5 for spraying the cleaning liquid and reaches the first drive roll 3. Since the cleaning liquid and the object to be cleaned are reduced in the film 1, slippage of the film is suppressed, and the film 1 runs stably following the rotation speed of the first drive roll 3.
  • the nozzle array 5 is arranged on the surface (surface A) on the side where the film 1 first contacts the first drive roll 3 when viewed from the cleaning tank 2 side.
  • the roll 4 which is a scraping means, efficiently removes the cleaning liquid including the object to be cleaned lifted from the cleaning tank before spraying the cleaning liquid. Therefore, even if the cleaning liquid is sprayed further downstream, the first drive roll 3 The slippage of the film on the film can be suppressed.
  • the film 1 continuously supplied, the coating machine 8 for coating the surface of the film, the cleaning tank 2 for cleaning the film 1 after coating, and the first drive roll. 3. It is provided with a roll 4 which is a means for scraping off the cleaning liquid and an object to be cleaned accompanying from the inside of the cleaning tank, a nozzle array 5 which is a means for spraying the cleaning liquid, and a drying furnace 6 for drying the film.
  • a roll 4 which is a means for scraping off the cleaning liquid and an object to be cleaned accompanying from the inside of the cleaning tank
  • a nozzle array 5 which is a means for spraying the cleaning liquid
  • a drying furnace 6 for drying the film.
  • the object to be cleaned is a substance contained in the cleaning liquid to be cleaned that is attached to the film 1.
  • the film 1 refers to a film, a coating layer on the surface of the film, and a laminate layer.
  • the object to be cleaned is a substance extracted from the film substrate or a part of a coating agent processed on the surface of the film substrate, which is a substance to be cleaned and removed from the film substrate.
  • the cleaning liquid that accompanies the film includes dust floating in the cleaning tank contained in the cleaning liquid, dust that has fallen off from the film, foreign substances such as film pieces, and a low-volatile liquid contained in the film.
  • examples include foreign objects (dust of the core used for the film core, fibers of work clothes) that are not a part of the film or coating liquid.
  • foreign objects dust of the core used for the film core, fibers of work clothes
  • additives such as plasticizers contained in the coating liquid can be mentioned.
  • the solvent used in the coating liquid examples include a good solvent that can dissolve a fluorine-containing resin and can be miscible (compatible with an arbitrary concentration) with a poor solvent (phase separation liquid) such as water.
  • a porous substrate coated with such a good solvent and a coating liquid containing a fluorine-containing resin dissolved in the good solvent is introduced into a cleaning tank filled with a cleaning liquid composed of a poor solvent, it is contained in the coating film.
  • the resin and the good solvent are phase-separated, and the resin is solidified to form a porous layer.
  • the concentration of the fluorine-containing resin in the coating liquid is preferably in the range of 2% by weight to 7% by weight, more preferably in the range of 3% by weight to 6% by weight.
  • the coating thickness can be set to 5 ⁇ m to 25 ⁇ m (one side).
  • the variation in the width direction of the coating thickness is preferably ⁇ 10% or less.
  • the drive roll is a roll provided with a drive motor for transporting the film.
  • the cleaning device of the present invention includes a first drive roll 3 on the outlet side of the cleaning tank 2.
  • the first drive roll 3 when the film is conveyed in the cleaning tank 2, frictional resistance with the cleaning liquid is applied to the film, so that a tension difference is generated between the outlet side and the entrance side of the cleaning tank 2.
  • the tension on the inlet side of the cleaning tank 2 is lower than that on the outlet side.
  • the first drive roll 3 is a drive roll that the film coming out of the washing tank comes into contact with first, and is used to compensate for the above-mentioned tension difference.
  • the tension is low, the film may loosen, meander, and wrinkle. Therefore, it is important to transport the film by the drive roll at a tension and speed that does not cause wrinkles, sagging, or meandering of the film.
  • a nip roll is a pair or a plurality of pairs of rolls that sandwich and convey the film, and may be composed of two drive rolls.
  • a free rotation roll that comes into contact with one drive roll and is driven by the drive roll. It may be a combination with.
  • the first drive roll is integrated with the washing tank on the same pedestal, but it can also be arranged as a separate body.
  • the cleaning tank is a step of transporting the film in the liquid to clean the object to be cleaned, which adheres to the film surface or is contained in the film itself or the coating layer provided on the film surface. Pure water, a solvent, or the like is generally used as the cleaning liquid, but there is no particular limitation as long as the purpose of cleaning can be achieved.
  • the scraping step is a step of scraping off the cleaning liquid and the object to be cleaned accompanying the film taken out from the cleaning tank, and is performed by using the scraping means 4. That is, the scraping step of the object to be cleaned is performed by using the scraping step 4 applied when scraping the cleaning liquid and the object to be cleaned accompanying the film taken out from the cleaning tank.
  • a doctor blade, an air nozzle, a roll, or the like can be used to obtain a uniform scraping effect in the width direction of the film.
  • There is no particular limitation as long as the object to be cleaned can be physically removed as long as the conveyed film is not damaged. Since the scraping efficiency is high, it is preferable to use a means for removing the cleaning liquid and the object to be cleaned by directly contacting the film.
  • freeroll for film is a method that has the lowest concern about wrinkles and film rupture, simplifies the apparatus, and can obtain a uniform scraping effect in the film width direction. It is preferable that the film is held by a roll (a roll that rotates when it comes into contact with the film but is not driven by a motor or the like) and scraped off.
  • the free roll has a large roll diameter because a larger area of the film in contact with the free roll enables efficient scraping.
  • the cleaning liquid spraying process In the step of spraying the cleaning liquid, it is preferable to use a shower nozzle or the like so that the cleaning liquid uniformly hits the film 1.
  • the shower shape generally includes a cylindrical type, a spray type, a fan type, and the like. From the results of the studies conducted by the inventors so far, it is determined that the cleaning effect is determined by the collision pressure of the cleaning liquid that hits the film when cleaning the film surface or the object to be cleaned that has penetrated into the porous membrane such as the battery separator. I know it.
  • a shower nozzle that gives a fan-shaped shower shape from the viewpoint that the collision pressure of the cleaning liquid that hits the film at a constant flow rate is high and the shower cleaning liquid is uniformly applied in the film width direction.
  • the reason why it is preferable to apply the shower uniformly is that if the shower is not applied uniformly, wrinkles or the like may occur on the film, causing poor transportation and causing poor appearance of the film product.
  • the collision pressure depends on the discharge pressure, the spraying method, and the distance between the films.
  • FIG. 3 shows a spraying means for spraying the cleaning liquid.
  • the means 5 for spraying the cleaning liquid uses a nozzle array that sprays the cleaning liquid in a fan-shaped shower shape, and is provided so as to hit the entire width of the film 1.
  • the first drive roll 3 that first contacts the film from the outlet side of the cleaning tank 2 is not a nip roll but a structure in which the drive roll contacts only one side of the film, cleaning is performed. It is preferable to spray the cleaning liquid on the surface (surface A) on the side where the film first contacts the first drive roll when viewed from the tank side.
  • the cleaning liquid When the first drive roll 3 comes into contact with both sides of the film like a nip roll, it is preferable to spray the cleaning liquid on both sides of the film when viewed from the cleaning tank side.
  • a means for spraying the cleaning liquid a plurality of nozzles for blowing out the cleaning liquid in a fan shape in the width direction of the film to be conveyed are provided, and each nozzle is at equal intervals and with the cleaning liquid blown out from the nozzles on the film surface. It is preferable that the width of the overlapping with the cleaning liquid blown out from the adjacent nozzles is 5% or more and 50% or less. With such a configuration, it becomes easy to obtain a uniform surface pressure and efficient cleaning. Is possible.
  • FIG. 4 is a front view of one of the nozzles that injects the cleaning liquid in a fan shape.
  • the cleaning effect cannot be obtained if the cleaning liquid colliding with the film 1 does not collide in the width direction of the film 1, so that the width of the film 1 is set.
  • the cleaning liquid that collides with the direction preferably hits the entire width of the film 1.
  • the spread angle of the injection shape 10 is such that the width of the injection shape 10 overlaps with the cleaning liquid ejected from the adjacent nozzles so that the cleaning liquids collide evenly in the entire width direction of the film 1. It is preferable to set the number of nozzles 9 so as to be 5% or more and 50% or less, and to cover the entire width of the film.
  • the distance between the film 1 and the means 9 for spraying the cleaning liquid is set by considering the degree of overlap between the cleaning liquid blown from the adjacent nozzles and the fan-shaped spreading angle of the shower nozzle, and the distance at which the cleaning liquid hits the film 1 evenly. It is preferable to do so.
  • FIG. 5 illustrates the positional relationship between the film 1 and the means 5 for spraying the cleaning liquid.
  • FIG. 5 is a cross-sectional view seen from the direction perpendicular to the longitudinal direction of the film.
  • a nozzle array provided with a plurality of nozzles for injecting cleaning liquid in a fan shape in the film width direction extends toward the back of the paper in FIG.
  • the angle of the cleaning liquid blowing hole with respect to the film transport direction in the means for spraying the cleaning liquid is related to the collision pressure of the cleaning liquid that hits the film.
  • the angle at which the collision pressure increases with respect to the film surface is effective for cleaning the object to be cleaned by applying it to the film surface from the normal direction. From this, it is preferable that the temperature is within the range of 60 ° or more and 120 ° or less with respect to the transport direction of the film.
  • the angle with respect to the transport direction of the film is an angle obtained on a plane perpendicular to the film surface, including the transport direction of the film.
  • the transport direction of the film surface is 0 ° and the angle between the film and the cleaning liquid 10 sprayed from the nozzle array is within the range of 60 ° or more and 120 ° or less. From the viewpoint of obtaining a high cleaning effect, it is preferably in the range of 80 ° or more and 100 ° or less.
  • the collision pressure of the cleaning liquid sprayed from the cleaning liquid spraying means 5 against the film is preferably 0.05 MPa to 0.50 MPa at a transport speed of 5 m / min to 300 m / min.
  • the means 4 for scraping off the cleaning liquid and the means 5 for spraying the cleaning liquid are arranged between the outlet side of the cleaning tank 2 and the first drive roll 3, and the film is the first when viewed from the cleaning tank side. It is arranged in this order so as to act on the surface (surface A) on the side that first contacts the drive roll 3 of 1. This is to prevent the object to be cleaned accompanying from the washing tank from reaching the first drive roll 3.
  • the present invention it is preferable to further provide means 4 for scraping off the cleaning liquid and means 5 for spraying the cleaning liquid so as to act on the surface opposite to the surface A. That is, in the present invention, the means 4 for scraping off the cleaning liquid and the means 5 for spraying the cleaning liquid are at least arranged toward the surface side of the first drive roll 3 with which the film first comes into contact after passing through the cleaning tank. A means 4 for scraping off the cleaning liquid in the order of being closer to the cleaning tank is arranged in the film transport direction, followed by a means 5 for spraying the cleaning liquid.
  • the means for scraping off the cleaning liquid and the means for spraying the cleaning liquid are films. It is preferable that the film is provided so as to face both sides of the.
  • FIG. 2 shows an example in which a coating machine such as a dip coat head is used.
  • the coating machine is preferably capable of applying a coating liquid having a viscosity of 10 mPa ⁇ s or more and 3000 mPa ⁇ s or less on one side of the film with a coating thickness of 1 ⁇ m or more and 100 ⁇ m or less, and the thickness variation in the width direction is ⁇ 10%.
  • the coating method is not particularly limited, and for example, dip coat, cast coat, spin coat, bar coat, spray coat, blade coat, slit die coat, gravure coat, reverse coat, lip direct coat, comma coat, screen.
  • wet coating methods such as printing, mold coating, printing transfer, and inkjet can be mentioned.
  • the lip direct method, comma coat method, and dip coat method which are scraping methods suitable for high viscosity, thin film, and high speed coating, are preferable. ..
  • the dip coating method is more preferable from the viewpoint that a porous layer can be formed on both sides at the same time. By adopting the dip coat method, it is possible to apply at a speed of 80 m / min or more.
  • the film transport speed can be set in the range of, for example, 5 m / min to 300 m / min, and is appropriately set according to the coating method from the viewpoints of productivity and uniformity of coating film thickness. can do.
  • the film used in the present invention is not particularly limited as long as it has a film-like shape, and examples thereof include a plastic film, a non-woven fabric sheet, and a carbon sheet.
  • examples of the plastic film include polyester films such as polyethylene terephthalate and polyethylene nitrate, polyolefin films such as polypropylene, polyethylene and composite films thereof, polyimide films, polyamides, and polyphenylene sulfide films.
  • it can be preferably a porous base material.
  • porous medium Demand for separator films for lithium-ion batteries has been increasing in recent years, and their functionality is increasing, such as by providing a coat layer with a functional layer coated on the surface.
  • Most of the porous composite films (separator films) are porous from the viewpoint of ionic conductivity. For this reason, a solvent such as an organic solvent is often used in the manufacturing process of the porous film and the forming process of the coat layer, and foreign substances and solid desorbed substances from the film are likely to occur.
  • the cleaning apparatus of the present invention is preferably used in those using such a porous material, particularly in a separator film.
  • As the porous substrate it is preferable to use a polyolefin porous membrane.
  • polyethylene and polypropylene are preferable. It may also be a single product or a mixture of two or more different polyolefin resins, for example a mixture of polyethylene and polypropylene.
  • the polyolefin may be a homopolymer or a copolymer.
  • polyethylene may be a homopolymer of ethylene, a copolymer containing another ⁇ -olefin unit, or polypropylene. May be a homopolymer of propylene or a copolymer containing another ⁇ -olefin unit.
  • the porous substrate may be a single-layer film or a laminated film composed of two or more layers.
  • the thickness of the porous substrate is preferably in the range of 3 ⁇ m to 25 ⁇ m, more preferably in the range of 3 to 20 ⁇ m.
  • the porosity of the porous substrate is preferably in the range of 30 to 70%, more preferably in the range of 35 to 60%.
  • the overall film thickness of the porous composite film can be set in the range of 4 ⁇ m to 30 ⁇ m, preferably in the range of 4 ⁇ m to 24 ⁇ m. By setting the thickness in such a range, it is possible to secure the mechanical strength and the insulating property while making the film as thin as possible.
  • the functional layer of the porous composite film is preferably porous, for example, when it is used as a separator for a lithium ion battery.
  • the thickness of the functional layer can be set in the range of 1 to 5 ⁇ m, preferably in the range of 1 to 4 ⁇ m, and more preferably in the range of 1 to 3 ⁇ m. By setting the thickness of the functional layer in such a range, it is possible to obtain a sufficient effect of forming the functional layer and adhesive strength with the minimum necessary thickness.
  • the porous substrate was processed using the apparatus configuration shown in FIG. Specifically, a coating liquid containing a solvent of N-methyl-2-pyrrolidone (NMP) in a coating machine 8 at a transport speed of 60 m / min for a separator (thickness 7 ⁇ m) of a lithium ion battery having a width of 900 mm. was applied, washed in a washing tank 2 containing pure water, and dried in a drying oven 6.
  • NMP N-methyl-2-pyrrolidone
  • the cleaning liquid As a means for spraying the cleaning liquid, pure water is used as the cleaning liquid, and MVVP115 manufactured by Ikeuchi Co., Ltd. is used as the shower nozzle for discharging the cleaning liquid.
  • the cleaning liquid from the adjacent cleaning nozzles at the landing point at equal intervals in the direction parallel to the film width direction.
  • the overlap with and is set to 5% when the reachable width of the cleaning liquid by each nozzle is 100%, and the number of nozzles is provided so that the cleaning liquid reaches the entire width of the film. As shown in FIG. 3, the cleaning liquid was sprayed beyond the film width.
  • a pressure gauge (Nagano Keiki Co., Ltd. "ordinary pressure gauge AA10-160") is installed just before the shower nozzle in the piping path from the gear pump to the shower nozzle, and a ball valve is installed in the piping path between the gear pump and the pressure gauge. Then, the value at which the flow rate was changed was read with a pressure gauge and used as the shower discharge pressure.
  • a flow meter (Keyence Co., Ltd. "Clamp-on type flow meter FD-Q15A / 20A") is installed just before the shower nozzle in the piping path from the gear pump to the shower nozzle, and a ball valve is connected to the piping path between the gear pump and the flow meter. was installed, and the value at which the flow rate was changed was read with a flow meter and used as the shower flow rate.
  • Shower angle It is the angle formed by the cleaning liquid discharged from the shower nozzle and the film, and is obtained as the angle formed by the cleaning liquid and the film when viewed from the downstream side in the film transport direction on a plane parallel to the film transport direction and perpendicular to the film surface ( (See FIG. 5). The same applies to the back surface of the film, and when the shower angle is an acute angle, the cleaning liquid is sprayed from the downstream side to the upstream side of the film.
  • the separator film immediately before passing through the first drive roll 3 was sampled, and the amount of the object to be cleaned (NMP) remaining on the film was determined and evaluated.
  • the residual NMP contained in the sampled separator film was determined by the following measuring method.
  • sample preparation> To prepare the standard solution, weigh the standard product (0.0104 g) in a measuring flask (10 mL), and then use N, N-dimethylacetamide (DMAc) to formulate the standard stock solution (concentration: 1040 ⁇ g / mL). , DMAc was diluted to prepare a standard solution for calibration lines.
  • DMAc N, N-dimethylacetamide
  • sample solution cut the sample of the separator film just before passing through the first drive roll 3 into 1 cm ⁇ 1 cm, weigh the sample (0.1 g) into a 20 mL screw tube, and add 10 mL of DMAc.
  • the sample solution was prepared by covering it with a lid, immersing it (24 hours), and sonicating it (30 minutes).
  • Examples 1 to 4 As shown in Table 1, the shower flow rate was changed to 5, 7, 9, 10 L / min, the shower discharge pressure was changed to 0.05, 0.10, 0.13, 0.16 MPa, the shower angle was 90 °, and the scraping process was performed. The coating was carried out under certain conditions. As a result, it was possible to obtain a separator film having a smaller residual NMP amount when the shower flow rate was 10 L / min and the shower discharge pressure was 0.16 MPa than when the shower flow rate was 5 L / min and the shower discharge pressure was 0.05 MPa.
  • Examples 5, 6 and 7 The shower angle was changed to 120 ° (Example 5), 60 ° (Example 6), and 30 ° (Example 7), respectively, the shower flow rate was 10 L / min, the shower discharge pressure was 0.16 MPa, and scraping was performed.
  • the coating was carried out under the condition of having a process. As a result, it was possible to obtain a separator film having a smaller residual NMP amount when the shower angle was 90 ° than when the shower angles were 30 °, 60 ° and 120 °.
  • Comparative Example 2 A separator film was produced in the same manner as in Example 1 except that there was no shower in the spraying step and no scraping step.

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  • Cleaning By Liquid Or Steam (AREA)

Abstract

The purpose of the present invention is to provide a cleaning device for cleaning a film while transporting the film, wherein the surface of the film can be cleaned with the improved cleaning effect of a cleaning liquid that is carried by the film and lifted to a driving roller from a cleaning tank, and the transporting speed can be increased while correctly performing tension control without causing wrinkle and damage to the transported film. To this end, a film cleaning device is provided, which is for cleaning a film and has a cleaning tank and a driving roll (the driving roll is referred to as a first driving roll) that is arranged downstream of the cleaning tank and firstly makes contact with a film out of the cleaning tank, wherein: a means for scraping off the cleaning liquid carried by the film out of the cleaning tank is provided at least on a film surface side that firstly makes contact with the first driving roll directly after passing through the cleaning tank; and a means for spraying the cleaning fluid onto the film is present between the means for scraping off the cleaning liquid and the first driving roll and is provided at least on the film surface side that firstly makes contact with the first driving roll.

Description

フィルム洗浄装置および洗浄済みフィルムの製造方法Film cleaning equipment and manufacturing method of cleaned film
 本発明は、フィルムの洗浄装置に関する。さらに、フィルムを搬送しながら洗浄を行う、洗浄済みフィルムの製造方法に関する。 The present invention relates to a film cleaning device. Further, the present invention relates to a method for producing a washed film, in which the film is washed while being conveyed.
 フィルムを搬送する方法として、駆動式のロールにフィルムを抱かせ、ロールを回転させることでフィルム進行方向に張力を付与し、搬送する方法が知られている。 As a method of transporting the film, a method is known in which the film is held by a driven roll and tension is applied in the film traveling direction by rotating the roll to transport the film.
 しかしながら、フィルムに溶媒や異物などの付着物があると駆動ロールに対してフィルムが滑り、搬送不良を起こすことがある。特に、洗浄液によるフィルム洗浄工程のある装置では、フィルムに溶媒や被洗浄物が残存しやすく、搬送不良を起こしやすい。これは、洗浄槽内に少なからず被洗浄物が存在していることから、一旦除去された被洗浄物がフィルムに再付着し、洗浄槽から取り出されたフィルム表面に被洗浄物が残るためである。 However, if there are deposits such as solvent or foreign matter on the film, the film may slip against the drive roll, causing poor transport. In particular, in an apparatus having a film cleaning step with a cleaning liquid, a solvent and an object to be cleaned tend to remain on the film, which tends to cause transport failure. This is because there are not a few objects to be cleaned in the cleaning tank, so the objects to be cleaned once removed reattach to the film, and the objects to be cleaned remain on the surface of the film taken out from the cleaning tank. is there.
 このような場合、駆動ロールにフィルムを抱かせる方法のみでは、フィルムと駆動ロールの間に被洗浄物が入り込み、フィルムと駆動ロール間の摩擦力が低下し、フィルムが滑りやすくなる。そして、フィルム搬送方向に正しく張力が付与できないこと等の搬送不良を引き起こすことがある。また、フィルム表面にコーティング等の加工を行い、その下流で洗浄を行う工程を含むフィルム洗浄装置においては、フィルムの搬送速度を速くし、生産性を向上することが望まれている。 In such a case, only by the method of holding the film in the drive roll, the object to be cleaned enters between the film and the drive roll, the frictional force between the film and the drive roll is reduced, and the film becomes slippery. Then, it may cause a transfer defect such that tension cannot be correctly applied in the film transfer direction. Further, in a film cleaning apparatus including a step of processing a film surface with a coating or the like and cleaning the film surface downstream thereof, it is desired to increase the transfer speed of the film and improve the productivity.
 特許文献1では、洗浄槽出口のフィルム表面へ純水を用いたスプレー洗浄を行うことで、フィルム表面に付着した溶液を落とす方式が提案されている。駆動ロールへ持ち込まれる被洗浄物が減少し、駆動ロールに対するフィルムの滑りが改善し、駆動ロールの回転速度に対するフィルム搬送速度の追従性が向上するため、フィルムへの張力制御性が向上して、シワや蛇行の発生を抑制することが知られている。 Patent Document 1 proposes a method of removing the solution adhering to the film surface by spray-cleaning the film surface at the outlet of the cleaning tank with pure water. The amount of material to be cleaned that is brought into the drive roll is reduced, the slip of the film with respect to the drive roll is improved, and the followability of the film transport speed with respect to the rotation speed of the drive roll is improved, so that the tension controllability to the film is improved. It is known to suppress the occurrence of wrinkles and meandering.
特開2007-246849号公報Japanese Unexamined Patent Publication No. 2007-246849
 本発明が解決しようとする課題は、洗浄性を向上し、しわ等が発生しくいフィルムの洗浄装置を提供することである。さらに、洗浄性が良好な洗浄済みフィルムを製造することにある。 An object to be solved by the present invention is to provide a film cleaning apparatus that improves detergency and is less likely to cause wrinkles. Another object of the present invention is to produce a washed film having good detergency.
 従来技術では、フィルムの搬送速度が速い場合、洗浄時間が短くなることや、従来の洗浄液でフィルム表面をスプレー洗浄する方法のみでは、フィルム表面の被洗浄物を洗浄する効果が減少してしまう。そのため、駆動ロールへ持ち込まれる被洗浄物により、フィルムと駆動ロールの間に搬送速度が遅い場合に比べて、被洗浄物がフィルムと駆動ロールとの間に多く入り込む。結果、フィルムと駆動ロールとの間の摩擦力が低下し、フィルムが滑り、正しくフィルム搬送方向に張力が付与できなくなって、搬送不良を引き起こすことがあった。 In the conventional technique, when the film transport speed is high, the cleaning time is shortened, and the effect of cleaning the object to be cleaned on the film surface is reduced only by the conventional method of spray cleaning the film surface with a cleaning liquid. Therefore, due to the object to be cleaned that is brought into the drive roll, a larger amount of the object to be cleaned enters between the film and the drive roll than when the transport speed is slow between the film and the drive roll. As a result, the frictional force between the film and the drive roll is reduced, the film slips, and tension cannot be correctly applied in the film transport direction, which may cause transport failure.
 搬送速度の増加に応じてスプレー洗浄液の流量を上げる方法があるが、流量を上げることにより、フィルムに洗浄液が当たる衝突圧が高くなることでシワ、破膜等の懸念があり、有効ではなかった。 There is a method of increasing the flow rate of the spray cleaning liquid according to the increase in the transport speed, but it was not effective because increasing the flow rate increases the collision pressure at which the cleaning liquid hits the film, which may cause wrinkles and film rupture. ..
 そこで、本発明の目的は、駆動ロールへ持ち上げられる洗浄槽からの洗浄液の洗浄効果を上げ、かつ、フィルム表面を洗浄するとともに、シワ、破膜を発生させることなく適正な張力制御を行いながら、搬送速度を上げることができる洗浄装置を提供することにある。 Therefore, an object of the present invention is to improve the cleaning effect of the cleaning liquid from the cleaning tank lifted to the drive roll, to clean the film surface, and to perform appropriate tension control without causing wrinkles or rupture of the film. An object of the present invention is to provide a cleaning device capable of increasing the transport speed.
 すなわち本発明の洗浄装置は、洗浄槽と該洗浄槽の下流に前記洗浄槽から出たフィルムが最初に接触する駆動ロール(該駆動ロールを第1の駆動ロールという)を有するフィルムを洗浄するための洗浄装置であって、洗浄槽を出たフィルムに随伴する洗浄液を掻き落とす手段が、洗浄槽を通過直後にあって、前記第1の駆動ロールと最初に接触するフィルム面側に少なくとも設けられ、さらに、洗浄液を前記フィルムに吹き付ける手段が、前記洗浄液を掻き落とす手段と第1の駆動ロールとの間にあって、前記第1の駆動ロールと最初に接触するフィルム面側に少なくとも設けられる、フィルム洗浄装置である。 That is, the cleaning apparatus of the present invention is for cleaning a film having a drive roll (the drive roll is referred to as a first drive roll) in which the film from the cleaning tank first comes into contact with the cleaning tank and downstream of the cleaning tank. A means for scraping off the cleaning liquid accompanying the film leaving the cleaning tank is provided at least on the film surface side that first comes into contact with the first drive roll immediately after passing through the cleaning tank. Further, a means for spraying the cleaning liquid onto the film is provided between the means for scraping off the cleaning liquid and the first driving roll, and is provided at least on the film surface side that first contacts the first driving roll. It is a device.
 また、下記I)~II)の特徴を有するフィルム洗浄装置である。
I)洗浄槽、および該洗浄槽の出側に駆動ロールを有する。
II)前記洗浄槽と前記駆動ロールとの間に、洗浄槽側からみて、前記フィルムが前記駆動ロールに最初に接触する側の面(係る面を以下、面Aという)に対して洗浄槽内から随伴される洗浄液を掻き落とす手段、および、該面に対して洗浄液を吹き付ける手段をこの順に有する。ここで、I)の駆動ロールは、洗浄槽の下流に設置された最初の駆動ロールにあたる。また、種々の改良された態様を提供せんとするものである。
Further, it is a film cleaning device having the following features I) to II).
I) It has a washing tank and a drive roll on the outlet side of the washing tank.
II) Between the washing tank and the driving roll, the inside of the washing tank with respect to the surface on the side where the film first contacts the driving roll (hereinafter, the surface is referred to as surface A) when viewed from the cleaning tank side. A means for scraping off the cleaning liquid accompanying the surface and a means for spraying the cleaning liquid on the surface are provided in this order. Here, the drive roll of I) corresponds to the first drive roll installed downstream of the washing tank. It also intends to provide various improved aspects.
 さらに、フィルムを搬送しながら洗浄する洗浄済みフィルムの製造方法であって、フィルム洗浄槽を通過後に、前記洗浄槽から前記フィルムに随伴する洗浄液を掻き落とし、次に、洗浄液を前記フィルムに吹き付け、前記フィルムを前記洗浄槽を通過後の最初に接触する駆動ロール(第1の駆動ロールという)の順に通過させ、かつ、前記掻き落としおよび前記吹き付けは、前記フィルムが第1の駆動ロールに接触する側のフィルム面に対して行う、洗浄済みフィルムの製造方法を提供する。 Further, it is a method for producing a washed film that is washed while transporting the film. After passing through the film washing tank, the cleaning liquid accompanying the film is scraped off from the washing tank, and then the cleaning liquid is sprayed onto the film. The film is passed through the washing tank in the order of the first contacting drive roll (referred to as the first drive roll), and the scraping and the spraying cause the film to come into contact with the first drive roll. Provided is a method for producing a washed film, which is performed on a film surface on the side.
 本発明によれば、フィルムが第1の駆動ロールと接触する前に、第1の駆動ロールと接触する面側に対して、フィルム表面の被洗浄物を掻き落とす工程を設け、更に掻き落とした面と同一の面に洗浄液を吹き付ける工程を設けることにより、フィルムに随伴して駆動ロールへ持ち上げられる被洗浄物および洗浄液が減少し、高い洗浄効果が得られる。さらに、フィルムと第1の駆動ロール間の摩擦抵抗の低下を防ぎ、駆動ロールの回転速度に対するフィルムの搬送速度の追従性が向上することで、搬送速度を上げても、張力制御性が向上するという効果が両立できる。 According to the present invention, before the film comes into contact with the first drive roll, a step of scraping off the object to be cleaned on the film surface is provided on the surface side in contact with the first drive roll, and the film is further scraped off. By providing the step of spraying the cleaning liquid on the same surface as the surface, the objects to be cleaned and the cleaning liquid that are lifted to the drive roll along with the film are reduced, and a high cleaning effect can be obtained. Further, by preventing a decrease in the frictional resistance between the film and the first drive roll and improving the followability of the film transfer speed with respect to the rotation speed of the drive roll, the tension controllability is improved even if the transfer speed is increased. The effect can be compatible.
本発明のフィルム洗浄装置が用いられた工程の一例を示す側面図である。It is a side view which shows an example of the process which used the film cleaning apparatus of this invention. 本発明のフィルム洗浄装置が用いられた工程の他の一例を示す側面図である。It is a side view which shows another example of the process in which the film cleaning apparatus of this invention was used. 洗浄液を吹き付ける手段の一例を示す斜視図である。It is a perspective view which shows an example of the means for spraying a cleaning liquid. ノズルから噴出された洗浄液について説明するための正面図である。It is a front view for demonstrating the cleaning liquid ejected from a nozzle. 搬送されるフィルムに洗浄液を吹き付ける態様について説明するための側面図である。It is a side view for demonstrating the mode of spraying a cleaning liquid on a film to be conveyed. 洗浄液を掻き落とす手段の一例を示す斜視図である。It is a perspective view which shows an example of the means for scraping off a cleaning liquid.
 次に、本発明の好ましい実施の形態について、図面を参照しつつ説明する。しかし、本発明は係る図面で示された態様に限定して解釈されるものではない。図1および図2は、搬送されるフィルムに対して本発明の洗浄装置が用いる工程を示す図である。 Next, a preferred embodiment of the present invention will be described with reference to the drawings. However, the present invention is not construed as being limited to the embodiments shown in the drawings. 1 and 2 are views showing the steps used by the cleaning apparatus of the present invention for the film to be conveyed.
 図1の例では、連続的に供給されるフィルム1と、該フィルム1を洗浄する洗浄槽2と、駆動ロール3と、洗浄槽内から随伴される洗浄液および被洗浄物をフィルム表面から掻き落とす手段であるロール4と、洗浄液を吹き付ける手段であるノズルアレイ5と、フィルムを乾燥させる乾燥炉6とを備えている。駆動ロールは、洗浄槽2を出たフィルムが最初に接触する駆動ロール(第1の駆動ロ―ルという)を示している。 In the example of FIG. 1, the continuously supplied film 1, the cleaning tank 2 for cleaning the film 1, the driving roll 3, and the cleaning liquid and the object to be cleaned accompanying from the inside of the cleaning tank are scraped off from the film surface. It includes a roll 4 as a means, a nozzle array 5 as a means for spraying a cleaning liquid, and a drying furnace 6 for drying the film. The drive roll indicates a drive roll (referred to as a first drive roll) to which the film leaving the cleaning tank 2 first contacts.
 図1において、フィルム1は矢印の向きに走行する。フィルム1は洗浄槽2の洗浄液中を走行した後、洗浄液2を持ち上げながら空中にあがる。フィルム1に付着した洗浄液は、被洗浄物を含んでいる。洗浄槽2から出た直後に、フィルム1は、掻き落とす手段であるロール4に接触し、被洗浄物を含む洗浄液が掻き落とされる。これは、フィルム1が、ロール4に接近し接触するまでの間に、フィルム1とロール4の間隙が徐々に狭くなっていくので、洗浄液が下流に流れるように掻き落とされるのである。その後、ロール4で走行方向を変えて、次のロール4に到達する。図1では、2本目のロール4は、1本目のロール4とフィルム1との接触面が反対になっている。2本目のロール4でフィルム1に付着した被洗浄物を含む洗浄液が掻き落とされる。 In FIG. 1, the film 1 runs in the direction of the arrow. After running in the cleaning liquid of the cleaning tank 2, the film 1 rises in the air while lifting the cleaning liquid 2. The cleaning liquid adhering to the film 1 contains an object to be cleaned. Immediately after leaving the cleaning tank 2, the film 1 comes into contact with the roll 4, which is a means for scraping off, and the cleaning liquid containing the object to be cleaned is scraped off. This is because the gap between the film 1 and the roll 4 gradually narrows until the film 1 approaches and comes into contact with the roll 4, so that the cleaning liquid is scraped off so as to flow downstream. After that, the traveling direction is changed by the roll 4 to reach the next roll 4. In FIG. 1, the contact surfaces of the first roll 4 and the film 1 of the second roll 4 are opposite to each other. The cleaning liquid containing the object to be cleaned adhering to the film 1 is scraped off by the second roll 4.
 続いて、フィルム1は、洗浄液を吹き付けるノズルアレイ5を通過し、第1の駆動ロール3に到達する。フィルム1は、洗浄液および被洗浄物が低減しているので、フィルムのスリップが抑制され、第1の駆動ロール3の回転速度に追従して安定に走行する。フィルムの走行性の観点からは、ノズルアレイ5は、洗浄槽2側からみて、フィルム1が第1の駆動ロール3に最初に接触する側の面(面A)に配置されている。なお、図1では両面に配置した態様である。ここで、掻き落とし手段であるロール4は、洗浄液を吹き付ける前に、洗浄槽から持ち上がった被洗浄物を含む洗浄液を効率的に除去するので、洗浄液をさらに下流で吹き付けても第1の駆動ロール3上でのフィルムのすべりを抑制できる。 Subsequently, the film 1 passes through the nozzle array 5 for spraying the cleaning liquid and reaches the first drive roll 3. Since the cleaning liquid and the object to be cleaned are reduced in the film 1, slippage of the film is suppressed, and the film 1 runs stably following the rotation speed of the first drive roll 3. From the viewpoint of film runnability, the nozzle array 5 is arranged on the surface (surface A) on the side where the film 1 first contacts the first drive roll 3 when viewed from the cleaning tank 2 side. In addition, in FIG. 1, it is the mode which arranged on both sides. Here, the roll 4, which is a scraping means, efficiently removes the cleaning liquid including the object to be cleaned lifted from the cleaning tank before spraying the cleaning liquid. Therefore, even if the cleaning liquid is sprayed further downstream, the first drive roll 3 The slippage of the film on the film can be suppressed.
 図2の例では、連続的に供給されるフィルム1と、該フィルムの表面に塗工を行なう塗工機8と、塗工後のフィルム1を洗浄する洗浄槽2と、第1の駆動ロール3と、洗浄槽内から随伴される洗浄液および被洗浄物を掻き落とす手段であるロール4と、洗浄液を吹き付ける手段であるノズルアレイ5と、フィルムを乾燥させる乾燥炉6とを備えている。以下、詳細に説明する。 In the example of FIG. 2, the film 1 continuously supplied, the coating machine 8 for coating the surface of the film, the cleaning tank 2 for cleaning the film 1 after coating, and the first drive roll. 3. It is provided with a roll 4 which is a means for scraping off the cleaning liquid and an object to be cleaned accompanying from the inside of the cleaning tank, a nozzle array 5 which is a means for spraying the cleaning liquid, and a drying furnace 6 for drying the film. The details will be described below.
 (被洗浄物)
 本発明の洗浄装置に適用ができる被洗浄物に特に制限はない。被洗浄物とは、洗浄液中に含まれる、フィルム1に付随していた洗浄すべき物質のことである。フィルム1には、フィルムおよびフィルム表面のコーティング層、ラミネート層のことをいう。被洗浄物は、フィルム基材から抽出される物質であったり、フィルム基材表面に加工されたコート剤の一部であって、フィルム基材から洗浄し取り除きたい物質である。
(Item to be cleaned)
There is no particular limitation on the object to be cleaned that can be applied to the cleaning device of the present invention. The object to be cleaned is a substance contained in the cleaning liquid to be cleaned that is attached to the film 1. The film 1 refers to a film, a coating layer on the surface of the film, and a laminate layer. The object to be cleaned is a substance extracted from the film substrate or a part of a coating agent processed on the surface of the film substrate, which is a substance to be cleaned and removed from the film substrate.
 例えば、フィルムに随伴する洗浄液には、洗浄液に含まれている洗浄槽内を浮遊している埃やフィルムから脱落した粉塵、フィルム片等の異物、フィルム内に含まれていた揮発性の低い液状物、フィルムや塗工液の一部ではない異物(フィルム巻き芯に使用するコアの埃、作業服の繊維)等が挙げられる。また、フィルムに対して塗工層を設けるなどの加工が行われた場合には、該洗浄液に含まれることとなると考えられる、塗工層に由来する異物や塗工液に用いられた溶媒、また、塗工液に含まれた可塑剤等の添加物が挙げられる。 For example, the cleaning liquid that accompanies the film includes dust floating in the cleaning tank contained in the cleaning liquid, dust that has fallen off from the film, foreign substances such as film pieces, and a low-volatile liquid contained in the film. Examples include foreign objects (dust of the core used for the film core, fibers of work clothes) that are not a part of the film or coating liquid. In addition, when the film is processed such as by providing a coating layer, foreign matter derived from the coating layer or a solvent used in the coating liquid, which is considered to be contained in the cleaning liquid, In addition, additives such as plasticizers contained in the coating liquid can be mentioned.
 塗工液に用いられた溶媒としては、例えば、フッ素含有樹脂を溶解でき、かつ水等の貧溶媒(相分離液)と混和(任意の濃度で相溶)可能な良溶媒などが挙げられる。このような良溶媒とこの良溶媒に溶解したフッ素含有樹脂を含む塗工液が塗布された多孔質基材が、貧溶媒からなる洗浄液を満たした洗浄槽に導入されると、塗膜中の樹脂と良溶媒が相分離し、樹脂が凝固して多孔質層が形成される。良溶媒としては、N,N-ジメチルアセトアミド(DMA)、N-メチル-2-ピロリドン(NMP)、リン酸ヘキサメチルトリアミド(HMPA)、N,N-ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)などが挙げられ、樹脂の溶解性に合わせて自由に選択できる。多孔質層を得るにおいて、前記塗工液のフッ素含有樹脂の濃度は、2重量%~7重量%の範囲にあることが好ましく、3重量%~6重量%の範囲がより好ましい。また、塗工厚は5μm~25μm(片面)に設定することができる。塗工厚の幅方向(フィルムの進行方向に垂直な方向)のばらつきが±10%以下が好ましい。 Examples of the solvent used in the coating liquid include a good solvent that can dissolve a fluorine-containing resin and can be miscible (compatible with an arbitrary concentration) with a poor solvent (phase separation liquid) such as water. When a porous substrate coated with such a good solvent and a coating liquid containing a fluorine-containing resin dissolved in the good solvent is introduced into a cleaning tank filled with a cleaning liquid composed of a poor solvent, it is contained in the coating film. The resin and the good solvent are phase-separated, and the resin is solidified to form a porous layer. Good solvents include N, N-dimethylacetamide (DMA), N-methyl-2-pyrrolidone (NMP), hexamethyltriamide phosphate (HMPA), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO). ), Etc., and can be freely selected according to the solubility of the resin. In obtaining the porous layer, the concentration of the fluorine-containing resin in the coating liquid is preferably in the range of 2% by weight to 7% by weight, more preferably in the range of 3% by weight to 6% by weight. The coating thickness can be set to 5 μm to 25 μm (one side). The variation in the width direction of the coating thickness (the direction perpendicular to the traveling direction of the film) is preferably ± 10% or less.
 (第1の駆動ロール)
 駆動ロールとは、フィルムを搬送するための駆動モーターを備えたロールである。本発明の洗浄装置は、洗浄槽2の出側に第1の駆動ロール3を具備している。第1の駆動ロール3は、フィルムが洗浄槽2内を搬送している時に、フィルムに対して洗浄液との摩擦抵抗が加わるため、洗浄槽2の出側と入側で張力差が発生し、洗浄槽2の出側よりも入側の方の張力が低くなってしまう。第1の駆動ロール3は、洗浄槽から出たフィルムが最初に接触する駆動ロールであって、前述の張力差を補償するために用いられる。張力が低くなると、フィルムが弛み、蛇行、シワ発生の原因になる。従って、駆動ロールによるフィルムの搬送においては、フィルムのシワやたるみや蛇行を生じさせることのない張力・速度で行うことが肝要である。
(First drive roll)
The drive roll is a roll provided with a drive motor for transporting the film. The cleaning device of the present invention includes a first drive roll 3 on the outlet side of the cleaning tank 2. In the first drive roll 3, when the film is conveyed in the cleaning tank 2, frictional resistance with the cleaning liquid is applied to the film, so that a tension difference is generated between the outlet side and the entrance side of the cleaning tank 2. The tension on the inlet side of the cleaning tank 2 is lower than that on the outlet side. The first drive roll 3 is a drive roll that the film coming out of the washing tank comes into contact with first, and is used to compensate for the above-mentioned tension difference. When the tension is low, the film may loosen, meander, and wrinkle. Therefore, it is important to transport the film by the drive roll at a tension and speed that does not cause wrinkles, sagging, or meandering of the film.
 また、第1の駆動ロールからフィルムへの力の伝達を効率的に行うために、第1の駆動ロールとしてニップロールを用いることが好ましい。ニップロールはフィルムを挟み込んで搬送する1対または複数対のロールであり、2本の駆動ロールで構成しても良く、1本の駆動ロールとこれに接触して該駆動ロールに従動する自由回転ロールとの組み合わせであっても良い。 Further, in order to efficiently transfer the force from the first drive roll to the film, it is preferable to use a nip roll as the first drive roll. The nip roll is a pair or a plurality of pairs of rolls that sandwich and convey the film, and may be composed of two drive rolls. A free rotation roll that comes into contact with one drive roll and is driven by the drive roll. It may be a combination with.
 なお、第1の駆動ロールは洗浄槽と同一架台上にある等の態様で一体化されていることが好ましいが、別体として配置することもできる。 It is preferable that the first drive roll is integrated with the washing tank on the same pedestal, but it can also be arranged as a separate body.
 (洗浄槽)
 洗浄槽は、その液中をフィルムを搬送させることで、フィルム表面に付着し、または、フィルム自身やフィルム表面に設けられた塗工層などに含まれた被洗浄物を洗浄する工程である。洗浄液は一般的に純水、溶媒等を用いるが、洗浄の目的を達せられるのであれば、特に制限はない。
(Washing tank)
The cleaning tank is a step of transporting the film in the liquid to clean the object to be cleaned, which adheres to the film surface or is contained in the film itself or the coating layer provided on the film surface. Pure water, a solvent, or the like is generally used as the cleaning liquid, but there is no particular limitation as long as the purpose of cleaning can be achieved.
 (洗浄液および洗浄液に含まれる被洗浄物の掻き落とし工程)
 掻き落とし工程とは洗浄槽から取り出されたフィルムに随伴された洗浄液と被洗浄物を掻き落とす工程であり、掻き落とし手段4を用いて行われる。つまり、被洗浄物の掻き落とし工程としては、洗浄槽から取り出されたフィルムに随伴された洗浄液と被洗浄物を掻き落とす際に適用される、掻き落とし工程4を用いて行われる。フィルムの幅方向で均一な掻き落とし効果を得るため、ドクターブレード、エアノズル、ロールなどを用いることができる。搬送されているフィルムを傷つけることが無い限りにおいて物理的に被洗浄物を除去できるのであれば、特に制限は無い。掻き落としの効率が高いことから、フィルムに直接接触して洗浄液と被洗浄物を取り除く手段であることが好ましい。
(Cleaning liquid and scraping process of the object to be cleaned contained in the cleaning liquid)
The scraping step is a step of scraping off the cleaning liquid and the object to be cleaned accompanying the film taken out from the cleaning tank, and is performed by using the scraping means 4. That is, the scraping step of the object to be cleaned is performed by using the scraping step 4 applied when scraping the cleaning liquid and the object to be cleaned accompanying the film taken out from the cleaning tank. A doctor blade, an air nozzle, a roll, or the like can be used to obtain a uniform scraping effect in the width direction of the film. There is no particular limitation as long as the object to be cleaned can be physically removed as long as the conveyed film is not damaged. Since the scraping efficiency is high, it is preferable to use a means for removing the cleaning liquid and the object to be cleaned by directly contacting the film.
 特に、発明者らのこれまでの検討の結果から、シワ、破膜の懸念が最も低く、装置を簡素化でき、且つフィルム幅方向均一に掻き落とし効果が得られる方法として、フリーロール(フィルムに接触することで回転はするが、モーター等による駆動はさせないロール)へフィルムを抱かせて掻き取りを行うことが好ましい。 In particular, based on the results of the studies conducted by the inventors so far, freeroll (for film) is a method that has the lowest concern about wrinkles and film rupture, simplifies the apparatus, and can obtain a uniform scraping effect in the film width direction. It is preferable that the film is held by a roll (a roll that rotates when it comes into contact with the film but is not driven by a motor or the like) and scraped off.
 フリーロールの掻き落とし効果として、フィルムがフリーロールに接触する面積が多い方が効率的な掻き落としが可能となるため、フリーロールのロール径は大きい方が好ましい。フリーロールにおけるフィルムの抱角は、大きい方が掻き落とし効果として効率的である。 As a free roll scraping effect, it is preferable that the free roll has a large roll diameter because a larger area of the film in contact with the free roll enables efficient scraping. The larger the holding angle of the film in the free roll, the more efficient the scraping effect.
 また、張力が高い方がフィルムに付着した、フィルムとフリーロール間の被洗浄物を効率的に掻き落とすことが可能である。 In addition, the higher the tension, the more efficiently the object to be cleaned between the film and the free roll, which has adhered to the film, can be scraped off.
 (洗浄液の吹き付け工程)
 洗浄液の吹き付け工程としては、フィルム1へ均一に洗浄液が当たるようにするべく、シャワーノズル等を使用することが好ましい。シャワー形状としては、一般的に円筒型、霧吹き型、扇型等がある。発明者らのこれまでの検討の結果から、フィルム表面又は、電池用セパレータのような多孔質膜内に侵入した被洗浄物への洗浄にはフィルムに当たる洗浄液の衝突圧で洗浄効果が決まることが分かっている。このことから、一定流量でフィルムにあたる洗浄液の衝突圧が高く、且つフィルム幅方向にシャワー洗浄液が均一に当てるという観点に鑑みて扇型のシャワー形状を与えるシャワーノズルを用いることが好ましい。なお、シャワーを均一に当てる方が好ましい理由としては、均一に当たらない場合、フィルムにシワなどが発生して搬送不良を起こし、フィルム製品の外観不良を引き起こす懸念があるためである。なお、衝突圧は吐出圧と吹き付け方法とフィルムの距離に依存する。
(Cleaning liquid spraying process)
In the step of spraying the cleaning liquid, it is preferable to use a shower nozzle or the like so that the cleaning liquid uniformly hits the film 1. The shower shape generally includes a cylindrical type, a spray type, a fan type, and the like. From the results of the studies conducted by the inventors so far, it is determined that the cleaning effect is determined by the collision pressure of the cleaning liquid that hits the film when cleaning the film surface or the object to be cleaned that has penetrated into the porous membrane such as the battery separator. I know it. From this, it is preferable to use a shower nozzle that gives a fan-shaped shower shape from the viewpoint that the collision pressure of the cleaning liquid that hits the film at a constant flow rate is high and the shower cleaning liquid is uniformly applied in the film width direction. The reason why it is preferable to apply the shower uniformly is that if the shower is not applied uniformly, wrinkles or the like may occur on the film, causing poor transportation and causing poor appearance of the film product. The collision pressure depends on the discharge pressure, the spraying method, and the distance between the films.
 図3は洗浄液を吹き付ける吹き付け手段を示している。洗浄液を吹き付ける手段5は、この図において、洗浄液を扇形のシャワー形状でシャワーを噴射するノズルアレイが用いられ、また、フィルム1の全幅に当たるように設けられている。本発明のフィルム洗浄装置にあっては、洗浄槽2の出側からフィルムに最初の接触する第1の駆動ロール3がニップロールではなく、フィルム片面のみに駆動ロールが接する構造の場合には、洗浄槽側からみて、フィルムが第1の駆動ロールに最初に接触する側の面(面A)に洗浄液を吹き付けることが好ましい。また、第1の駆動ロール3がニップロールのようにフィルム両面に接触する場合には、洗浄槽側からみて、フィルムの両面に洗浄液を吹き付けることが好ましい。また、洗浄液を吹き付ける手段としては、搬送されるフィルムの幅方向に向かって洗浄液を扇形に吹き出すノズルを複数具備し、各々のノズルは等間隔に、かつ、フィルム面においてノズルから吹き出された洗浄液と隣接するノズルから吹き出された洗浄液とが重なる幅が5%以上50%以下となるよう配置されていることが好ましく、かかる構成とすることで、均一な面圧にしやすくなるとともに、効率的な洗浄が可能となる。 FIG. 3 shows a spraying means for spraying the cleaning liquid. In this figure, the means 5 for spraying the cleaning liquid uses a nozzle array that sprays the cleaning liquid in a fan-shaped shower shape, and is provided so as to hit the entire width of the film 1. In the film cleaning apparatus of the present invention, when the first drive roll 3 that first contacts the film from the outlet side of the cleaning tank 2 is not a nip roll but a structure in which the drive roll contacts only one side of the film, cleaning is performed. It is preferable to spray the cleaning liquid on the surface (surface A) on the side where the film first contacts the first drive roll when viewed from the tank side. When the first drive roll 3 comes into contact with both sides of the film like a nip roll, it is preferable to spray the cleaning liquid on both sides of the film when viewed from the cleaning tank side. Further, as a means for spraying the cleaning liquid, a plurality of nozzles for blowing out the cleaning liquid in a fan shape in the width direction of the film to be conveyed are provided, and each nozzle is at equal intervals and with the cleaning liquid blown out from the nozzles on the film surface. It is preferable that the width of the overlapping with the cleaning liquid blown out from the adjacent nozzles is 5% or more and 50% or less. With such a configuration, it becomes easy to obtain a uniform surface pressure and efficient cleaning. Is possible.
 図4は、扇形に洗浄液を噴射するノズルの1つを正面から見た図である。ノズル9の配置数と噴射形状10の広がり角度を設定する場合、フィルム1に衝突する洗浄液がフィルム1の幅方向で衝突していない箇所があると洗浄効果が得られないため、フィルム1の幅方向に衝突する洗浄液はフィルム1の全幅に当たることが好ましい。このことから、フィルム1の全幅方向に斑なく洗浄液が衝突するように、噴射形状10の広がり角度は、隣接するノズルから噴射される洗浄液と重なる幅が、1個当たりのシャワーノズルの噴射の幅に対して5%以上50%以下になるようにし、また、フィルムの全幅がカバーされるようにノズル9の配置数を設定することが好ましい。 FIG. 4 is a front view of one of the nozzles that injects the cleaning liquid in a fan shape. When setting the number of nozzles 9 arranged and the spread angle of the injection shape 10, the cleaning effect cannot be obtained if the cleaning liquid colliding with the film 1 does not collide in the width direction of the film 1, so that the width of the film 1 is set. The cleaning liquid that collides with the direction preferably hits the entire width of the film 1. From this, the spread angle of the injection shape 10 is such that the width of the injection shape 10 overlaps with the cleaning liquid ejected from the adjacent nozzles so that the cleaning liquids collide evenly in the entire width direction of the film 1. It is preferable to set the number of nozzles 9 so as to be 5% or more and 50% or less, and to cover the entire width of the film.
 フィルム1と洗浄液を吹き付ける手段9の距離は、隣接するノズルから吹き出される洗浄液との重なりの程度と、シャワーノズルの扇型の広がり角度を考慮し、フィルム1へ洗浄液が斑なく当たる距離を設定することが好ましい。 The distance between the film 1 and the means 9 for spraying the cleaning liquid is set by considering the degree of overlap between the cleaning liquid blown from the adjacent nozzles and the fan-shaped spreading angle of the shower nozzle, and the distance at which the cleaning liquid hits the film 1 evenly. It is preferable to do so.
 図5はフィルム1と洗浄液を吹き付ける手段5との、位置的な関係を説明している。図5は、フィルム長手方向と垂直方向から見た断面図である。この図では、扇形に洗浄液を噴射するノズルがフィルム幅方向に複数個具備されたノズルアレイが、図5紙面の奥に向けて延在している。 FIG. 5 illustrates the positional relationship between the film 1 and the means 5 for spraying the cleaning liquid. FIG. 5 is a cross-sectional view seen from the direction perpendicular to the longitudinal direction of the film. In this figure, a nozzle array provided with a plurality of nozzles for injecting cleaning liquid in a fan shape in the film width direction extends toward the back of the paper in FIG.
 洗浄液を吹き付ける手段における洗浄液の吹き出し孔のフィルムの搬送方向に対する角度は、フィルムへ当たる洗浄液の衝突圧が関係する。フィルム表面に対して衝突圧が高くなる角度は力のベクトルについて考えてみると、フィルム面に対して、法線方向から当てることが被洗浄物の洗浄に対して効果的である。このことから、フィルムの搬送方向に対して60°以上120°以下の範囲内にあることが好ましい。なおここで、フィルムの搬送方向に対する角度とは、フィルムの搬送方向を含み、フィルム面に垂直な平面において求められる角度である。すなわち、フィルム面の搬送方向を0°とし、フィルムとノズルアレイからの吹き付けられる洗浄液10との角度が60°以上120°以下の範囲内が好ましい。高い洗浄効果を得る観点では、好ましくは、80°以上100°以下の範囲内である。 The angle of the cleaning liquid blowing hole with respect to the film transport direction in the means for spraying the cleaning liquid is related to the collision pressure of the cleaning liquid that hits the film. Considering the force vector, the angle at which the collision pressure increases with respect to the film surface is effective for cleaning the object to be cleaned by applying it to the film surface from the normal direction. From this, it is preferable that the temperature is within the range of 60 ° or more and 120 ° or less with respect to the transport direction of the film. Here, the angle with respect to the transport direction of the film is an angle obtained on a plane perpendicular to the film surface, including the transport direction of the film. That is, it is preferable that the transport direction of the film surface is 0 ° and the angle between the film and the cleaning liquid 10 sprayed from the nozzle array is within the range of 60 ° or more and 120 ° or less. From the viewpoint of obtaining a high cleaning effect, it is preferably in the range of 80 ° or more and 100 ° or less.
 洗浄液を吹き付ける手段5から、吹き付けられる洗浄液のフィルムに当たる衝突圧は、実験的知見から搬送速度5m/min~300m/minにおいては、衝突圧0.05MPa~0.50MPaであることが好ましい。 From the experimental knowledge, the collision pressure of the cleaning liquid sprayed from the cleaning liquid spraying means 5 against the film is preferably 0.05 MPa to 0.50 MPa at a transport speed of 5 m / min to 300 m / min.
 (洗浄液を掻き落とす手段と洗浄液を吹き付ける手段の配置)
 本発明において、洗浄液を掻き落とす手段4と洗浄液を吹き付ける手段5は、洗浄槽2の出側と第1の駆動ロール3との間に配置され、また、洗浄槽側からみて、フィルムが前記第1の駆動ロール3に最初に接触する側の面(面A)に対して作用するように、この順に配置される。洗浄槽から随伴される被洗浄物が第1の駆動ロール3に到達しないようにするためである。
(Arrangement of means for scraping off cleaning liquid and means for spraying cleaning liquid)
In the present invention, the means 4 for scraping off the cleaning liquid and the means 5 for spraying the cleaning liquid are arranged between the outlet side of the cleaning tank 2 and the first drive roll 3, and the film is the first when viewed from the cleaning tank side. It is arranged in this order so as to act on the surface (surface A) on the side that first contacts the drive roll 3 of 1. This is to prevent the object to be cleaned accompanying from the washing tank from reaching the first drive roll 3.
 また、本発明においては好ましく、面Aとは反対側の面に対して作用するように、さらに、洗浄液を掻き落とす手段4と洗浄液を吹き付ける手段5を設けることが好ましい。つまり、本発明において、洗浄液を掻き落とす手段4と洗浄液を吹き付ける手段5は、フィルムが前記洗浄槽を通過後に最初にフィルムが接する第1の駆動ロール3の面側に向けて少なくとも配置され、かつ、フィルムの搬送方向に洗浄槽に近い順に洗浄液を掻き落とす手段4を、続いて、洗浄液を吹き付ける手段5を配置している。また、前記洗浄槽後最初の駆動ロール(第1の駆動ロール3)が従動するロールと対をなしたニップロールを構成している場合は、前記洗浄液を掻き落とす手段および前記洗浄液を吹き付ける手段はフィルムの両面側に向けて設けられていることが好ましい。 Further, in the present invention, it is preferable to further provide means 4 for scraping off the cleaning liquid and means 5 for spraying the cleaning liquid so as to act on the surface opposite to the surface A. That is, in the present invention, the means 4 for scraping off the cleaning liquid and the means 5 for spraying the cleaning liquid are at least arranged toward the surface side of the first drive roll 3 with which the film first comes into contact after passing through the cleaning tank. A means 4 for scraping off the cleaning liquid in the order of being closer to the cleaning tank is arranged in the film transport direction, followed by a means 5 for spraying the cleaning liquid. When the first drive roll (first drive roll 3) after the cleaning tank constitutes a nip roll paired with the driven roll, the means for scraping off the cleaning liquid and the means for spraying the cleaning liquid are films. It is preferable that the film is provided so as to face both sides of the.
 (塗工機)
 図2は、ディップコートヘッドなどの塗工機を用いた例を示している。塗工機は、好ましく、フィルムの片面に粘度10mPa・s以上3000mPa・s以下の塗工液を塗工厚1μm以上100μm以下で塗布可能であり、その幅方向の厚みバラツキが±10%となるように塗布できるものを用いることができる。また、塗工方式には特に制限はなく、例えば、ディップコート、キャストコート、スピンコート、バーコート、スプレーコート、ブレードコート、スリットダイコート、グラビアコート、リバースコート、リップタイレクトコート、コンマコート、スクリーン印刷、鋳型塗布、印刷転写、インクジェットなどのウエットコート法等を挙げることができる。特に、連続的かつ塗工速度30m/分以上で塗工を望む場合は、高粘度、薄膜、高速塗工に適した、かき取り方式であるリップダイレクト方式やコンマコート方式、ディップコート方式が好ましい。さらに、両面同時に多孔質層を形成できるという点から、ディップコート方式がより好ましい。ディップコート方式を採用することで、80m/分以上の速度で塗工することが可能になる。
(Coating machine)
FIG. 2 shows an example in which a coating machine such as a dip coat head is used. The coating machine is preferably capable of applying a coating liquid having a viscosity of 10 mPa · s or more and 3000 mPa · s or less on one side of the film with a coating thickness of 1 μm or more and 100 μm or less, and the thickness variation in the width direction is ± 10%. Those that can be applied can be used. The coating method is not particularly limited, and for example, dip coat, cast coat, spin coat, bar coat, spray coat, blade coat, slit die coat, gravure coat, reverse coat, lip direct coat, comma coat, screen. Wet coating methods such as printing, mold coating, printing transfer, and inkjet can be mentioned. In particular, when continuous coating is desired at a coating speed of 30 m / min or more, the lip direct method, comma coat method, and dip coat method, which are scraping methods suitable for high viscosity, thin film, and high speed coating, are preferable. .. Further, the dip coating method is more preferable from the viewpoint that a porous layer can be formed on both sides at the same time. By adopting the dip coat method, it is possible to apply at a speed of 80 m / min or more.
 連続的にコーティングを行う場合、フィルムの搬送速度は例えば5m/分~300m/分の範囲に設定でき、生産性と塗膜の厚みの均一性等の点から、塗工方式に応じて適宜設定することができる。 When continuous coating is performed, the film transport speed can be set in the range of, for example, 5 m / min to 300 m / min, and is appropriately set according to the coating method from the viewpoints of productivity and uniformity of coating film thickness. can do.
 (フィルム)
 本発明に用いられるフィルムとしては、フィルム状の形状を有していれば特に制限はないが、プラスチックフィルム、不織布シート、カーボンシートなどが挙げられる。特にプラスチックフィルムとしてはポリエチレンテレフタラート、ポリエチレンナイトレートなどのポリエステルフィルムや、ポリプロピレンやポリエチレン、その複合フィルム等のポリオレフィンフィルム、ポリイミドフィルム、ポリアミド、ポリフェニレンサルファイドフィルム等が挙げられる。また、好ましく多孔質基材であることができる。
(the film)
The film used in the present invention is not particularly limited as long as it has a film-like shape, and examples thereof include a plastic film, a non-woven fabric sheet, and a carbon sheet. In particular, examples of the plastic film include polyester films such as polyethylene terephthalate and polyethylene nitrate, polyolefin films such as polypropylene, polyethylene and composite films thereof, polyimide films, polyamides, and polyphenylene sulfide films. Moreover, it can be preferably a porous base material.
 (多孔質基材)
 リチウムイオン電池のセパレータフィルムは近年需要が伸びており、表面に機能層を塗布したコート層が設けられるなどして高機能化が進んでいる。多孔複合フィルム(セパレータフィルム)の多くはイオン伝導性の観点から多孔質である。このため、多孔フィルムの製造過程やコート層の形成過程で有機溶媒等の溶剤が用いられることが多く、また、異物やフィルムからの固形状の離脱物が発生し易い。本発明の洗浄装置はこのような多孔質材が用いられたもの、とりわけセパレータフィルムにおいて好適に用いられる。多孔質基材としては、ポリオレフィン多孔質膜を用いることが好ましい。ポリオレフィンとしては、ポリエチレンやポリプロピレンが好ましい。また、単一物または2種以上の異なるポリオレフィン樹脂の混合物、例えばポリエチレンとポリプロピレンの混合物であってもよい。また、ポリオレフィンは単独重合体であっても共重合体であってもよく、例えばポリエチレンはエチレンの単独重合体でもよいし、他のαオレフィンの単位を含む共重合体であってもよく、ポリプロピレンはプロピレンの単独重合体であってもよく、他のαオレフィンの単位を含む共重合体であってもよい。多孔質基材は単層膜であっても二層以上の複数の層からなる積層膜であってもよい。多孔質基材の厚みは、3μm~25μmの範囲にあることが好ましく、3~20μmの範囲がより好ましい。多孔質基材の空孔率は、30~70%の範囲にあることが好ましく、35~60%の範囲がより好ましい。このような厚み、空孔率を有することにより、十分な機械的強度と絶縁性が得られ、また十分なイオン伝導性を得ることができる。
(Porous medium)
Demand for separator films for lithium-ion batteries has been increasing in recent years, and their functionality is increasing, such as by providing a coat layer with a functional layer coated on the surface. Most of the porous composite films (separator films) are porous from the viewpoint of ionic conductivity. For this reason, a solvent such as an organic solvent is often used in the manufacturing process of the porous film and the forming process of the coat layer, and foreign substances and solid desorbed substances from the film are likely to occur. The cleaning apparatus of the present invention is preferably used in those using such a porous material, particularly in a separator film. As the porous substrate, it is preferable to use a polyolefin porous membrane. As the polyolefin, polyethylene and polypropylene are preferable. It may also be a single product or a mixture of two or more different polyolefin resins, for example a mixture of polyethylene and polypropylene. Further, the polyolefin may be a homopolymer or a copolymer. For example, polyethylene may be a homopolymer of ethylene, a copolymer containing another α-olefin unit, or polypropylene. May be a homopolymer of propylene or a copolymer containing another α-olefin unit. The porous substrate may be a single-layer film or a laminated film composed of two or more layers. The thickness of the porous substrate is preferably in the range of 3 μm to 25 μm, more preferably in the range of 3 to 20 μm. The porosity of the porous substrate is preferably in the range of 30 to 70%, more preferably in the range of 35 to 60%. By having such a thickness and porosity, sufficient mechanical strength and insulating property can be obtained, and sufficient ionic conductivity can be obtained.
 (フィルムの厚み)
 前記多孔複合フィルムの全体の膜厚は、4μm~30μmの範囲に設定でき、4μm~24μmの範囲が好ましい。このような範囲に厚みを設定することで、できるだけ薄膜にしながらも、機械強度と絶縁性を確保することができる。
(Film thickness)
The overall film thickness of the porous composite film can be set in the range of 4 μm to 30 μm, preferably in the range of 4 μm to 24 μm. By setting the thickness in such a range, it is possible to secure the mechanical strength and the insulating property while making the film as thin as possible.
 前記多孔複合フィルムの機能層としては例えばリチウムイオン電池のセパレータに用いられる場合、多孔質であることが好ましい。機能層の厚みは、1~5μmの範囲に設定でき、1~4μmの範囲が好ましく、1~3μmがより好ましい。機能層の厚みをこのような範囲に設定することで、必要最小限の厚みで、十分な機能層の形成効果と接着強度を得ることができる。 The functional layer of the porous composite film is preferably porous, for example, when it is used as a separator for a lithium ion battery. The thickness of the functional layer can be set in the range of 1 to 5 μm, preferably in the range of 1 to 4 μm, and more preferably in the range of 1 to 3 μm. By setting the thickness of the functional layer in such a range, it is possible to obtain a sufficient effect of forming the functional layer and adhesive strength with the minimum necessary thickness.
 以下、本発明を具体的に説明するために、実施例を挙げて説明する。なお、本発明はこれらの例に限定して解釈されるものではない。 Hereinafter, in order to specifically explain the present invention, examples will be given. The present invention is not limited to these examples.
 (用いた装置構成とフィルム(塗工あり))
 図2に示す装置構成を用いて多孔質基材を加工した。具体的には、幅900mmのリチウムイオン電池のセパレータ(厚さ7μm)を搬送速度60m/minにて、塗工機8でN-メチル-2-ピロリドン(NMP)の溶媒を含んだ塗工液を塗布した後、純水を入れた洗浄槽2で洗浄し、乾燥炉6で乾燥した。
(Device configuration and film used (with coating))
The porous substrate was processed using the apparatus configuration shown in FIG. Specifically, a coating liquid containing a solvent of N-methyl-2-pyrrolidone (NMP) in a coating machine 8 at a transport speed of 60 m / min for a separator (thickness 7 μm) of a lithium ion battery having a width of 900 mm. Was applied, washed in a washing tank 2 containing pure water, and dried in a drying oven 6.
 掻き落とし手段としては、図6に示すような構成の2本のフリーロール(材質:SUS304+表面処理[Hcrめっき]、直径80mm)を用いた。 As the scraping means, two free rolls (material: SUS304 + surface treatment [Hcr plating], diameter 80 mm) having the configuration shown in FIG. 6 were used.
 洗浄液を吹き付ける手段としては、洗浄液は純水、洗浄液を吐出するシャワーノズルは株式会社いけうち製のMVVP115を用い、フィルム幅方向と平行な方向に等間隔で、着地点において隣接する洗浄ノズルからの洗浄液との重なりが、一個当たりのノズルによる洗浄液の到達幅を100%としたとき、5%となるようにし、また、ノズルの数はフィルムの全幅に洗浄液が届くよう設けた。なお、図3で示したようにフィルム幅を超えて洗浄液を吹き付けた。 As a means for spraying the cleaning liquid, pure water is used as the cleaning liquid, and MVVP115 manufactured by Ikeuchi Co., Ltd. is used as the shower nozzle for discharging the cleaning liquid. The cleaning liquid from the adjacent cleaning nozzles at the landing point at equal intervals in the direction parallel to the film width direction. The overlap with and is set to 5% when the reachable width of the cleaning liquid by each nozzle is 100%, and the number of nozzles is provided so that the cleaning liquid reaches the entire width of the film. As shown in FIG. 3, the cleaning liquid was sprayed beyond the film width.
 (シャワー吐出圧)
 ギアポンプからシャワーノズルへ繋がる配管経路中のシャワーノズル直前へ圧力計(長野計器株式会社「普通型圧力計AA10-160」)を設置し、更にギアポンプと圧力計の間の配管経路へボールバルブを設置し、流量を変更した値を圧力計で読み取り、シャワー吐出圧とした。
(Shower discharge pressure)
A pressure gauge (Nagano Keiki Co., Ltd. "ordinary pressure gauge AA10-160") is installed just before the shower nozzle in the piping path from the gear pump to the shower nozzle, and a ball valve is installed in the piping path between the gear pump and the pressure gauge. Then, the value at which the flow rate was changed was read with a pressure gauge and used as the shower discharge pressure.
 (シャワー流量)
 ギアポンプからシャワーノズルへ繋がる配管経路中のシャワーノズル直前へ流量計(株式会社キーエンス「クランプオン式流量計FD-Q15A/20A」)を設置し、更にギアポンプと流量計の間の配管経路へボールバルブを設置し、流量を変更した値を流量計で読み取り、シャワー流量とした。
(Shower flow rate)
A flow meter (Keyence Co., Ltd. "Clamp-on type flow meter FD-Q15A / 20A") is installed just before the shower nozzle in the piping path from the gear pump to the shower nozzle, and a ball valve is connected to the piping path between the gear pump and the flow meter. Was installed, and the value at which the flow rate was changed was read with a flow meter and used as the shower flow rate.
 (シャワー角度)
 シャワーノズルから吐出された洗浄液とフィルムとがなす角度であり、フィルムの搬送方向に平行でフィルム面とは垂直な面において、フィルム搬送方向下流側からみて洗浄液とフィルムとがなす角度として求めた(図5参照)。なお、フィルム裏面においても同様であり、シャワー角度が鋭角である場合はフィルム下流側から上流側に向かって洗浄液が吹き付けられることとなる。
(Shower angle)
It is the angle formed by the cleaning liquid discharged from the shower nozzle and the film, and is obtained as the angle formed by the cleaning liquid and the film when viewed from the downstream side in the film transport direction on a plane parallel to the film transport direction and perpendicular to the film surface ( (See FIG. 5). The same applies to the back surface of the film, and when the shower angle is an acute angle, the cleaning liquid is sprayed from the downstream side to the upstream side of the film.
 (シャワー位置)
 各実施例および比較例1においては、シャワーノズルの先端から洗浄液の着地点(但し、ノズル先端から最も近い着地点)までの距離を50mmに設定した。
(Shower position)
In each of the examples and Comparative Example 1, the distance from the tip of the shower nozzle to the landing point of the cleaning liquid (however, the landing point closest to the tip of the nozzle) was set to 50 mm.
 (搬送性の評価)
 搬送制御性の評価方法として、駆動ロールを通過する際に、フィルムの搬送状態を目視で観察した。しわや蛇行が発生しない場合を「良好」とし、しわや蛇行が発生する場合を「不良」とした。
(Evaluation of transportability)
As a method for evaluating the transport controllability, the transport state of the film was visually observed when passing through the drive roll. The case where wrinkles and meandering did not occur was regarded as "good", and the case where wrinkles and meandering occurred was regarded as "bad".
 さらに、第1の駆動ロール3へ持ち上げられるセパレータフィルムの表面に付着した被洗浄物が少ない方が、セパレータフィルムと駆動ロール間の摩擦力が高く、搬送制御性が向上することで、シワ、蛇行が発生しないことを鑑みて、第1の駆動ロール3を通過する直前のセパレータフィルムをサンプリングし、フィルムに残留している被洗浄物(NMP)の量を求めて評価を行った。 Further, the less the object to be cleaned adheres to the surface of the separator film lifted to the first drive roll 3, the higher the frictional force between the separator film and the drive roll, and the improved transport controllability, resulting in wrinkles and meandering. The separator film immediately before passing through the first drive roll 3 was sampled, and the amount of the object to be cleaned (NMP) remaining on the film was determined and evaluated.
 次に、フィルム洗浄装置を用いた際の洗浄効果について、評価方法を以下に示す。 Next, the evaluation method for the cleaning effect when using the film cleaning device is shown below.
 (フィルムに残留するNMP量の測定)
 サンプリングしたセパレータフィルムに含まれる残留NMPは以下の測定方法によって求めた。
(Measurement of the amount of NMP remaining on the film)
The residual NMP contained in the sampled separator film was determined by the following measuring method.
  <試料作製>
 標準溶液の調製として、メスフラスコ(10mL)に標準品(0.0104g)を秤量後、N、N-ジメチルアセトアミド(DMAc)で定容したものを標準原液(濃度:1040μg/mL)とし、また、DMAcで希釈して、検量線用標準溶液を調整した。
<Sample preparation>
To prepare the standard solution, weigh the standard product (0.0104 g) in a measuring flask (10 mL), and then use N, N-dimethylacetamide (DMAc) to formulate the standard stock solution (concentration: 1040 μg / mL). , DMAc was diluted to prepare a standard solution for calibration lines.
 試料溶液の調製として、第1の駆動ロール3を通過する直前のセパレータフィルムをサンプリングした試料を1cm×1cmへ裁断し、そのうち試料(0.1g)を20mLスクリュー管に秤量し、DMAcを10mL加えて蓋をし、浸漬(24時間)し、超音波処理(30分間)したものを試料溶液とした。 To prepare the sample solution, cut the sample of the separator film just before passing through the first drive roll 3 into 1 cm × 1 cm, weigh the sample (0.1 g) into a 20 mL screw tube, and add 10 mL of DMAc. The sample solution was prepared by covering it with a lid, immersing it (24 hours), and sonicating it (30 minutes).
 <測定条件>
装置:GCMS-TQ8040(島津製作所)
カラム:DB-WAX、30m×0.25mm、膜厚0.25μm
    (Agilent Technorogies)
カラム温度:40℃(1min)-20℃/min-220℃(1min)
注入口ガス圧:150.6kpa(ヘリウム、定圧モード)
スプリット比:1/20
注入口温度:250℃
注入量:1μL
イオン化法:EI(電子イオン化)
検出モード:SIM(選択イオン検出)
モニターイオン:m/z 99.10
 <サンプルの測定>
 測定した試料溶液をGC/MS測定し、検量線法を用いてNMP量を算出した。
<Measurement conditions>
Equipment: GCMS-TQ8040 (Shimadzu Corporation)
Column: DB-WAX, 30m x 0.25mm, film thickness 0.25μm
(Agilent Technologies)
Column temperature: 40 ° C (1 min) -20 ° C / min-220 ° C (1 min)
Injection gas pressure: 150.6 kpa (helium, constant pressure mode)
Split ratio: 1/20
Injection port temperature: 250 ° C
Injection volume: 1 μL
Ionization method: EI (Electron Ionization)
Detection mode: SIM (selective ion detection)
Monitor ion: m / z 99.10
<Measurement of sample>
The measured sample solution was measured by GC / MS, and the amount of NMP was calculated using the calibration curve method.
 (実施例1~4)
 表1に示すとおり、シャワー流量を5、7、9、10L/min、シャワー吐出圧を0.05、0.10、0.13、0.16MPaに変更し、シャワー角度90°、掻き落とし工程有の条件で塗工搬送を行った。その結果、シャワー流量5L/min、シャワー吐出圧0.05MPaに比べ、シャワー流量10L/min、シャワー吐出圧0.16MPaの方が、残留NMP量が少ないセパレータフィルムを得ることができた。
(Examples 1 to 4)
As shown in Table 1, the shower flow rate was changed to 5, 7, 9, 10 L / min, the shower discharge pressure was changed to 0.05, 0.10, 0.13, 0.16 MPa, the shower angle was 90 °, and the scraping process was performed. The coating was carried out under certain conditions. As a result, it was possible to obtain a separator film having a smaller residual NMP amount when the shower flow rate was 10 L / min and the shower discharge pressure was 0.16 MPa than when the shower flow rate was 5 L / min and the shower discharge pressure was 0.05 MPa.
 (実施例5,6,7)
 シャワー角度を120°(実施例5)、60°(実施例6)、および、30°(実施例7)に各々変更し、シャワー流量を10L/min、シャワー吐出圧を0.16MPa、掻き落とし工程有の条件で塗工搬送を行った。その結果、シャワー角度30°、60°、120°に比べ、シャワー角度90°の方が、残留NMP量が少ないセパレータフィルムを得ることができた。
(Examples 5, 6 and 7)
The shower angle was changed to 120 ° (Example 5), 60 ° (Example 6), and 30 ° (Example 7), respectively, the shower flow rate was 10 L / min, the shower discharge pressure was 0.16 MPa, and scraping was performed. The coating was carried out under the condition of having a process. As a result, it was possible to obtain a separator film having a smaller residual NMP amount when the shower angle was 90 ° than when the shower angles were 30 °, 60 ° and 120 °.
 (比較例1)
 掻き落とし工程の無い条件以外は、実施例4と同様にしてセパレータフィルムを作製した。
(Comparative Example 1)
A separator film was produced in the same manner as in Example 4 except under the condition that there was no scraping step.
 (比較例2)
 吹き付け工程のシャワーが無く、且つ掻き落とし工程の無い条件以外は、実施例1と同様にしてセパレータフィルムを作製した。
(Comparative Example 2)
A separator film was produced in the same manner as in Example 1 except that there was no shower in the spraying step and no scraping step.
 結果を表1にまとめた。 The results are summarized in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 1:フィルム
 2:洗浄槽
 3:第1の駆動ロール
 4:洗浄液の掻き落とし手段(ロール)
 5:洗浄液を吹き付ける手段(ノズルアレイ)
 6:乾燥炉
 8:塗工機
 9:ノズル
10:ノズルから噴射された洗浄液
1: Film 2: Cleaning tank 3: First drive roll 4: Cleaning liquid scraping means (roll)
5: Means for spraying cleaning liquid (nozzle array)
6: Drying furnace 8: Coating machine 9: Nozzle 10: Cleaning liquid sprayed from the nozzle

Claims (13)

  1. 洗浄槽と該洗浄槽の下流に前記洗浄槽から出たフィルムが最初に接触する駆動ロール(該駆動ロールを第1の駆動ロールという)を有するフィルムを洗浄するための洗浄装置であって、
    洗浄槽を出たフィルムに随伴する洗浄液を掻き落とす手段が、洗浄槽を通過直後にあって、第1の駆動ロールと最初に接触するフィルム面側に少なくとも設けられ、
    さらに、洗浄液を前記フィルムに吹き付ける手段が、前記洗浄液を掻き落とす手段と第1の駆動ロールとの間にあって、第1の駆動ロールと最初に接触するフィルム面側に少なくとも設けられる、フィルム洗浄装置。
    A cleaning device for cleaning a film having a drive roll (the drive roll is referred to as a first drive roll) in which the film from the cleaning tank first contacts the cleaning tank and the film downstream of the cleaning tank.
    A means for scraping off the cleaning liquid accompanying the film leaving the cleaning tank is provided at least on the film surface side that first contacts the first drive roll immediately after passing through the cleaning tank.
    Further, a film cleaning device in which a means for spraying the cleaning liquid onto the film is provided between the means for scraping off the cleaning liquid and the first drive roll, and is provided at least on the film surface side that first contacts the first drive roll.
  2. 前記掻き落とし手段および前記吹き付け手段が、フィルムの両面に対して設けられている、請求項1記載のフィルム洗浄装置。 The film cleaning apparatus according to claim 1, wherein the scraping means and the spraying means are provided on both sides of the film.
  3. 前記第1の駆動ロールが、従動するロールと対をなしたニップロールを構成する洗浄装置であって、前記掻き落とし手段および前記吹き付け手段が、フィルムの両面に対して設けられている、請求項1または2に記載のフィルム洗浄装置。 1. A cleaning device in which the first driving roll constitutes a nip roll paired with a driven roll, and the scraping means and the spraying means are provided on both sides of the film. Or the film cleaning apparatus according to 2.
  4. 洗浄槽に搬送中のフィルムを導入し、該フィルムを洗浄するための装置であって、下記I)~II)の特徴を有するフィルム洗浄装置。
    I)洗浄槽、および該洗浄槽の出側に駆動ロールを有する。
    II)前記洗浄槽と前記駆動ロールとの間に、洗浄槽側からみて、前記フィルムが前記駆動ロールに最初に接触する側の面に対して洗浄槽から随伴される洗浄液を掻き落とす手段、および、該面に対して洗浄液を吹き付ける手段をこの順に有する。
    A film cleaning device for introducing a film being conveyed into a cleaning tank and cleaning the film, which has the following characteristics I) to II).
    I) It has a washing tank and a drive roll on the outlet side of the washing tank.
    II) A means for scraping off the cleaning liquid accompanying from the cleaning tank between the cleaning tank and the driving roll with respect to the surface on the side where the film first contacts the driving roll when viewed from the cleaning tank side. , The means for spraying the cleaning liquid on the surface is provided in this order.
  5. 前記駆動ロールの前記洗浄槽側の最初のロールが、駆動するロールと前記駆動するロールに従動するロールとが対をなしたニップロールを構成し、かつ、前記洗浄槽内からの洗浄液を掻き落とす手段および前記洗浄液を吹き付ける手段はフィルムの両面に対して設けられていることを特徴とする請求項4記載のフィルム洗浄装置。 A means for the first roll of the drive roll on the cleaning tank side to form a nip roll in which a driving roll and a roll driven by the driving roll are paired, and to scrape off the cleaning liquid from the inside of the cleaning tank. The film cleaning apparatus according to claim 4, wherein the means for spraying the cleaning liquid is provided on both sides of the film.
  6. 前記吹き付け手段における洗浄液の吹き出し孔は、前記フィルムの搬送方向に対して30°以上120°以下の角度をなすように設けられていることを特徴とする、請求項1~5いずれかに記載のフィルム洗浄装置。 The method according to any one of claims 1 to 5, wherein the cleaning liquid blowing holes in the spraying means are provided so as to form an angle of 30 ° or more and 120 ° or less with respect to the transport direction of the film. Film cleaning equipment.
  7. 前記吹き付け手段は、搬送されるフィルムの幅方向に向かって洗浄液を扇形に吹き出すノズルを複数具備し、各々のノズルは幅方向に等間隔に、かつ、フィルム面においてノズルから吹き出された洗浄液と隣接するノズルから吹き出された洗浄液とが重なる幅が5%以上50%以下となるよう配置されていることを特徴とする請求項1~6のいずれかに記載のフィルム洗浄装置。 The spraying means includes a plurality of nozzles that blow out the cleaning liquid in a fan shape in the width direction of the film to be conveyed, and each nozzle is equidistant in the width direction and adjacent to the cleaning liquid blown from the nozzles on the film surface. The film cleaning apparatus according to any one of claims 1 to 6, wherein the width of overlap with the cleaning liquid blown out from the nozzle is 5% or more and 50% or less.
  8. 前記吹き付け手段は、搬送されるフィルムの幅の全体にわたって洗浄液を吹き付けるよう構成されていることを特徴とする請求項1~7のいずれかに記載のフィルム洗浄装置。 The film cleaning apparatus according to any one of claims 1 to 7, wherein the spraying means is configured to spray the cleaning liquid over the entire width of the film to be conveyed.
  9. 前記フィルムは塗工処理が施されたものであることを特徴とする1~8のいずれかに記載のフィルム洗浄装置。 The film cleaning device according to any one of 1 to 8, wherein the film is coated.
  10. 有機溶媒を洗浄するために用いられるものである1~9のいずれかに記載のフィルム洗浄装置。 The film cleaning apparatus according to any one of 1 to 9, which is used for cleaning an organic solvent.
  11. 固形状態である被洗浄物を洗浄するために用いられるものであることを特徴とする1~10のいずれかに記載のフィルム洗浄装置。 The film cleaning apparatus according to any one of 1 to 10, wherein the film cleaning apparatus is used for cleaning an object to be cleaned in a solid state.
  12. 電池用セパレータフィルムを洗浄するために用いられるものであることを特徴とする1~11のいずれかに記載のフィルム洗浄装置。 The film cleaning apparatus according to any one of 1 to 11, wherein the film cleaning apparatus is used for cleaning a separator film for a battery.
  13. フィルムを搬送しながら洗浄する洗浄済みフィルムの製造方法であって、フィルム洗浄槽を通過後に、前記洗浄槽から前記フィルムに随伴する洗浄液を掻き落とし、次に、洗浄液を前記フィルムに吹き付け、前記フィルムを前記洗浄槽を通過後の最初に接する駆動ロール(該駆動ロールを第1の駆動ロールという)の順に通過させ、かつ、前記掻き落としおよび前記吹き付けは、前記フィルムの前記第1の駆動ロールに接触する側のフィルム面に対して行う、洗浄済みフィルムの製造方法。 A method for producing a washed film in which the film is washed while being conveyed. After passing through the film washing tank, the cleaning liquid accompanying the film is scraped off from the washing tank, and then the cleaning liquid is sprayed onto the film to perform the film. Is passed through the washing tank in the order of the first contacting drive roll (the drive roll is referred to as a first drive roll), and the scraping and the spraying are applied to the first drive roll of the film. A method for producing a washed film, which is performed on the film surface on the contact side.
PCT/JP2020/009105 2019-03-27 2020-03-04 Film cleaning device and method for manufacturing cleaning-completed film WO2020195635A1 (en)

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