JP2011194593A - Film processor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film processor which can make quality and productivity compatible in continuous liquid treatment even in the case of an easily injurable film, an electrolyte film for a fuel cell having a large dimensional change rate by water absorption and an ion exchange capacity, or the like.SOLUTION: The film processor has a film liquid treatment part for liquid-treating a film, a film washing part for washing the liquid-treated film, a film drying part for drying the washed film, and a film winding part for winding the dried film. The film drying part is equipped with a suction conveyance roll in which at least the roll surface is made of a nonmetallic porous material, a pressure reducing device, and a hot air blower. The pressure reducing device is connected to a suction roll to keep the pressure of the surface of the suction conveyance roll negative, and the hot air blower is installed to make its blast opening face the suction conveyance roll with the film held between them.

Description

  The present invention relates to a processing apparatus for a long polymer film. More specifically, the present invention relates to a film processing apparatus capable of reducing scratches, wrinkles, drying unevenness and the like generated on the film surface during liquid treatment while transporting an organic polymer film and obtaining a high-quality film.

  The organic polymer film is generally formed by an extrusion method using a T die or the like, or a casting method in which a polymer solution is cast on a substrate. In addition, in order to improve the quality and add value to the formed film, a process may be used in which the film is processed in a liquid and then dried.

  In the case of a film that does not absorb the liquid, such as a metal film, it can be transported in the liquid without special measures. In the case of an organic polymer film, the physical properties of the film change by absorbing the liquid. Under the same transport conditions as in the air, problems such as poor quality such as wrinkles and scratches on the film and breakage of the film may occur. In particular, when the film swells and changes its size, when the elastic modulus or breaking strength of the film decreases, or when the film is a thin film, handling becomes very difficult.

  In addition, the liquid-treated film is dried after removing the droplets with an air blow or water-absorbing roll, etc., but the air blow may not sufficiently remove the droplets, leaving traces of water drops or uneven drying. The water absorbing roll causes wrinkles because the roll sandwiches the film being dried. Furthermore, in a film having a high water absorption and a large dimensional change rate, the quality of the film such as wrinkles or scratches due to changes in the size of the film as it dries and scratches become noticeable. There was a problem that it was very difficult to dry continuously.

  As a method for solving such a problem, there is known a method in which a film is fixed to a frame or the like and liquid processing is performed on a single sheet, but a continuous processing process is desirable in order to increase production efficiency.

  As described above, there are various problems in transporting and processing the film in the liquid. Especially in the film that is easily damaged and the electrolyte film for the fuel cell having a large dimensional change rate due to water absorption, both quality and productivity are compatible. It was very difficult to do.

  On the other hand, Patent Document 1 discloses a method in which an organic polymer is applied on a substrate and dried, and then the obtained organic polymer film is liquid-treated without peeling from the substrate.

  However, even in this method, since the film is dried together with the substrate by means of a hot air dryer or the like without fixing the film together with the substrate, the difference in thermal shrinkage, film thickness, and rigidity between the substrate film and the organic polymer film As a result, there was a problem that the whole curled up, resulting in poor conveyance and unwinding.

  If a sufficiently thick base film is used, curling can be suppressed to the extent that there is no hindrance to winding, but a cost increase due to the thick base film and handling problems due to weight increase have occurred.

In the method disclosed in Patent Document 1, the tension of the continuous film passing through a series of processes from unwinding to winding is such that the winding portion has the largest tension and the unwinding portion has the smallest. However, since the film is wound with an excessive tension, there is a problem that the product film is scratched or the films are fixed due to tightening and cannot be peeled off during use. This phenomenon was prominent when a thick base film was used to prevent curling in the drying section.
Furthermore, in Patent Document 1, although the film forming / liquid treatment is performed using the sulfonated polymer, the material of the transporting roll is not mentioned, and a commonly used metal transporting roll is used for the fuel cell electrolyte film. Thus, when it applied to conveyance of the film which has ion exchange ability, ion exchange was performed when a film contacted metal conveyance rolls, and there existed a problem of causing incompatibility on quality.

  Further, in Patent Document 2, a raw material polymer is cast on a support and then peeled to form a web, and then the web is dried, and in the film manufacturing apparatus for winding as a film, between a plurality of drying apparatuses, A hollow drive roll having a plurality of suction ports on the surface is provided, and the inside of the drive roll is depressurized by the pressure reducing means to adsorb the web to the outer peripheral surface of the drive roll, and the rotational force of the drive roll is transmitted to the web to nip the web. It is disclosed that the web is conveyed without the occurrence of wrinkles to prevent the generation of wrinkles and recover the residual solvent in the web. However, even in this method, when applied to an electrolyte film for a fuel cell having a large dimensional change rate due to water absorption, the film is not fixed in the front and back processes of the hollow drive roll by a means such as a hot air dryer in a free space. Since it is dried, there is a problem that the whole film curls due to differences in heat shrinkage, film thickness, and rigidity between the base film and the organic polymer film, resulting in poor conveyance and unwinding.

Further, the hollow drive roll disclosed in Patent Document 2 has a suction port on the surface of 1 to 100 mm ² , and the outer periphery of the suction port has a mesh or through-hole size of 0.5. A cover made of a wire mesh or a perforated plate of ˜50 mm ² is provided. Therefore, when applied to an electrolyte film for a fuel cell that has a large dimensional change rate due to water absorption and has ion exchange capacity, the ion exchange is performed by transferring the pattern of the suction port or the cover or the film coming into contact with the cover. There was a problem of being.

  In this way, with conventional technologies, it is difficult to achieve both quality and productivity in continuous liquid processing, especially for easily scratched films and electrolyte film for fuel cells that have a large dimensional change rate due to water absorption and ion exchange capacity. Met.

JP 2006-21172 A JP 2003-94467 A

  An object of the present invention is a film capable of achieving both quality and productivity in continuous liquid processing, such as a film that is easily scratched, a large dimensional change rate due to water absorption, and an electrolyte film for fuel cells that has ion exchange capacity. It is to provide a processing apparatus.

The present invention for achieving the above object is characterized by any one of the following configurations (1) to (10).
(1) A film liquid processing unit for liquid-processing a film, a film cleaning unit for cleaning a liquid-processed film, a film drying unit for drying the cleaned film, and a film winding unit for winding the dried film The film drying unit includes a suction conveyance roll having at least a roll surface made of a nonmetallic porous material, a decompression device, and a hot air blower, and the decompression device is adapted to keep the suction conveyance roll surface at a negative pressure. The film processing apparatus is characterized in that the hot air blower is provided so that the air blowing port faces the suction conveyance roll with the film interposed therebetween.
(2) The film processing apparatus according to (1), wherein the suction conveyance roll is a drive roll.
(3) The film processing apparatus according to (1) or (2), wherein the nonmetallic porous material is a granular polymer binder, a porous polymer, a porous ceramic, or a nonwoven fabric.
(4) the suction conveying roll, wherein the average surface opening area 0.005～0.4Mm ^2, maximum surface opening area 1 mm ² or less, and surface porosity is 15% to 50%, the ( The film processing apparatus as described in 3).
(5) The roll in contact with the film in the film cleaning unit, the film drying unit, and the film winding unit has a surface made of a non-metallic material, according to any one of the above (1) to (4) The film processing apparatus as described.
(6) The film drying unit is a position between the position where the film starts to be sucked and adhered to the suction conveyance roll or the position downstream from the position with respect to the film conveyance direction to the position where the warm air from the warm air blower is blown. The film processing apparatus according to any one of (1) to (5), further comprising a pressing roll that presses the film against a suction conveyance roll.
(7) Furthermore, a film tension detecting mechanism is provided between the film drying section and the film winding section, and a winding speed control mechanism for controlling the speed of the film winding section so that the detected tension becomes a desired value. The film processing apparatus according to any one of (1) to (6), wherein the film processing apparatus is provided.
(8) Further, a film unwinding section is provided, and a film tension detecting mechanism is provided between the film unwinding section and the film drying section, and the speed of the film unwinding section is controlled so that the detected tension becomes a desired value. The film processing apparatus according to any one of (1) to (7), wherein an unwinding speed control mechanism is provided.
(9) The film liquid processing section includes a liquid processing tank for storing the processing liquid, and the film cleaning section includes a cleaning tank for storing the cleaning liquid. (1) to (8), wherein the submerged guide roll is immersed in a treatment liquid so that a balance between a vertically downward load and buoyancy by the roll is maintained. ).
(10) The film cleaning unit includes a cleaning tank configured of a plurality of tanks for storing the cleaning liquid, and the plurality of tanks are adjacent to the washing water that has flowed out from the upper part of the downstream tank in the film transport direction. The film processing apparatus according to any one of (1) to (9), wherein the film processing apparatus is connected so as to be able to flow in from the bottom of the upstream tank.

  Here, in this invention, a film unwinding part means the mechanism which hold | maintains the elongate film wound by roll shape, and unwinds with desired tension | tensile_strength and speed | rate.

  The film liquid processing section refers to a mechanism for immersing and processing a long film being conveyed in a processing liquid with a desired tension. For example, a liquid processing tank for storing the processing liquid, and a roll entering the liquid processing tank. And a submerged guide roll that changes the running direction of the film in the exit roll and the liquid treatment tank.

  The film cleaning unit refers to a mechanism for cleaning the film processed in the film liquid processing unit with the cleaning liquid. For example, the cleaning tank for storing the cleaning water, the roll entering the cleaning tank, the exit roll, and the film running on the upper part of the cleaning tank. It consists of an aerial guide roll that changes the direction, a submerged guide roll that changes the running direction of the film in the washing tank, and a finish washing nozzle installed above the exit roll.

  The film drying section refers to a mechanism that transports the film at a desired speed without niping it by fixing the film to the surface of the suction transport roll, and prevents the film from curling, during drying. Drying can be performed while preventing generation of scratches and wrinkles due to shrinkage.

  And a film winding part means the mechanism which winds a long film in roll shape with desired tension.

  In the present invention, the average surface opening area means the number average of the area of each opening existing on the roll surface, and the maximum surface opening area means the maximum value of the area of each opening existing on the roll surface. . Furthermore, the surface opening ratio refers to the ratio of the total area of the openings present in the portion to the total area (including the opening) of the portion in contact with the film on the roll surface.

  According to the present invention, the film drying section includes a suction conveyance roll having at least a roll surface made of a nonmetallic porous material, a decompression device, and a hot air blower, and the decompression device sets the suction conveyance roll surface to a negative pressure. Since the hot air blower is provided so that the blower opening faces the suction conveyance roll with the film interposed therebetween, the surface is attached to the roll of the non-metallic porous material. It is possible to apply hot air to the film that is in close contact with the roll, and to damage the film, such as a film that is easily scratched or a film that has a large dimensional change rate due to water absorption and that has an ion exchange capacity. It can be dried while preventing changes and ion exchange. Therefore, it is possible to achieve both quality and productivity in continuous liquid processing, and the film subjected to liquid processing according to the present invention is an electrolyte membrane for fuel cells, an ion exchange membrane for salt electrolysis, an electrolyte membrane for water electrolysis, an ion It can also be suitably used as a water treatment membrane such as an exchange membrane, a humidifying membrane, or a secondary battery separator film.

It is a schematic diagram of the film processing apparatus which is one Embodiment of this invention which can be used at the manufacturing process of the electrolyte membrane for fuel cells.

  Hereinafter, a case where an embodiment of the present invention is applied to an electrolyte membrane acid treatment apparatus for a fuel cell will be described as an example with reference to the drawings.

  FIG. 1 is a schematic diagram of a film processing apparatus according to the present invention that is preferably used for acid treatment in producing an electrolyte membrane for a fuel cell.

  The apparatus shown in FIG. 1 includes a film unwinding unit 1, a film liquid processing unit 2, a film cleaning unit 3, a film drying unit 4, and a film winding unit 5. The film 10 is unwound from the film roll 11 to be processed in the film unwinding unit 1, then subjected to liquid treatment in a desired condition in the film liquid processing unit 2, subsequently washed in the film washing unit 3, and then the film drying unit 4. And dried at the film winding unit 5.

  A film tension detecting mechanism 12 is provided between the film unwinding section 1 and the film liquid processing section 2 and the film unwinding section 1 unwinds so that the tension detected by the mechanism becomes a desired value. By controlling the speed and unwinding brake, the film 10 is fed into the film liquid processing unit 2 with a desired tension.

  In addition, although the film 10 is unwound from the to-be-processed film roll 11 in the film unwinding part 1, the to-be-processed film roll 11 is wound in the state of a film with a base material, and the liquid process is a single film which peeled from the base material. In the case of carrying out the process, a substrate winding mechanism (not shown) may be provided, and the film may be unwound while peeling off the film from the substrate.

  Moreover, the film unwinding part 1 does not necessarily need to be provided, and the formed film may be directly introduced into the film liquid processing part 2 without being wound once.

  In the liquid processing tank, the film processing unit 2 includes a liquid processing tank 20 for storing the processing liquid, an entrance roll 21 for guiding the film to the liquid processing tank, an exit roll 22 for guiding the film from the liquid processing tank to the next step, and the liquid processing tank. It is comprised from the submerged guide rolls 23a-23e etc. which change the traveling direction of a film. The film 10 continuously fed from the film unwinding section 1 to the film liquid processing section 2 is transferred to the entrance roll 21 of the film liquid processing section 2, the submerged guide rolls 23a, 23b, 23c, 23d, 23e, and the output roll 22. By being wound in this order, the film processing unit 2 performs liquid processing while being inverted a plurality of times.

  In addition, although the film 10 reciprocates up and down 3 times in the film liquid processing part 2 of FIG. 1, what is necessary is just to change suitably the frequency | count of inversion according to required processing time. That is, the number of submerged guide rolls is not limited to five, and may be one or a plurality of two or more. By using a plurality of lines and turning back multiple times in the processing liquid, the length of the film immersed in the processing liquid can be increased without increasing the length of the processing tank itself. And if the length of the film of the part immersed in the processing liquid is decided, liquid processing time can be adjusted to desired time by adjusting a film running speed.

  The submerged guide rolls 23a to 23e are preferably immersed in the treatment liquid so that the balance between the vertically downward load and the buoyancy by the roll is maintained. When the submerged guide roll is a free roll, the roll comes into contact with the film and rotates due to friction with the film. However, if the roll in liquid is heavy, the roll will not rotate and the film will roll. There is a high possibility that the film will be stretched even if it is rubbed, or the film will stretch even if it is rotated. Therefore, it is preferable that the roll can be rotated with a light force by balancing the vertically downward load and buoyancy by the submerged guide roll to make the weight of the roll in the liquid almost zero. . Thereby, damage to the film can be further reduced. Furthermore, it is preferable from a viewpoint of weight reduction that the guide rolls 23a-23e in liquid are hollow structures.

  Further, in the apparatus shown in FIG. 1, a cleaning nozzle 25 is installed at a portion where the film is carried out from the film liquid processing unit 2, so that the film surface can be cleaned using the drain water from the film cleaning unit 3. It is configured. More specifically, a cleaning nozzle 25 is installed between the exit roll 22 of the film liquid processing unit 2 and the entrance roll 31 of the film cleaning unit 3, and the cleaning nozzle 25 is disposed above the first cleaning tank 36 via a pump. It is connected to the provided cleaning shower water suction port, and is configured such that water can be sucked from the first cleaning tank 36 and ejected to the film surface. As a result, the amount of the processing liquid that adheres to the film surface and is brought into the film cleaning section 3 can be reduced, and the cleaning efficiency in the film cleaning section 3 can be increased, and the film liquid processing section 2 to the film cleaning section 3 It is possible to prevent wrinkles from being generated due to the film drying during conveyance. At this time, it is preferable to adjust the pump so that the amount of water sucked from the washing shower water suction port is balanced with the amount of RO water supplied to the washing nozzle 35 described later.

  Although not shown, the film liquid processing unit 2 is provided with a processing liquid heating mechanism and a processing liquid circulation mechanism, and heating the processing liquid to a desired temperature and using it while circulating can improve the efficiency and uniformity of the liquid processing. It is preferable from the viewpoint. Further, when heated, a vapor of the processing liquid may be generated from the film liquid processing unit 2, and the processing liquid is a chemically active liquid such as acidic or alkaline. In this case, it is also preferable to provide a semi-sealed upper cover 24 provided with a slit only at the film entrance / exit to perform evacuation.

  Further, at this time, it is preferable to install the exit roll 22 and the entrance roll 31 so as to have a downward slope from the exit roll 22 of the film solution processing section 2 toward the entrance roll 31 of the film cleaning section 3 described later. By carrying out like this, it can prevent that the water which wash | cleaned the film surface enters into the film liquid process part 2. FIG.

  The film cleaning unit 3 includes cleaning tanks (first cleaning tank 36 and second cleaning tank 37) for storing cleaning water, an entrance roll 31 for introducing the film into the cleaning tank, and an exit roll 32 for extracting the film from the cleaning tank. The aerial guide rolls 34a and 34b for changing the traveling direction of the film in the upper part of the cleaning tank, the submerged guide rolls 33a and 33b for changing the traveling direction of the film in the cleaning tank, and the finish installed above the outlet roll 32 The cleaning nozzle 35 and the like are included. The film 10 sent out from the film solution processing unit 2 is placed in this order into the entrance roll 31 of the film cleaning unit 3, the in-liquid guide roll 33a, the in-air guide roll 34a, the in-liquid guide roll 33b, the in-air guide roll 34b, and the out-roll 32. In the film cleaning unit 3, the film is cleaned while being turned upside down a plurality of times.

  The submerged guide rolls 33a and 33b are immersed in the cleaning liquid for the same reason as the submerged guide rolls 23a to 23e of the film liquid processing unit 2 so that the balance between the vertically downward load and the buoyancy by the roll is maintained. It is preferable to have a hollow structure from the viewpoint of weight reduction.

  In addition, the submerged guide roll and the in-air guide roll in the film washing | cleaning part 3 are not limited to two, respectively, You may use each one or two or more two or more. By using a plurality of lines and turning back multiple times in the cleaning water, the length of the film immersed in the cleaning water can be increased without increasing the length of the cleaning tank itself.

  Then, the film 10 that has risen after being wound around the output roll 32 is subjected to finish cleaning by ejecting RO water from a cleaning nozzle 35 provided so as to face both surfaces thereof.

  The RO water that has finished and cleaned the film 10 is collected in a cleaning water receiving tank 38 provided at the bottom of the outlet roll 32. The drain port provided in the upper part of the washing water receiving tank 38 and the bottom part of the second washing tank 37 are connected by a washing water communication pipe 39b, and the RO water accumulated in the washing water receiving tank 38 passes through the washing water communication pipe 39b. And flows into the bottom of the second cleaning tank 37. Similarly, the drain port provided in the upper part of the second cleaning tank 37 and the bottom of the first cleaning tank 36 are connected by a cleaning water communication pipe 39a, and the water accumulated in the second cleaning tank 37 is connected to the cleaning water communication pipe 39a. And flows into the bottom of the first cleaning tank 36.

  In this way, the film cleaning section is composed of a plurality of tanks such as a first cleaning tank 36 and a second cleaning tank 37, and the plurality of tanks flow out from the upper part of the downstream tank in the film transport direction. By connecting the washed water so that it can flow from the bottom of the adjacent upstream tank, each tank (the first washing tank 36 and the second washing tank 37) is formed efficiently from the bottom to the top. Cleansing can be performed.

  Further, in the embodiment shown in FIG. 1, a cleaning shower water suction port is provided in the upper part of the first cleaning tank 36 so that water accumulated in the first cleaning tank 36 is supplied to the cleaning nozzle 25 as cleaning water. It is configured. At the same time, a liquid draining roll is installed in front of the entrance roll 31 of the film cleaning unit 3 so that the used cleaning water flowing on the film surface flows down into the overflow receiving tank 30 and is accumulated in the overflow receiving tank 30. The cleaning water after use is appropriately discharged out of the apparatus.

  In addition, at this time, each drain port and the feed port are arranged in the order from the highest, the drain port of the cleaning water receiving tank 38> the drain port of the second cleaning tank 37> the overflow level of the first cleaning tank 36> the first cleaning tank 36. Needless to say, the cleaning shower water suction port is in a positional relationship.

  And although the film washing | cleaning part 3 is comprised by two washing tanks in FIG. 1, what is necessary is just to change the number of washing tanks suitably according to washing | cleaning efficiency.

  The film 10 wound up and rolled up on the output roll 32 of the film cleaning unit 3 is finished and cleaned with a RO water shower by a cleaning nozzle 35 installed obliquely downward, and then conveyed to the film drying unit 4.

  The film drying unit 4 includes at least a suction conveyance roll 41 whose surface is a nonmetallic porous material, a decompression device 42, a hot air blower 43, a pressing roll 44, a sponge roll 45 with a suction mechanism, a suction device 46, and the like. Yes.

  The sponge roll 45 with the suction mechanism is composed of a pair of sponge rolls provided above the cleaning nozzle 35 with the film 10 interposed therebetween, and the inside of the roll is hollow and connected to the suction device 46. With this configuration, the water adsorbed by the sponge roll 45 is discharged, and the sponge roll 45 is always kept in a state capable of adsorbing water. Further, the center positions of the pair of sponge rolls 45 are shifted vertically so that the film 10 is not in a nip state, and the film 10 is disposed so as to contact the pair of sponge rolls 45 in an S shape. Thereby, the surface adhering water can be adsorbed and removed without scratching the film 10.

The suction conveyance roll 41 is formed in a hollow shape using a nonmetallic porous material at least on the surface, and the surface of the suction conveyance roll 41 is made negative pressure by connecting a central hollow portion to the decompression device 42. be able to. Thereby, the film 10 can be adhered and fixed to the surface of the suction conveyance roll 41 to prevent curling of the film 10 and to prevent generation of scratches and wrinkles due to shrinkage during drying. Further, since at least the surface thereof is a non-metallic porous material, even when a film having an H ⁺ group at the terminal and having an ion exchange ability is dried by liquid treatment, the H ⁺ group Even when the film is not replaced with metal and a film having a weakly acidic cleaning liquid attached to the surface is dried, rust generation of the roll can be prevented.

  Even when the film to which ion exchange capability is imparted by liquid treatment is dried, ion exchange is not performed between the suction conveyance roll 41 and the film, and the performance degradation of the film can be prevented.

  Examples of the non-metallic porous material that can be used for the suction conveyance roll 41 include a porous polymer in which a granular polymer is bound, a sponge-like porous polymer, a porous ceramic, and a nonwoven fabric. May be processed into a roll shape, or the surface of the perforated metal roll may be coated with the non-metallic material. Above all, in addition to being lightweight and inexpensive, there are no residual metal ions, and since it has moderate surface elasticity and the opening pattern is difficult to transfer, a porous polymer bound with a granular polymer, sponge-like A porous polymer and a nonwoven fabric are particularly preferred.

What is necessary is just to determine the surface opening area and surface opening rate of the nonmetallic porous material part of the suction conveyance roll 41 from the rigidity, water absorption rate, etc. of the film to process. However, if the surface opening area is too large, the pattern of the roll surface is transferred to the film and the film quality is deteriorated. If the opening area is too small, clogging is likely to occur, and the load on the decompression device 42 becomes excessive. The surface opening area is preferably in the range of 0.005 to 0.4 mm ² . On the other hand, if the surface opening ratio is too low, the load on the decompression device 42 becomes excessive and the pattern on the roll surface is easily transferred to the film. On the other hand, if the surface opening ratio is too high, the mechanical strength decreases. preferable. Since the average surface open area includes an opening having a 1 mm ² or more areas in the even apertures distributed in a range of 0.005～0.4Mm ² pattern roll surface is easily transferred to the film The maximum opening area is preferably 1 mm ² or less. Furthermore, it is preferable that the average surface opening area is 0.01 to 0.2 mm ² , the opening ratio is 20 to 40%, and the maximum surface opening area is 0.8 mm ² or less.

  In order to improve machine accuracy, a perforated metal roll is used as a metal core, and the surface thereof is covered with the nonmetallic porous material. If the thickness of the porous material is small, even if the surface opening area of the non-metallic porous material itself is small, it is substantially sucked by the opening pattern of the porous metal roll. The film to be treated is sucked together with the non-metallic coating material, and the opening pattern of the perforated metal roll is easily transferred to the film to be treated. The thickness of the non-metallic porous material that is preferably set so that the aperture pattern of the perforated metal roll is not transferred to the film to be treated is the structure of the perforated metal roll, the aperture pattern, the average aperture area, and the non-perforated metal roll. Although it depends on the strength of the metallic porous material, the average opening area of the nonmetallic porous material, and the opening ratio, it is preferably at least larger than the average opening diameter of the porous metal roll, and more than twice the average opening diameter. More preferably, the thickness is

  Further, with respect to the film transport direction, from the position where the film 10 starts to be sucked and adhered to the suction transport roll 41 or from the downstream side to the position on the film where hot air from a hot air blower 43 described later is blown. Between them, a small-diameter pressing roll 44 is installed. The pressure roll 44 is in contact with the film 10 on the suction conveyance roll 41 with a force of about its own weight, prevents hot air from a hot air blower 43 described later from flowing down the film surface, and from the sponge roll 45 to the suction conveyance roll 41. The film 10 in the middle is prevented from vibrating. As a result, the film adhesion start position can be fixed, and the generation of wrinkles can be prevented.

  More specifically, the hot air blower 43 is located at a position where the blower opening does not contact the film 10 from the top of the suction conveyance roll 41 to the film peeling portion so as to face the suction conveyance roll 41 with the film 10 interposed therebetween. And it is installed so as to face the film, and has a structure capable of blowing air uniformly over the entire width of the film. According to such a structure, the film can be dried in a state of being in close contact with the suction conveyance roll, and dimensional change and curling can be suppressed during drying.

  At this time, it is also preferable to direct the blowing direction from the warm air blower 43 toward the pressing roll 44 along the surface of the suction conveyance roll. In this way, not only the drying of the film but also the pressing roll 44 can be simultaneously performed, and there is no need to separately provide a drying means for the pressing roll 44.

  The film 10 dried on the suction conveyance roll 41 is then conveyed to the film winding unit 5 and taken up as a processed film roll 51.

  Here, in the embodiment shown in FIG. 1, a film tension detection mechanism 52 is provided between the suction conveyance roll 41 and the film winding unit 5 so that the tension detected by the mechanism becomes a desired value. In addition, the winding speed and winding torque of the film winding unit 5 are controlled. Specifically, there is a problem that if the film is wound with an excessive tension, the product film is scratched or the films are fixed due to tightening and cannot be peeled off during use. It is preferable to wind up at 3 to 3 MPa.

  Such low tension is achieved by using the suction conveyance roll 41 as a drive roll, controlling the film conveyance speed while sucking / adhering the film 10 with the roll, and individually setting the tension before and after the suction conveyance roll. It becomes possible.

Furthermore, in the said apparatus, it is preferable that at least the roll surface of the roll which conveys a film of the film washing | cleaning part 3, the film drying part 4, and the film winding part 5 is a nonmetallic material. By comprising in this way, similarly to the above-mentioned suction conveyance roll 41, even if it is a case where the film which has an H ⁺ group at the terminal and has an ion exchange ability is conveyed by liquid processing, it is H ^+. The group is not replaced with metal, and rust generation of the roll itself can be prevented.

  Examples of such a non-metallic material include a porous polymer bound with a granular polymer, a sponge-like porous polymer, a porous ceramic, and a nonwoven fabric. These may be processed into a roll shape, or the surface of the metal roll may be coated with the non-metallic material.

  Examples of the film to be treated by the apparatus as described above include an organic polymer film, and the organic polymer film is preferably a polymer film having a sulfonic acid group. Such an organic polymer film is modified to a film having ion exchange capacity by a liquid treatment with an acid, preferably a sulfuric acid aqueous solution, and is suitably used as an electrolyte film for a fuel cell.

  Here, when an electrolyte film for a fuel cell is produced by liquid treatment of an organic polymer film with sulfuric acid water, the concentration of sulfuric acid in the sulfuric acid water is preferably in the range of 3 to 20% by weight. The liquid temperature in the range of room temperature to 80 ° C., the liquid treatment time with the sulfuric acid solution is preferably 1 to 60 minutes, and the liquid treatment time is preferably 5 to 30 minutes.

  The organic polymer film may be processed as it is cast on a polyethylene terephthalate film substrate, or peeled off from the substrate after casting and wound with the organic polymer film alone. What was taken may be used, and you may process, peeling this organic polymer film from this base material in an unwinding part. Which condition is used may be determined in consideration of the thickness, characteristics, necessary characteristics after liquid treatment, treatment time, and the like of the organic polymer film.

  When processing with the base film attached, the surface contacting the suction conveyance roll may be either the base film surface or the surface of the film to be processed, but the electrolyte film is dried by the hot air from the hot air blower, Therefore, it is preferable that the surface of the film to be processed is in contact with the suction conveyance roll in order to remove the vapor by suction.

  Further, if the film is cast on both sides of the base film and then processed with the base film attached, the films to be processed on both sides can be processed simultaneously, and the productivity can be improved twice.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. In addition, about the obtained film, it evaluated by the following method.

[Evaluation methods]
<Film transport state>
The film conveyance state (wrinkle, meandering) in the processing apparatus was visually determined, and classified into OK: normal running and NG: abnormal running.

<Surface properties>
Judged visually and classified into 3 ranks A to C (A: non-defective product, B: accepted product but NG product, C: NG product) depending on the size and frequency of wrinkles and scratches, and the presence or absence of droplet marks. .

<Average surface opening area, maximum surface opening area, and surface opening ratio>
A CCD camera TI-324A manufactured by NEC was attached to a stereo microscope KSZ-T manufactured by Kyowa Optical Industry Co., Ltd., and the roll surface was imaged with a visual field width of 16.5 mm and a resolution of 25.8 μm. The obtained image was analyzed using Matrox Image Analysis Software Matrox Inspector to determine the area distribution of pores, and the average surface opening area, maximum surface opening area, and surface opening ratio were calculated. The measurement is performed at three locations for each sample, and the average surface opening area and the surface opening ratio are the average values of the three locations as the characteristic values of the sample, and the maximum surface opening area is the maximum value of the three locations of the sample. Characteristic values were used.

<Metal ion content>
In order to confirm whether or not the liquid-treated electrolyte film was normally ion-exchanged, the metal ion content of the film before and after acid treatment was measured using a tabletop fluorescent X-ray analyzer “SEA2120” manufactured by Seiko Instruments Inc. . The measurement was performed at three locations for each sample, and the average value at the three locations was used as the characteristic value of the sample.

The electrolyte precursor film before the treatment mainly has K ions. Since the ion-exchange group portion becomes H ⁺ by acid treatment, the amount of K ions per unit thickness was measured. In some comparative examples, a SUS316 roll covered with a nickel-plated wire mesh was used for the suction conveyance roll, so the amount of Ni ions in the film was measured in the same manner.

[Production Example 1] Method for producing film to be treated (1) Synthesis example 1 (monomer having a protecting group)
Montmorillonite clay K10 (1500 g) and 990 g of dihydroxybenzophenone were reacted at 110 ° C. while distilling a by-product formed in 2420 mL of ethylene glycol / 990 mL of trimethyl orthoformate. After 18 hours, 660 g of trimethyl orthoformate was added and reacted for 48 hours of synthesis. To the reaction solution was added 3000 mL of ethyl acetate, and after filtration, extraction was performed 4 times with a 2% aqueous sodium hydrogen carbonate solution.

  Further, after concentration, the desired 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane was obtained by recrystallization from dichloroethane.

(2) Synthesis example 2 (monomer having an ionic group)
Next, 1090 g of 4,4′-difluorobenzophenone (Aldrich reagent) was reacted in 1500 mL of fuming sulfuric acid (50% SO ₃ ) (Wako Pure Chemicals reagent) at 100 ° C. for 10 hours. Thereafter, the solution was poured little by little into a large amount of water and neutralized with NaOH, and then 2000 g of sodium chloride was added to precipitate the composite. The resulting precipitate was filtered off and recrystallized with an aqueous ethanol solution to obtain disodium 3,3′-disulfonate-4,4′-difluorobenzophenone. The purity was 99.3%.

(3) Synthesis Example 3 (Polymerization Example of Electrolyte Polymer)
In a 5 L reaction vessel equipped with a stirrer, nitrogen introduction tube and Dean-Stark trap, 43 g of 4,4′-dihydroxybenzophenone (Aldrich reagent 0.2 mol), 2,2-bis (4-hydroxyphenyl) -1, 207 g (0.8 mol) of 3-dioxolane, 87 g of 4,4′-difluorobenzophenone (0.2 mol of Aldrich reagent), and disodium 3,3′-disulfonate-4,4′- which is a monomer containing an ionic group 338 g (0.8 mol) of difluorobenzophenone was added, and after nitrogen substitution, 2500 g of N-methyl-2-pyrrolidone (NMP), 500 g of toluene, and 186 g of 18-crown-6 as a cyclic metal scavenger (Wako Pure Chemical Reagent) were added, After confirming that all the monomers were dissolved, 248 g of potassium carbonate (Aldrich Drugs, 1.8 mol) and the mixture was dehydrated at 160 ° C. under reflux, heated and then toluene is removed and subjected to 1 hour desalting polycondensation 200 ° C.. The weight average molecular weight of the obtained polymer was 280,000. Next, NMP was added so that the viscosity of the polymerization stock solution was 0.5 Pa · s to obtain a polymerization stock solution.

(4) Production Example of Electrolyte Coating Liquid The polymerization stock solution was centrifuged using an inverter / compact high-speed cooling centrifuge manufactured by Kubota Manufacturing Co., Ltd. . Since the precipitated solid (cake) and the supernatant (coating solution) could be separated cleanly, the supernatant was collected and transferred to a separable flask. Next, the solution was distilled under reduced pressure at 80 ° C. with stirring, NMP was removed until the viscosity of the supernatant liquid reached 2 Pa · s, and further filtered under pressure with a 5 μm polytetrafluoroethylene (PTFE) filter. Got.

(5) Example of film formation Using a PET film ("Lumirror (registered trademark)" manufactured by Toray Industries, Inc.) having a thickness of 125 μm and a width of 35 cm as a base material, the above electrolyte is applied by a coater (coater part; slit die coater) capable of continuous coating. The coating solution was applied by continuous casting. The coating speed is such that the solvent in the film can be dried at 150 ° C. for 10 minutes, the coating conditions are adjusted so that the thickness of the electrolyte membrane after solvent evaporation is 20 μm, and the resulting film is wound into a roll Film A was obtained. This film A had a width of 300 mm and a length of 100 m.

[Example 1]
Using the processing apparatus shown in FIG. 1, the acid treatment was performed on the film A having the PET film (base material) obtained in the above film forming example, and hydrolysis and ion exchange of the protective group in the polymer were performed. .

  In addition, 10% sulfuric acid was stored in the liquid processing tank 20 of this processing apparatus, and the inside of the tank was circulated while heating to 60 ° C. The residence time of the film in the liquid treatment tank 20 was 20 minutes.

  The submerged guide roll has a hollow structure, and the thickness of the roll wall is designed so that the buoyancy by volume and the load in the vertical downward direction by the roll are balanced, and finally the balance is adjusted by grinding the end face of the roll. .

  When unwinding the film A, the unwinding part brake of the film A is adjusted so that the tension detecting mechanism 12 provided at the entrance of the liquid processing tank has a tension of 20N, while the tension detecting mechanism 52 becomes 20N at the time of winding. The winding torque was adjusted as follows. Moreover, it set so that the electrolyte membrane side of the film A might contact a suction conveyance roll.

  Moreover, the exit roll and the entrance roll were installed so as to have a downward gradient of 10 degrees from the exit roll 22 of the film solution processing unit 2 toward the entrance roll 31 of the film cleaning unit 3.

  The pressing roll 44 is a free roll made of polyurethane rubber having a smaller diameter than the suction conveyance roll 41, and is installed at a position where the film starts to be sucked / adhered to the suction conveyance roll 41, and the film is pressed against the suction conveyance roll 41. The contact pressure was equal to that of its own weight.

As the suction conveyance roll 41, a granular polypropylene polymer having a center particle diameter of 100 μm was put into a hollow mold, sintered and bound, formed into a hollow shape, and then the surface was polished with a polishing cloth. The average surface opening area of the roll was 0.08 mm ² , the maximum opening area was 0.47 mm ² , and the surface opening ratio was 24%.

  And the hollow part of this suction conveyance roll 41 is connected to a decompression device (Vortex blower VB-015-G2 manufactured by Hitachi Industrial Equipment Systems Co., Ltd.), and a negative pressure of 3 kPa is generated on the surface of the suction conveyance roll 41, The film was adhered and fixed to the surface of the suction conveyance roll.

  Further, the hot air blower 43 is located at a position where it does not come into contact with the film from the top of the suction conveyance roll 41 to the film peeling portion, and the blower opening faces the suction conveyance roll across the film, and the surface of the suction conveyance roll 41 In order to blow the air toward the pressing roll 44, the film was dried by uniformly blowing warm air of 80 ° C. over the entire width of the film, and the pressing roll 44 was simultaneously dried.

  Furthermore, the conveyance roll which contacts the film 10 after a film drying part coat | covers a heat-shrinkable polymer film on a metal roll surface, and does not make a metal surface the non-metal so that ion exchange may not be performed in contact with a film. It was assumed. Moreover, each roll of a liquid processing part and a washing | cleaning part was made into the roll made from heat resistant vinyl chloride.

  Table 1 shows the evaluation results of the film wound by performing the liquid treatment under the above conditions.

[Example 2]
In Example 1, it processed like Example 1 except having peeled and unwinding PET film which is a base material from film A, and obtained film A-2. However, in Example 2, since the processing was performed without the PET film as the base material, the unwinding and winding tensions were both set to 5 N in consideration of the thickness of the base PET film.

  Table 1 shows the evaluation results of the film A-2 wound up by the liquid treatment.

[Comparative Example 1]
Except for using the suction conveyance roll 41, a granular polypropylene polymer having a center particle diameter of 1 mm was put into a hollow mold, sintered and bound, formed into a hollow shape, and then the surface was polished with a polishing cloth. In the same manner as in Example 2, the PET film as the base material was unwound from the film A while being unwound and subjected to liquid treatment to obtain a film A-3. The roll had an average surface opening area of 0.25 mm ² , a maximum opening area of 1.5 mm ² , and a surface opening ratio of 35%.

  A wound mark having a diameter of about 1 mm was scattered on the wound film surface. In winding the liquid-treated film, wrinkles were not generated, and the film was transported and wound normally. Table 1 shows the evaluation results of the film A-3 wound up by liquid treatment.

[Comparative Example 2]
Other than using a SUS316 hollow roll wall surface with a 3 mm diameter through-hole provided as a suction transfer roll 41 with a mesh opening of mesh # 125 and a nickel-plated wire mesh with a wire diameter of 80 μm on a surface of a porous metal roll with an opening ratio of 20% Performed acid treatment of film A in the same manner as in Example 1 to obtain film A-4. The average surface open area at this time is 0.014 mm ^2, the maximum open area 0.02 mm ^2, surface porosity was 36%.

  The wound film surface clearly had a suction mark having a diameter of about 3 mm due to the through hole. In winding the liquid-treated film, wrinkles were not generated, and the film was transported and wound normally. Table 1 shows the evaluation results of the film A-4 wound up by the liquid treatment.

[Comparative Example 3]
The hot air blower 43 is opposed to the position of the free space where the film is not fixed, on the downstream side of the suction conveyance roll and the upstream side of the film tension detection mechanism 52, not on the position where the blower opening faces the suction conveyance roll. The film A was acid-treated in the same manner as in Example 1 except that the film A-5 was installed. Thus, a film A-5 was obtained.

  Although the film was fixed without wrinkles on the suction conveyance roll, the whole substrate film was curled because it was dried by receiving hot air in a low tension state after leaving the suction conveyance roll. For this reason, the film meandered on the downstream roll, and the end of the wound film was scratched. Table 1 shows the evaluation results of Film A-5 wound up by liquid treatment.

[Comparative Example 4]
The hot air blower 43 is opposed to the position of the free space where the film is not fixed, on the downstream side of the suction conveyance roll and the upstream side of the film tension detection mechanism 52, not on the position where the blower opening faces the suction conveyance roll. In the same manner as in Example 2 except that the film was installed as described above, the film A was unwound while peeling off the PET film as the base material, and liquid treatment was performed to obtain a film A-6.

  The film was fixed without wrinkles on the suction conveyance roll, but after exiting the suction conveyance roll, the film was dried by receiving warm air in a low tension state, so that wakame-shaped wrinkles entered the vertical direction. It was difficult to take up normally because it was taken up while holding. Table 1 shows the evaluation results of the film A-6 wound up by the liquid treatment.

  The present invention is not limited to an acid treatment device for obtaining an electrolyte membrane for a fuel cell, but a treatment device for obtaining a water treatment membrane or a humidification membrane such as a salt electrolysis ion exchange membrane, an electrolyte membrane for water electrolysis, an ion exchange membrane, It can be applied to a processing apparatus for obtaining a secondary battery separator film. Furthermore, processing devices for optical recording substrates such as TFT LCD, STN LCD, PDP and other display device substrates, light guide plates, protective films, retardation films, touch panels, transparent electrode substrates, CDs, MDs and DVDs However, the application range is not limited to these.

DESCRIPTION OF SYMBOLS 1 Film unwinding part 2 Film liquid processing part 3 Film washing | cleaning part 4 Film drying part 5 Film winding part 10 Film 11 Processed film roll 20 Liquid processing tank 21, 31 Roll containing
22, 32 Outlet rolls 23a, 23b, 23c, 23d, 23e, 33a, 33b In-liquid guide roll 24 Upper cover 25, 35 Cleaning nozzles 34a, 34b In-air guide roll 30 Overflow receiving tank 36 First cleaning tank 37 Second cleaning tank 38 Washing water receiving tanks 39a, 39b Washing water communication pipes 41 Suction conveyance rolls 42 Depressurization devices 43 Hot air blowers 44 Press rolls 45 Sponge rolls with suction mechanisms 46 Suction devices 12, 52 Film tension detection mechanisms 51 Processed film rolls

Claims (10)

  A film liquid processing section for liquid processing a film, a film cleaning section for cleaning a liquid processed film, a film drying section for drying the cleaned film, and a film winding section for winding the dried film, and drying the film The section includes a suction conveyance roll whose roll surface is a non-metallic porous material, a decompression device, and a hot air blower, and the decompression device is connected to the suction roll so as to keep the suction conveyance roll surface at a negative pressure. And a warm air blower is provided so that an air blowing port may oppose a suction conveyance roll on both sides of a film, The film processing apparatus characterized by the above-mentioned.   The film processing apparatus according to claim 1, wherein the suction conveyance roll is a drive roll.   3. The film processing apparatus according to claim 1, wherein the non-metallic porous material is a granular polymer binder, a porous polymer, a porous ceramic, or a nonwoven fabric. The suction conveyance roll has an average surface opening area of 0.005 to 0.4 mm ² , a maximum surface opening area of 1 mm ² or less, and a surface opening ratio of 15 to 50%. Film processing equipment.   The film processing apparatus according to any one of claims 1 to 4, wherein a surface of the roll that comes into contact with the film in the film cleaning unit, the film drying unit, and the film winding unit is a non-metallic material.   The film drying unit is a film between the position where the film starts to be sucked and adhered to the suction conveyance roll or the position downstream from the position to the position where the warm air blows from the warm air blower. The film processing apparatus according to claim 1, further comprising: a pressing roll that presses the suction conveyance roll.   Furthermore, a film tension detecting mechanism is provided between the film drying section and the film winding section, and a winding speed control mechanism for controlling the speed of the film winding section so that the detected tension becomes a desired value. The film processing apparatus according to claim 1, wherein the film processing apparatus is a film processing apparatus.   In addition, a film unwinding section is provided, and a film tension detecting mechanism is provided between the film unwinding section and the film drying section, and the speed of the film unwinding section is controlled so that the detected tension becomes a desired value. The film processing apparatus according to claim 1, further comprising a speed control mechanism.   The film liquid processing section includes a liquid processing tank for storing the processing liquid, and the film cleaning section includes a cleaning tank for storing the cleaning liquid, and a submerged guide roll for changing the direction of the film and transporting is provided in these tanks. The liquid guide roll is immersed in a treatment liquid so as to maintain a balance between a vertically downward load and buoyancy by the roll. Film processing equipment.   The film cleaning unit includes a cleaning tank configured of a plurality of tanks for storing cleaning liquid, and the plurality of tanks are upstream of the cleaning water that has flowed out from the upper part of the downstream tank with respect to the film transport direction. The film processing apparatus according to claim 1, wherein the film processing apparatus is connected so as to be able to flow in from the bottom of the tank.

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