TWI500458B - Casting unit, dope applying method, and solution casting method - Google Patents

Description

Casting unit, coating liquid application method and solution casting method

The present invention relates to a solution casting die, a coating liquid application method, and a solution casting method.

Since optical transparency and flexibility are excellent, and weight and thickness are small, a polymer film (hereinafter referred to as a film) functions as an optical functional film in many fields. The polymer film has a deuterated cellulose film formed of deuterated cellulose. For example, a cellulose triacetate (hereinafter referred to as TAC) film formed of cellulose triacetate having an average degree of acetylation of preferably from 57.5% to 62.5% is used. Due to its strength and flammability, it uses a TAC film as a film base for a film material such as a photosensitive material. Further, since the optical isotropy of the TAC film is excellent, a liquid crystal display or the like which has become large in the market in recent years is used as an optical functional film such as an optical compensation film, a viewing angle film, and a polarizing plate protective film.

The film production method includes a melt extrusion method and a solution casting method. In the melt extrusion method, the polymer is heated and melted, and then the molten polymer is extruded to form a film. Melt extrusion has the advantages of high productivity and very low equipment cost. However, it is difficult to adjust the film thickness accuracy, and it is easy to form streaks (referred to as mold lines). Therefore, the melt extrusion method is difficult to be a high quality film of an optical functional film. In the solution casting method, a coating liquid containing a polymer and a solvent is cast on a support to form a cast film, and the cast film is peeled off from the support into a wet film after having a self-supporting property. The wet film is dried into a film, and then the film is rolled up. The optical isotropy and thickness uniformity of the solution casting method are superior to those of the melt extrusion method. In addition, in the solution casting method, the film is produced Less material than the melt extrusion method. Therefore, the solution casting method is applied to a film production method, particularly for producing an optical functional film.

It is known that the viscoelasticity causes a neck-in phenomenon, and when the casting solution is discharged from the casting die, the width of the casting particles of the discharged casting liquid becomes smaller than the outlet of the casting die. If a bottleneck occurs, the thickness of the cast pellet becomes smaller in the central region and becomes larger at the side portion (hereinafter, it is separated from the two side edges of the cast pellet by a maximum of 1%). The occurrence of the bottleneck phenomenon is related to the physical properties of the polymer and the processing conditions (the length of the casting grain, the slit width of the casting die, etc.). For example, if the elastic properties of the polymer become small, or if the tensile tension, the grain length, and the slit length of the casting die become large, bottlenecks often occur. If the bottleneck causes the side to be extremely thick, stripping troubles occur, such as cracking during stripping. Therefore, in order to prevent the peeling trouble, it is necessary to adjust the thickness of the side portion of the casting grain.

The method of adjusting the thickness of the side portion of the casting grain is disclosed in Japanese Patent Laid-Open Publication Nos. 2005-007808, 2001-79924, 2005-279956, and U.S. Patent No. 5,451,357. In the publication No. 2005-007808, the width of the coating liquid passage provided in the casting die is adjusted in such a manner that the width of the coating liquid passage can be made larger at the outlet side of the casting die. In the publications Nos. 2001-79924 and 5451357, the inner frame is slidable in the width direction to adjust the width of the coating liquid passage. In the publication No. 2005-279956, it separates the coating liquid flowing in the casting die into a central flow (or main flow) for forming the central portion of the casting grain, and a side flow for forming the side portion of the casting grain. (substantial flow), and adjust the flow of the side stream.

In recent years, solution casting methods have increased rapidly due to the demand for liquid crystal displays. And need high productivity. In addition, the liquid crystal display is thinned and has a small weight. Therefore, the development of the solution casting method and the solution casting apparatus makes it possible to efficiently manufacture a thin optical functional film.

In order to increase the productivity of the solution casting method, it sometimes makes the film manufacturing speed large. As is known, the film manufacturing speed is dependent on the casting speed of the casting process. Therefore, in order to increase the casting speed and productivity, it attempts to increase the traveling speed of the support (for example, more than 40 m/min) in the casting process. However, as the traveling speed of the support increases, the adhesion of the cast film to the surface of the support deteriorates. If the adhesion is deteriorated, entrained air is generated as the surface of the support travels into the space between the casting film and the support, which causes surface defects such as the unevenness of the cast film. Therefore, in order to compensate for the reduction in adhesion, it is necessary to decompress the back surface side (upstream side) of the casting grain in the traveling direction of the support.

However, when the back surface side is decompressed to carry out the solution casting method, the cast grain is vibrated and unstable, which causes thickness unevenness of the cast film. As a result, the film produced had thickness unevenness. Further, the side portions of the casting grains are more likely to vibrate than the central portion between the two side portions. Therefore, in the case where it is designed to manufacture a film which is thinner than a conventional one (for example, 60 μm thick), the grain thickness becomes thin. Therefore, the cast grain becomes less stable, and the film produced is more likely to have thickness unevenness.

Therefore, when it is designed to efficiently manufacture a film, it is necessary to adjust not only the thickness of the central portion of the cast grain but also the thickness of the side portion.

The method disclosed in the publication No. 2005-007808 must change or adjust the frame provided in the casting die, so that it takes a long time to make the thickness of the side portion a suitable value. Therefore, it is necessary to adjust the side when changing the composition of the coating liquid and the manufacturing conditions of the film. The thickness is time, so productivity is low, and this method is not suitable for manufacturing various types of films.

In the method disclosed in the publications Nos. 2001-79924 and 5,451,357, there is a slight space between the coating liquid passage of the casting die and the frame. Since the viscosity of the coating liquid used for the solution casting method is lower than that of the molten polymer, this space forms streaks on the coating liquid passing through the coating liquid passage having a space, and thus the film surface of the produced film has streaks. In addition, the coating liquid sometimes remains in the space, which causes the coating liquid in the coating liquid passage to gel. If a gelatinous material is mixed into the film, thickness unevenness occurs and the optical properties of the film deteriorate.

Further, in order to stably carry out the casting process, it is necessary to form a coating liquid passage and a frame in a casting die from a material (stainless steel or the like) which is never deformed under the influence of the coating liquid pressure. In the method disclosed in the publications No. 2001-79924 and No. 5,451,357, the frame slides on a component disposed near the frame, and dust is generated by sliding. If dust is mixed into the coating liquid, it is difficult to manufacture an excellent film. Therefore, in order to prevent the occurrence of dust, it uses a frame formed of a resin. However, in this case, the frame is easily deformed under the influence of the casting liquid pressure, so that it is extremely difficult to appropriately adjust the thickness of the side portion.

In addition, the method disclosed in Announcement No. 2005-279956 cannot independently adjust the pressure of mainstream and substantive flow. Therefore, it is difficult to adjust only the thickness of the side portion to a predetermined value in accordance with the film manufacturing conditions.

An object of the present invention is to provide a casting die which is effective for producing an optical functional film for preventing thickness unevenness and peeling trouble.

Another object of the present invention is to provide a method for preventing uneven thickness A coating liquid discharge method and a solution casting method for efficiently producing an optical functional film which are troublesome and stripped.

In the coating liquid casting method of the present invention, in a solution casting method for forming a cast film to be dried into a polymer film on a moving support, the preparation is for a self-casting die to a support constituent particle. The side coating liquid on the side, the casting die discharges the side coating liquid through the slit extending in the width direction of the support, and prepares an intermediate coating liquid for constituting the intermediate portion between the sides of the pellet. Then, the side coating liquid flow and the intermediate coating liquid flow are combined in the casting die, and the casting die has a partition member having a slit so that the partition member can form a side flow passage for the side coating liquid flow, and an intermediate flow for the intermediate coating liquid flow. aisle. The downstream end of the partition member is disposed upstream of the slit so that the side coating liquid and the intermediate coating liquid can be combined before flowing out of the slit. The side coating liquid and the intermediate coating liquid are then applied together.

Preferably, the distance from the outlet to the downstream end is in the range of 0.1 mm to 40 mm. Further, the side flow passage has a width W1 of at least 0.1 mm in the longitudinal direction of the slit.

Preferably, the side coating liquid is supplied to the side feed passage by a side feed means for the feed side coating liquid. It is particularly preferable to supply the intermediate coating liquid to the intermediate feed passage by means of an intermediate feeding device for feeding the intermediate coating liquid, and to control the side coating flowing in the side flow passage independently using the side feeding device and the intermediate feeding device. The flow rate between the liquid and the intermediate coating flowing in the intermediate flow passage.

Preferably, the intermediate coating liquid, the first side coating liquid to be supplied to one of the side flow passages, and the second side coating liquid to be supplied to the other side flow passage are the same.

It is preferred that the side coating liquid has a higher elongation viscosity than the intermediate coating liquid. In particular If the elongation viscosity of the side coating liquid is ηe and the tensile viscosity of the intermediate coating liquid is ηc, the ηe/ηc value is at most 3. Further, in particular, each solvent of the intermediate coating liquid and the side coating liquid contains a good solvent component and a poor solvent component, and the solvent component of the poor solvent component to the side coating liquid is higher than the solvent content of the poor solvent component to the intermediate coating liquid. In particular, the content of the polymer in the side coating liquid is lower than the content of the polymer in the intermediate coating liquid.

Preferably, the partition portion has at least one contact surface for contacting one of the intermediate coating liquid and the side coating liquid, and the contact surface is coated with a polymer compound.

In a solution casting method for applying a coating liquid to a moving support to manufacture a polymer film, which prepares a side coating liquid for combining a side portion of a pellet from a casting die to a support, the casting die is pressed according to the width of the support The direction extending slit discharges the side coating liquid, and prepares an intermediate coating liquid for constituting the intermediate portion between the sides of the pellet. Then, the side coating liquid flow and the intermediate coating liquid flow are combined in the casting die, and the casting die has a partition member having a slit so that the partition member can form a side flow passage for the side coating liquid flow, and an intermediate flow for the intermediate coating liquid flow. aisle. The downstream end of the partition member is disposed upstream of the slit so that the side coating liquid and the intermediate coating liquid can be combined before flowing out of the slit. The side coating liquid and the intermediate coating liquid are then applied together. After the cast film has self-supporting properties, the cast film is peeled off from the support into a polymer film, and the polymer film is dried.

In the present invention, a casting unit for applying a coating liquid to form a granule on a moving pylon includes a casting die for discharging a coating liquid, and the casting die has a side for supplying a side coating liquid to constitute a granule a side inlet, an intermediate inlet for supplying an intermediate coating liquid to form an intermediate portion between the side portions, a groove for forming a side coating liquid and an intermediate coating liquid, and a slit for collectively discharging the side coating liquid and the intermediate coating liquid And a manifold for retaining the intermediate coating liquid. Further, the casting unit includes a partition portion disposed in the groove, the partition portion partitions the groove into a side flow passage for the side coating liquid flow, and an intermediate flow passage for the intermediate coating liquid flow, and the downstream end of the partition member has an incision with an acute angle, the slit It is disposed in the range of 0.1 mm to 40 mm from the upstream side of the slit. Furthermore, the casting unit comprises a feeding device for feeding the side coating liquid to the side inlet.

Preferably, the side coating liquid is supplied to the side feed passage by a side feed means for the feed side coating liquid. It is particularly preferable to supply the intermediate coating liquid to the intermediate feed passage by means of an intermediate feeding device for feeding the intermediate coating liquid, and independently control the flow side in the side feed passage using the side feeding device and the intermediate feeding device. The flow rate between the coating liquid and the intermediate coating liquid flowing in the intermediate feed passage.

Preferably, the partition portion has at least one contact surface for contacting one of the intermediate coating liquid and the side coating liquid, and the contact surface is coated with a polymer compound.

According to the present invention, the groove in the casting die has two partitions for dividing the groove into the groove intermediate portion and the groove side portion, and feeding the first casting coating liquid into the groove intermediate portion and the second and the second The three-coating solution is fed into the side of the tank. The first-third casting solution is then combined and then fed to the exit of the casting die to form a casting pellet between the outlet and the support. Further, the flow rates of the second and third casting liquids are independently controlled, and the thickness of the side portions of the casting grains can be easily adjusted to a predetermined value. Thus, the peeling trouble and the thickness unevenness are reduced, so that the optical functional film can be efficiently produced.

Preferred embodiments are explained in detail below. However, the invention is not limited to the description.

[raw material] (polymer)

As the polymer of this specific embodiment, a known polymer which can be used in a solution casting method can be used. For example, it is preferably cellulose deuterated, and particularly preferably triacetyl cellulose (TAC). The deuterated cellulose is preferably a degree of substitution of a mercapto group with a hydrogen atom on the cellulose hydroxyl group, and preferably satisfies all of the following formulas (I) to (III). In the formulae (I) to (III), A is a degree of substitution of a hydrazine group with a hydrogen atom on a cellulose hydroxyl group, and B is a degree of substitution of a fluorenyl group having a carbon atom number of 3 to 22 with respect to a hydrogen atom. It should be noted that at least 90% by weight of the TAC is particles having a diameter of 0.1 mm to 4 mm.

Further, the polymer used in the present invention is not limited to deuterated cellulose.

The glucose unit constituting the cellulose having a β-1,4 bond has a free hydroxyl group at the second, third and sixth positions. Deuterated cellulose is a polymer in which a hydrogen atom of a part or all of a hydroxyl group is substituted with a mercapto group having at least two carbon atoms by esterification. The degree of deuteration is the degree of esterification of the hydroxyl groups in the second, third, and sixth positions. If the esterification of each hydroxyl group is 100%, the degree of deuteration is 1.

Here, if the thiol system replaces the hydrogen atom at the second position in the glucose unit, the degree of deuteration is referred to as DS2 (the degree of deuteration substitution at the second position), and if the thiol system replaces the third position in the glucose unit The hydrogen atom is referred to as DS3 (the degree of deuteration substitution at the third position). In addition, if the thiol system replaces the hydrogen atom in the sixth position in the glucose unit, then The degree of deuteration is called DS6 (the degree of substitution in the sixth position). The sum of the degree of deuteration DS2+DS3+DS6 is preferably 2.00 to 3.00, particularly 2.22 to 2.90, and particularly 2.40 to 2.88. Furthermore, DS6/(DS2+DS3+DS6) is preferably at least 0.28, in particular at least 0.30, and in particular from 0.31 to 0.34.

In the present invention, the amount and type of thiol groups in the deuterated cellulose may be only one or at least two. If there are at least two fluorenyl groups, one of them is preferably an acetamino group. If the hydrogen atoms of the hydroxyl groups at the second, third and sixth positions are substituted with an ethyl hydrazide group, the total degree of substitution is referred to as DSA, and if the hydrogen atoms of the hydroxyl groups at the second, third and sixth positions are via an ethyl hydrazide group The thiol group is substituted, and the total degree of substitution is called DSB. In this case, the DSA+DSB value is preferably from 2.22 to 2.90, particularly from 2.40 to 2.88. Furthermore, the DSB is preferably at least 0.30, and in particular at least 0.7. According to the DSB, the percentage of the replacement of the sixth position to the second, third and sixth positions is at least 20%. This percentage is preferably at least 25%, in particular at least 30%, and in particular at least 33%. Furthermore, the DSA+DSB of the sixth position of the deuterated cellulose is preferably at least 0.75, in particular at least 0.80, and in particular at least 0.85. When these kinds of deuterated cellulose are used, they can produce a solution (or coating liquid) having a preferable solubility, and in particular, a solution having a preferable solubility to a non-chlorine type organic solvent can be produced. Further, when the above deuterated cellulose is used, the produced solution has low viscosity and good filtration power. It should be noted that the coating liquid contains a polymer and a solvent for dissolving the polymer. In addition, if necessary, an additive is added to the coating liquid.

Cellulose as a raw material for deuterated cellulose can be obtained from one of wood pulp and cotton wool.

In the deuterated cellulose, the mercapto group having at least 2 carbon atoms may be an aliphatic group or an aryl group. This deuterated cellulose is, for example, an alkylcarbonyl ester of an cellulose and an alkenylcarbonyl ester. Further, there are an aromatic carbonyl ester, an aromatic alkylcarbonyl ester and the like, and these compounds may have a substituent. Preferred examples of the compound are acrylyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecanoyl , octadecyl decyl, isobutyl decyl, tributyl decyl, cyclohexanecarbonyl, oleoyl, benzhydryl, naphthylcarbonyl, cinnamyl and the like. Among them, the preferred base is propyl sulfonyl, dodecyl fluorenyl, octadecyl fluorenyl, tert-butyl fluorenyl, oleyl benzhydryl, naphthylcarbonyl, cinnamyl, and the like. Base and Ding Yanji.

(solvent for coating liquid)

Further, the solvent used for preparing the coating liquid is an aromatic hydrocarbon (for example, benzene, toluene, etc.), a halogenated hydrocarbon (for example, dichloromethane, chlorobenzene, etc.), an alcohol (for example, methanol, ethanol, n-propanol, n-butanol, and diethyl ether). A diol or the like), a ketone (e.g., acetone, methyl ethyl ketone, etc.), an ester (e.g., methyl acetate, ethyl acetate, propyl acetate, etc.), an ether (e.g., tetrahydrofuran, methyl acesulfame, etc.). It should be noted that the coating liquid is a polymer solution or dispersion in which a polymer or the like is dissolved or dispersed in a solvent. It should be noted in the present invention that the coating liquid is a polymer solution or dispersion obtained by dissolving or dispersing a polymer or the like in a solvent.

The solvent is preferably a halogenated hydrocarbon having 1 to 7 carbon atoms, and particularly dichloromethane. Regarding the solubility of deuterated cellulose, the stripping force of the cast film from the support, the mechanical strength of the film, the optical properties of the film, etc., it is preferred to mix one or more alcohols having 1 to 5 carbon atoms with dichloride. Methane. alcohol The content is preferably in the range of 2% by weight to 25% by weight, and particularly in the range of 5% by weight to 20% by weight, based on the total solvent. Specifically, there are methanol, ethanol, n-propanol, isopropanol, n-butanol and the like. Preferred examples of the alcohol are methanol, ethanol, n-butanol, or a mixture thereof.

Incidentally, in order to minimize the influence on the environment, a solvent composition which does not use dichloromethane has been gradually considered. For this purpose, it is preferably an ether having 4 to 12 carbon atoms, a ketone having 3 to 12 carbon atoms, an ester having 3 to 12 carbon atoms, and an alcohol having 1 to 12 carbon atoms. Further, a mixture thereof can also be used as appropriate. For example, there is a mixture of methyl acetate, acetone, ethanol, and n-butanol. These ethers, ketones, esters, and alcohols may have a ring structure. Further, a compound having an ether, a ketone, an ester, and at least two functional groups with an alcohol (i.e., -O-, -CO-, -COO-, and -OH) can be used for the solvent.

It is to be noted that the detailed description of the deuterated cellulose is explained in [0140] to [0195] of Japanese Patent Laid-Open Publication No. 2005-104148, and the description of this publication can be applied to the present invention. It should be noted that the detailed explanation of the solvent and additive additive materials (such as plasticizer, degradation inhibitor, UV absorber, optical anisotropy control agent, dye, matting agent, release agent, hysteresis control agent, etc.) is disclosed in Japanese Patent Publication. [0196] to [0516] of Announcement No. 2005-104148.

[coating method]

The coating liquid is produced from the above raw materials. As shown in Fig. 1, the coating liquid production line 10 is composed of a solvent tank 11 for storing a solvent, a mixing tank 13 for mixing TAC and a solvent therein, an addition funnel 14 for supplying TAC, and a storage additive. The additive tank 15 is configured. In addition, the coating liquid production line 10 has A heating device 18 for heating the expanding liquid (detailed below), a temperature controller 19 for controlling the temperature of the prepared coating liquid, and a filtering device 20. Further, the coating liquid production line 10 has a flashing device 21 for concentrating the coating liquid, and a filtering device 22. Further, the coating liquid production line 10 has a recovery device 23 for recovering solvent vapor, and a refining device 24 for recycling the recovered solvent. The coating liquid production line 10 is connected to the film production line 32.

In the coating liquid production line 10, the main coating liquid 48 is produced in the following order. The valve 35 disposed in the line connecting the solvent tank 11 to the mixing tank 13 is opened so that the solvent in the solvent tank 11 can be fed to the mixing tank 13.

The TAC in the addition funnel 14 is then fed to the mixing tank 12 in its measured amount. The valve 36 is then opened and closed so that the necessary amount of additive can be sent from the additive tank 15 to the mixing tank 13. The method of feeding the additive to the mixing tank is not limited to the above description. In the case where the additive is liquid at room temperature, it can be fed to the mixing tank 13 in a liquid state without having to prepare an additive solution. In the case where a plurality of additive compounds are used, they may be accumulated together in the additive tank 15 with additives containing various additive compounds. Alternatively, a plurality of additive tanks may be used to contain the respective additive compounds, which are sent to the mixing tank 13 via separate lines.

In the above explanation, it sequentially delivers the solvent, TAC, and additives to the mixing tank 13. However, the order of feeding is not limited to this. For example, after a predetermined amount of TAC is sent to the mixing tank 13, a predetermined amount of solvent and additive feed may be applied to obtain a TAC solution. Alternatively, the additive may not be previously sent to the mixing tank 13, and the additive may be added to the mixture of TAC and solvent in a later procedure.

The mixing tank 13 has a jacket 37 covering the outer surface of the mixing tank 13, a first agitator 39 rotated by the motor 38, and a second agitating by the motor 40. Mixer 41. The mixing tank 13 stores a mixed solvent 28, a TAC, and an additive liquid. Further, the first agitator 39 preferably has a fixed vane, and the second agitator 41 is preferably a dissolver type concentric agitator. It should be noted that the dissolved liquid 28 may be an expanded liquid in which TAC may expand in a solvent.

The internal temperature of the mixing tank 13 is controlled by the heat transfer medium in the jacket 37. The preferred internal temperature is in the range of -10 ° C to 55 ° C. It should be noted that the first agitator 39 and the second agitator 41 are selected in accordance with the conditions of the preparation of the coating liquid.

It drives the pump 25 so that the dissolved liquid 28 in the mixing tank 13 can be sent to the heating device 18, which is preferably a jacketed line. The heating device 18 may preferably have a pressurizing device to effectively dissolve. When the heating device 18 is used, the dissolution of the solid compound is carried out under heating or hot pressing conditions, so that a coating liquid can be obtained. This method is called thermal dissolution. The temperature at which the liquid 28 is dissolved is preferably in the range of 0 ° C to 97 ° C. In order to sufficiently dissolve the TAC in the solvent, it is preferred to carry out not only the thermal dissolution method but also the cold dissolution method. It sends the heated dissolved liquid 28 to the temperature controller 19 to control the temperature of the dissolved liquid 28 to almost room temperature. Filtration of the coating liquid is then completed at the filtering device 20 so that impurities and insoluble materials can be removed from the coating liquid. The filter material of filter unit 20 preferably has an average nominal diameter of up to 100 microns. The filtration flow rate in the filtration unit 20 is preferably at least 50 liters per hour. The filtered coating liquid is fed through a valve 46, and thus stored as a main coating liquid 48 in the raw material tank 30.

The coating liquid can be used as the main coating liquid 48 for film production explained below. However, in the method in which the TAC is dissolved after the preparation of the dissolved liquid 28, if it is designed to produce a high-concentration coating liquid, the manufacturing time of the coating liquid becomes long. As a result, the manufacturing cost becomes high. Therefore, it is preferred to first prepare a coating liquid having a concentration lower than a predetermined value, and then complete concentration of the coating liquid. In this embodiment, the filtered coating liquid is sent to the flash unit 21 via valve 46. The solvent of the coating liquid is partially evaporated in a flash unit. The solvent vapor generated by evaporation is condensed into a liquid state by a condenser (not shown), and recovered by a recovery device 23. The recovered solvent is recycled and reused by the refining unit 24. According to this method, since the manufacturing efficiency becomes high and the solvent is reused, it can be designed to reduce the cost.

The coating liquid concentrated as described above is taken out from the flash device 21 via the pump 26. Further, in order to remove the foam generated in the coating liquid, it is preferred to carry out the bubble removing treatment. There are many known methods for removing bubbles, such as ultrasonic irradiation. The coating liquid is then fed to a filtration device 20 where undissolved material is removed. It should be noted that the temperature of the coating liquid in the filtering device 20 is preferably in the range of 0 ° C to 200 ° C.

The filtered coating liquid is stored in the raw material tank 30 as a main coating liquid 48 having a stirrer 30b that is rotated by a motor 30a. The coating liquid thus produced preferably has a TAC concentration in the range of 5 to 40% by weight.

It is to be noted that the method of producing the main coating liquid 48 is disclosed in detail in [0517] to [0616] of Japanese Patent Laid-Open Publication No. 2005-104148, for example, a dissolution method and an addition method for a material, and a solution casting for forming a TAC film. Raw materials and additives in the method, filtration methods, bubble removal methods, and the like. This description also applies to the present invention.

[Film film method]

The film preparation method is explained below. As shown in FIG. 2, the film manufacturing method 50 includes a casting coating liquid process 52, a casting process 54, a stripping process 56, and a drying process. Order 58. In the casting coating liquid preparation method 52, the first to third casting coating liquids 51a to 51c are prepared from the main coating liquid 48 obtained in the coating liquid production line of Fig. 1. In the casting program 54, it produces the first-third casting solution liquids 51a-51c so that the casting film 53 can be obtained. In the stripping program 56, the cast film 53 is peeled off to become the wet film 55. In the drying process 58, it dries the wet film 55 into a film 57. It should be noted that the film forming process 50 further has a winding process in which the film 57 is wound into a film roll.

[solution casting method]

A specific embodiment of the solution casting method will now be described with reference to FIG. However, the invention is not limited to this specific embodiment. As shown in FIG. 3, the film production line 32 includes a casting chamber 62, a path roller 63, a pin tenter 64, an edge cutting device 65, a drying chamber 66, a cooling chamber 67, and a winding chamber 68.

The material tank 30 has a motor 30a, an agitator 30b that is rotated by the motor 30a, and a jacket 30c. The raw material tank 30 stores the main coating liquid 48, turns the agitator 30b, and controls the inner temperature of the raw material tank 30 by supplying a temperature control medium (not shown) to the outer casing 30c. The agglomeration of the polymerization or the like is thus lowered so that the main coating liquid 48 can be made uniform in the raw material tank 30.

The material tank 30 is connected to the casting chamber 62 via lines 71a-71c. The line 71a has a gear pump 73a, a filter unit 74a, and a static mixer 75a as an in-line mixer. The line 71b has a gear pump 73b, a filter unit 74b, and a static mixer 75b as an in-line mixer. The line 71c has a gear pump 73c, a filtering device 74c, and a static mixer 75c as an in-line mixer.

Upstream of the static mixers 75a-75c, the additive supply line connection tube Lines 71a-71c are fed with an additive compound (at least one of a predetermined amount of a UV absorber, a matting agent, a retarder, etc.) or a polymer solution containing an additive compound. It should be noted that the additive compound and the polymer solution containing the additive compound are hereinafter referred to as a mixed additive.

Gear pumps 73a-73c are connected to the casting controller 79. The casting controller 79 thus controls the driving of the gear pumps 73a-73c to feed the main coating liquid 48 from the material tank 30 to the casting die 81 provided by the casting chamber 62 at a predetermined flow rate. The additive compound or polymer solution is then added to the main coating liquid 48 fed through lines 71a-71c. The mixing of the main coating liquids 48 is then completed in the respective lines 71a-71c with static mixers 75a-75c so that the first-third casting coating liquids 51a-51c are available.

The casting chamber 62 includes a casting die 81, a casting cylinder 82 that rotates in the rotational direction Z1, a stripping roller 83, a temperature control device 86, a condenser 87, a recovery device 88, and a decompression chamber 165. In the casting chamber 62, the first-third casting coating liquids 51a-51c are cast on the casting cylinder 82 by the casting die 81 to form a casting grain between the casting die 81 and the casting cylinder 82. 80. The cast film 53 is then peeled off into a wet film 55 supported by a stripping roller 83. The internal temperature of the casting chamber 62 is controlled by a temperature control device 86, and the solvent vapor generated by evaporation of the solvent by the condenser 87 is condensed and recovered by the recovery unit 88. The recovered solvent is then used in a coating solution. The recovery device 88 thus controls the solvent vapor pressure of the atmosphere in the casting chamber 62 to a predetermined range.

<casting barrel>

The casting cylinder 82 is disposed below the casting die 81 and has a cylindrical or cylindrical shape. The casting cylinder 82 has a shaft 82a that is connected to the casting controller 79. Such as The casting controller 79 also controls the rotation speed of the casting cylinder 82 in the rotational direction Z1 such that the speed of the circumference 82b of the casting cylinder 82 against the casting die 81 can be a predetermined value.

In order to control the surface temperature of the casting cylinder 82 to a predetermined value, it is preferable to provide a heat transfer medium circulator 89. The heat transfer medium passing through the path (not shown) is controlled by the heat transfer medium circulator 89. The temperature T1 of the circumference 82b of the casting drum 82 is thus maintained at a predetermined value.

The width of the casting cylinder 82 is not particularly limited. However, the width of the casting cylinder 82 is preferably 1.1 to 2.0 times the width of the casting. Preferably, the circumference is ground such that the surface roughness of the circumference 82b is preferably at most 0.01 microns. Further preferably, the surface defects of the circumference 82b are minimized. Specifically, it has no pinholes of at least 30 microns per square meter, up to one pinhole of at least 10 microns and less than 30 microns, and up to two pinholes of less than 10 microns. The rotation speed of the casting cylinder 82 fluctuates by a maximum of 3% with respect to a predetermined value, and when the casting cylinder 82 is rotated once, the width in the width direction is at most 3 mm.

The material of the casting cylinder 82 is preferably stainless steel, and particularly SUS 316, so that the casting cylinder 82 can have sufficient corrosion resistance and strength. Preferably, the circumference 82b is chrome plated. Such a circumference 82b has sufficient corrosion resistance and strength.

(stripping roller)

The stripping roller system is disposed on the downstream side of the casting die 81 in the "moving direction Z1" to approach the circumference 82b. When the cast film 53 is peeled off from the casting drum 82 to become the wet film 55, the peeling roller 83 supports the wet film 55 and guides the wet film to the path roller 63.

The temperature control device 86 is for maintaining the internal temperature of the casting chamber 62 within a predetermined range. In the casting chamber 62, solvent vapor is generated by evaporation of a solvent such as the first to third casting liquids 51a to 51c, the casting film 53, and the wet film 55. The solvent vapor is condensed by the condenser 87 and then recovered by the recovery unit 88. The recovered solvent is recycled as a solvent for preparing a coating liquid. Therefore, the vapor pressure of the solvent vapor is maintained at a predetermined value in the casting chamber 62.

A plurality of path rollers 63, a pin tenter 64, and an edge cutting device 65 are disposed downstream of the casting chamber 62.

After the wet film 55 is fed out from the casting chamber 62, the path roller 63 supports the wet film 55 and is guided to the pin tenter 64. It should be noted that the approach path roller 63 has an air feeder (not shown). The air feeder supplies dry air to the wet film 55 on the path roller 63 or a portion of the wet film 55 between the path rollers on the feed path to dry the wet film 55.

The pin tenter 64 includes a plurality of pins (not shown) as a holding member for holding the wet film 55. The pin is attached to the endless chain and moves cyclically as the chain travels. In the pin tenter 64, it inserts a plurality of pins into the two side edge portions near the entrance. The two side edge portions are thus held and transported by pins. The pin tenter 64 has a blower (not shown) for feeding dry air to the wet film 55. Therefore, the residual solvent content in the wet film 55 is lowered when the wet film 55 is transported in the pin tenter 64. The pins are removed from the two side edge portions of the film 57 near the exit of the pin tenter 64.

The film 57 is fed to the edge cutting device 65, and the two side edge portions are cut away. The edge cutting device 65 is connected to the crusher 95, and the two side edge portions are pressed into pieces by the crusher 95. Fragments contain TAC and several additive Compound. The fragments are therefore dissolved in the solvent and the additives are removed. So only get TAC and then use it.

It should be noted that there is a clip tenter 97 for drying the film 57 between the pin tenter 64 and the edge cutting device 65. The clip-on tenter 97 is a drying device including a plurality of clips as the jaw members of the two side edge portions of the film 57. The clip-on tenter 97 stretches the film 57 under predetermined conditions to provide the film 57 with predetermined optical properties.

There are a plurality of rolls 100 and adsorption means 101 in the drying chamber 66. The film 57 is transported into the cooling chamber 67 and cooled. On the downstream side of the cooling chamber, there is a forced neutralization device (or neutralization rod) 104 for discharging the charged electrostatic potential of the film 57 to a predetermined value. Further, in this embodiment, there is a embossing roll 105 for providing a film on the downstream side of the forced neutralization device 104.

The internal temperature of the drying chamber 66 is not particularly limited. However, it is preferably in the range of 50 ° C to 160 ° C. The film 57 is transported by overlapping the plurality of rolls 100 in the drying chamber 66. The solvent vapor evaporated from the film 57 by the drying chamber 66 is adsorbed by the adsorption device 101. It reuses air from the solvent component as dry air in the drying chamber 66. It should be noted that the drying chamber 66 preferably has a plurality of compartments to vary the drying temperature. Further, a front drying device (not shown) is provided between the edge cutting device 65 and the drying chamber 66 to perform drying before the film 57. This prevents the temperature of the film 57 from rapidly increasing, thus reducing the shape change of the film 57.

It transports the film 57 to the cooling chamber 67 and is cooled therein to about room temperature. A humidity control chamber (not shown) may be provided between the drying chamber 66 and the cooling chamber 67 to adjust the humidity. Preferably, the temperature and humidity are controlled in the humidity control room Controlled air is applied to the membrane 57. Thus, curling and winding defects of the film 57 can be reduced in the winding process.

The neutralization device (or neutralization bar) 104 is then forced to exclude the charged electrostatic potential of the film 57 to a predetermined value (e.g., in the range of -3 kV to +3 kV). After the neutralization, embossing of the two side portions of the film 57 is performed by the embossing roller to provide embossing. The embossing height from the bottom to the top of the embossing ranges from 1 micron to 200 microns.

The winding chamber 68 has a winding shaft 107 and a pressing roller 108. The film 57 is wound by the winding shaft 107 in the winding chamber 68. At this time, a tension of a predetermined value is applied to the pressing roller 108.

(casting die)

As shown in Figs. 4 and 5, the casting die 81 is composed of the lips 120, 121, and the side plates 122, 123, and has an inlet 81a through which the first casting coating liquid 51a flows from the line 71a, and discharges the first - The third casting solution 51a-51c is a cast outlet. The first to third casting liquids 51a to 51c are fed through the respective inlets and joined in the casting die 81.

The lip plate 120 has contact faces 120a, 120b for contacting the first-third casting solution liquids 51a-51c at the inlet 81a to the outlet 81b. The lip plate 121 has contact faces 121a to 121d for contacting the first to third casting liquids 51a to 51c at the inlets 81a to 81b. The contact faces 120a, 120b, 121a-121d are combined to form a coating liquid passage 81c that connects all of the inlets 81a to 81b. On the coating liquid passage 81c, a manifold 125 and a slit 126 are formed. The manifold 125 is formed by the contact faces 120a, 121a arranged in the direction TD of the casting die 81 in the width direction (or the longitudinal direction of the slit 126). The slit 126 is the contact surface 120b The area between the contact faces 121a-121d. It should be noted that the lips 120, 121 extend in the direction TD, and the lip 120 is disposed on the upstream side of the lip 121 in the rotational direction of the casting cylinder 82.

The slit 126 in the upper region has a gap width SW1 between the contact faces 120b and 121b, and the slit 126 in the lower region has a slit width SW2 between the contact faces 120b and 121d. It should be noted that the upper region is the upstream side region of the casting coating liquid 51a in the flow direction, and the lower region is the downstream side region of the casting coating liquid 51a in the flow direction. The slit width SW2 is smaller than the slit width SW1. The intermediate portion of the slit 126 is formed between the region above the slit width SW1 and the region below the slit width SW2, and is composed of the contact faces 120b and 121c. In the intermediate portion, the contact surface 121c connects the contact surface 121b to the contact surface 121d, and tends to contact the surfaces 121b and 121d so that the slit width can be made smaller at a position closer to the lower portion, and the slit width can be continuously reduced from SW1 to SW2. small.

The inner frame plates 130 and 131 are disposed on the two side edges of the coating liquid passage 81c in the direction TD. The inner frame plates 130, 131 adhere the lips 120, 121 and the side plates 122, 123 by means of a filler (not shown). The inner frame plates 130 and 131 extend in the direction TH such as the width direction of the manifold 125 and the slit 126, and the inner frame plate 130 is disposed on the upstream side of the inner frame plate 131 in the rotation direction of the casting tube 82.

The inner frame plate 130 has contact faces 130a, 130b that contact the first to third coating liquids 51a-51c. The inner frame plate 131 has contact faces 131a, 131b that contact the first to third coating liquids 51a to 51c. The contact faces 130a, 131a are formed such that the width of the coating liquid passage 81c can be almost fixed. The contact faces 130b, 131b tend to be 130a, 131a such that the width of the coating liquid passage 81c can be large.

In the casting die 81, a passage formed by the inner frame plate 130 and the side plate 122 is formed. 135, 136. Channel 136 connects line 71b with channel 135. The passage 135 extends downwardly and has a size or width W1 in the direction TD, and connects the passage 136 with the slit 126. The outlet 135a of the passage 135 is formed on the contact surface 130b of the inner frame plate 130. The inner frame plate 130 has a partition portion 140 for partitioning the passage 135 and the coating liquid passage 81c. The partition portion 140 has an acute end 140a on the side of the outlet 81b. The apex of the end 140a is disposed near the center in the direction TD. Further, the end 140a is formed to have a clearance CL1 to the outlet 81b.

The casting die 81 is a passage 145, 146 formed by the inner frame plate 131 and the side plate 123. Channel 146 connects line 71c with channel 145. Channel 145 extends downwardly and connects channel 146 with slit 126. The outlet 145a of the passage 145 is formed on the contact surface 131b of the inner frame plate 131. The inner frame plate 131 has a partition portion 150 for partitioning the passage 145 from the coating liquid passage 81c. The partition portion 150 has an acute end 150a on the side of the outlet 81b. The apex of the end 150a is disposed near the center in the direction TD. Further, the end 150a is formed to have a clearance CL1 to the outlet 81b.

The thickness D1 of each of the partition portions 140, 150 in the direction TD is preferably at most 2 mm. If the thickness exceeds 2 mm, it is sometimes difficult to form the casting pellet 80 stably. Further, the lower limit of the thickness D1 is not particularly limited as long as the partition portions 140, 150 are not deformed or damaged by the pressure of the first-third casting coating liquids 51a-51c.

(material)

The material for manufacturing the lip plates 120, 121 and the inner frame plates 130, 131 of the casting die 81 preferably has resistance to oxidation and corrosion caused by contact with the casting solution 51. Further, in order to keep the distances CL1 - CL4 within a predetermined range, it is preferable that the size variation hardly occurs in the casting process. Therefore, the materials for the lips 120, 121 and the inner frame plates 130, 131 preferably have the following characteristics: (1) corrosion resistance in the forced corrosion test in the aqueous electrolyte solution is the same as that of SUS316, and (2) at the gas-liquid interface No plaque (or etched corrosion) occurs, even if the material is immersed in a mixed liquid of methylene chloride, methanol and water for three months, and (3) the coefficient of thermal expansion is at most 2 × 10 ^-5 (°C ^{- 1} ).

Therefore, the materials for the lips 120, 121 and the inner frame plates 130, 131 are preferably stainless steel and ceramics, particularly preferably Worstian iron type stainless steel, and particularly SUS316, SUS316L, precipitation hardening type stainless steel such as SUS630, SUS631, and the like.

If the above adjustment method is carried out, it is preferable to further satisfy not only the above conditions (1) to (3) but also the following conditions: (4) the lips 120, 121 and the inner frame plates 130, 131 are formed during the forming process. The volume change rate is at most 0.05%, and (5) the inner frame plates 130, 131 are not hard to damage the lips 120, 121.

In the present invention, it is preferable that the volume change rate of the lips 120, 121 and the inner frame plates 130, 131 satisfy the above condition (4). The volume change rate indicates the maximum value of the dimensional change rates a _x , a _y , and a _z in the x, y, and z rectangular coordinate systems. When the external force F (about 90 Newtons) is applied per unit size (1 mm 2 ) in the x-axis direction, the size of the inner frame plates 130 and 131 is changed to Δb _x , and the size of the inner frame plate before the external force is applied is b _x In the case, the rate of change in size a _x is defined as Δb _x /b _x . If the size of the inner frame plates 130, 131 is changed to Δb _y when the external force F is applied in the y-axis direction, and the size of the inner frame plate is b _y before the external force is applied, the magnitude change rate a _y is defined as Δb _y / b _y . When the external force F is applied in the z-axis direction, the size of the inner frame plates 130, 131 is changed to Δb _z , and the size of the inner frame plate before the application of the external force is b _z , and the magnitude change rate a _z is defined as Δb _z /b _z .

According to the condition (5), for example, if the precipitation-hardened stainless steel is used as the material for the lips 120, 121, it is preferable that the material for the inner frame plates 130, 131 has a Vickers hardness in the range of 200 Hv to 1000 Hv. Therefore, it is preferable to use stainless steel or ceramic as the material for the inner frame plates 130 and 131. Further, the material for the inner frame plate is preferably magnetic.

Depending on the contact faces 120a, 120b, 121a-121d, 130a, 130b, 131a, 131b of the lip plates 120, 121 and the inner frame plates 130, 131, the trimming accuracy is preferably a surface roughness of at most 1 micrometer and any The linearity of the direction is a maximum of 1 micron. When the trimming accuracy of the contact faces 120a, 120b, 121a-121d, 130a, 130b, 131a, 131b satisfies the above conditions, it prevents streaking and unevenness from being formed on the cast film. The smoothness of the ends of the inner frame plates 130, 131 on the side of the outlet 81b is preferably at most 2 μm. The average of the clearances SW1, SW2 of the slit 126 of the casting die 81 can be automatically adjusted in the range of 0.5 mm to 3.5 mm. Depending on the edge of the contact portion of the casting solution 81, the lip end of the casting die 81 is R (R is a chamfer radius) of a maximum width of 50 μm at all.

Preferably, a hardened layer is preferably formed on the ends of the lips 120, 121 and the inner frame plates 130, 131 on the side of the outlet 81b. The method of forming the hardened layer is not limited. However, it is, for example, a ceramic hard coat layer, hard chrome plating, nitrification treatment or the like. In the case where ceramic is used as the hardened layer, it is preferred that the ceramic used is grindable but not brittle, has low porosity, high corrosion resistance, and does not adhere to the casting die 81. Specifically, it is tungsten carbide (WC), Al ₂ O ₃ , TiN, Cr ₂ O ₃ or the like. The special ceramic is tungsten carbide. The tungsten carbide coating can be produced by a spray method.

The width of the casting die 81 is not particularly limited. However, the width is preferably at least 1.1 times and at most 2.0 times the width of the film. Further preferably, the casting die 81 is provided with a temperature controller 160 so that a predetermined temperature can be maintained during film manufacture. In order to adjust the film thickness, the casting die 81 preferably has an automatic thickness adjusting device. For example, the thickness adjustment bolt (hot bolt) is disposed at a predetermined distance in the direction TD. Because of the thermal bolts, the gaps W1, SW2 of the slits 126 and the widths W1 of the passages 135, 145 can each be adjusted to a predetermined value. Depending on the heat bolt, it is preferred to set the profile based on a predetermined program at the feed rate of the pump (preferably a high precision gear pump) during film manufacture. Further, feedback control of the thermal bolt adjustment value can be performed by an adjustment program based on the shape of a thickness gauge (not shown) such as an infrared thickness gauge. The difference in thickness between any two points in the direction TD (outside the side edge portion) of the cast film is preferably controlled to a maximum of 1 μm. The difference between the maximum and minimum values of the direction TD thickness is a maximum of 3 microns, and in particular a maximum of 2 microns. Further, the accuracy of the specified target value of the thickness is preferably ±1.5 μm. Further, it is preferable to control the shear rate of the coating liquid 51 to a range of 1 (1/sec) to 5000 (1/sec).

(decompression chamber)

In order to stably form the coating liquid granules 80, the decompression chamber 90 (see Fig. 3) supplies air on the upstream side in the rotational direction Z1 such that the pressure on the upstream side is lower by 10 Pa to 2000 Pa than the downstream side. In addition, the decompression chamber 90 has a jacket (not That is, the internal temperature of the decompression chamber 90 can be controlled to a predetermined value. The internal temperature is not particularly limited. However, it is preferably lower in boiling point than the solvent used.

An example of a method of manufacturing the film 57 is explained below with reference to FIG. In the film production line 32, the main coating liquid 48 is made uniform by stirring the agitator 30b. An additive such as a plasticizer or the like may be added to the main coating liquid 48 after stirring. Further, a heat transfer medium is fed into the jacket 30c to maintain the temperature of the primary coating liquid 48 at a predetermined value in the range of about 25 ° C to 35 ° C.

The casting controller 79 drives the gear pumps 73a-73c to feed the main coating liquid 48 into the lines 71a-71c via the filtering means 74a-74c. Filtration of the primary coating liquid 48 is accomplished in the filtration unit 74. The additive containing the matting agent solution, the UV absorber solution, and the like is fed through the additive supply line to the line 71a-71c. Then, the main coating liquid 48 is stirred by the static mixers 75a-75c to become the casting coating liquid 51. When the static mixers 75a-75c are stirred, the temperature of the main coating liquid 48 is preferably maintained at a fixed value in the range of 30 °C to 40 °C. The casting coating liquid is then fed to the casting die 81 in the casting chamber 62 by the gear pumps 73a-73c.

The recovery device 88 maintains the vapor pressure of the solvent vapor in the atmosphere in the casting chamber 62 near a predetermined value. The temperature control device 86 controls the temperature of the atmosphere in the casting chamber to a fixed value in the range of -10 ° C to 57 ° C.

The casting die 81 is covered with a jacket (not shown) in which a heat transfer medium is supplied. The temperature of the heat transfer medium is controlled by the temperature controller 160 to be almost 36 °C. The temperature of the casting die 81 was thus maintained at almost 36 °C.

Further, the casting controller 79 controls the rotation of the casting cylinder 82 with the rotating shaft 82a. Thus, the rotational speed of the rotational direction Z is maintained such that the circumferential moving speed can range from 50 m/min to 200 m/min. In addition, the thermal transfer medium circulator 89 will The temperature T1 of the circumference 82b is maintained in the range of -10 ° C to 10 ° C.

The casting die 81 discharges the casting coating liquid 51 from the die outlet 81a. The casting coating liquid 51 is thus cast on the circumference 82b of the casting cylinder 82 to form a casting film 53. The casting film 53 is then cooled on the circumference 82b so that gelation in the casting film 53 is performed. It should be noted that a detailed explanation regarding the discharge of the casting dope 51 from the die outlet 81a is performed later.

When the casting film 53 has self-supporting properties, it is peeled off from the casting cylinder 82 to become the wet film 55 supported by the peeling roller 83, and is conveyed by the path roller 63. The blower applies dry air to the wet film 55 above the path roller 63 to dry the wet film 55. The wet film 55 is then sent to a pin tenter 64.

The pin tenter 64 borrows at its entrance to hold the two side edge portions. The pin moves to convey the wet film 55 while drying under predetermined conditions. The wet film 55 is then released and shipped as a film 57 to a clip tenter 97. The clip-on tenter 97 grips the two side edge portions of the film 57 by the clip at its entrance. The clip is moved to transport the film 57 while drying and stretching the film 57 under predetermined conditions.

Drying is carried out in the pin tenter 64 and the clip tenter 97 so that the residual solvent content can become a predetermined value, and the film 57 is sent to the edge cutting device 65. The two side edge portions are cut away from the film 57 in the edge cutting device 65. It feeds the side edge portion of the cut to the crusher 95 by a cutter blower (not shown) and is crushed into pieces by a crusher 95.

After cutting, the film 57 is sent to the drying chamber 66 for drying again. The residual solvent content is preferably such that it becomes a maximum of 5% by weight. Regarding the residual solvent content, it is necessary to sample a portion of the film 57 and dry the sample. If sampling The sample weight is x and the sample weight after drying is y, and the solvent content on a dry basis is calculated according to the formula {(x-y)/y}×100. The film 57 is cooled to room temperature in the cooling chamber 67.

It provides a forced neutralization device 104 such that the charged electrostatic potential of the film during transport can range from -3 kV to +3 kV. Further, film rolling is performed on the surface of each side of the film 57 by the embossing roll 105. Then, in the winding chamber 68, the pressing roller 108 applies a tension toward the reel 107 to the film 57 to wind the film 57 around the reel 107. It is preferably that the tension gradually changes from the start to the end of the winding.

In the present invention, the length of the film 57 is preferably at least 100 meters. The width of the film 57 is preferably at least 600 mm, and particularly in the range of 1400 mm to 3000 mm. Further, the present invention is effective even if the width exceeds 3000 mm. The present invention can be preferably applied even in the range of 20 μm to 80 μm in thickness. Further, the present invention is particularly preferably applied if the thickness is in the range of 20 μm to 60 μm, and the present invention is particularly preferably applied if the thickness is in the range of 20 μm to 40 μm.

The casting program 54 is explained in detail below. In Figs. 4 and 5, the drive gear pump 73a feeds the first casting coating liquid 51a via the line 71a, and the first casting coating liquid 51a enters the manifold 125 through the inlet 81a and then flows into the slit 126. The drive gear pump 73b feeds the second casting solution liquid 51b to the passage 135 via the line 71b, and the second casting coating liquid 51b enters the slit 126 through the outlet 135a to bond the first casting coating liquid 51a. The drive gear pump 73c feeds the third casting solution liquid 51c to the passage 145 via the line 71c, and the third casting coating liquid 51c enters the slit 126 through the outlet 145a to be combined The first casting liquid 51a.

The end '140a of the partitioning portion 140 and the end 150a of the partitioning portion 150 are formed to have an acute angle, so that the first and second casting coating liquids 51a, 51b and the first and third casting coating liquids 51a, 51c are each combined and close to each other. The outlets 135a, 145a do not stay. The first-third casting solution liquids 51a-51c are thus discharged from the outlet 81b to form the casting pellets 80. If the ends 140a, 150a do not have a sharp shape, the stay of the first-third casting solution 51a-51c sometimes occurs, which causes streaks at the interface close to the first-third casting solution 51a-51c. . In this case, it is difficult to form the casting pellet 80 stably.

Since the second and third casting liquids 51b, 51c are fed to the slit by the respective gear pumps 73b, 73c, the second and third casting liquids are controlled by the casting controller 79 via the gear pumps 73b, 73c. The flow of 51b, 51c. The flow control of the second and third casting liquids is independently performed with respect to the first casting liquid 5la, so that the thickness of the side portions of the casting grains 80 can be independently controlled with respect to the intermediate portion.

Therefore, in the present invention, the thickness of the intermediate portion (i.e., product portion) and the side portion (non-product portion) of the film 57 can be independently controlled. Further, since the control of the thickness of the side portions is completed by adjusting the flow rates of the second and third casting liquids 51b, 51c, the thickness of the side portions can be appropriately controlled without excessive or insufficient. Therefore, the present invention can effectively produce a film of a predetermined thickness by preventing thickness unevenness and peeling trouble.

The flow rates of the widths of the first to third casting liquids 51a to 51c in the lines 71a to 71c are each adjusted using the gear pumps 73a to 73c. The thickness of the side portion is now defined as Df1 and the thickness of the intermediate portion is defined as Df2. In this case, The value of Df1/Df2 is preferably in the range of 0.75 to 3, and particularly in the range of 1 to 2. This reduces stripping troubles and thickness unevenness.

Since the width W1 of the passages 135, 145 is adjusted to a predetermined range, it stably forms the casting pellets 80. The width W1 is preferably at least 0.1 mm. If the width W1 is less than 0.1 mm, the first-third casting coating liquids 51a to 51c cannot be properly bonded, and thus the casting pellets 80 cannot be stably formed. It should be noted that the width W1 can be large. In this case, the second and third casting liquids 51b, 51c may form not only the side portion of the casting pellet 80 but also the intermediate portion.

Further, the position of the end 140a is adjusted to maintain the clearance CL1 of the outlet 81b within a predetermined range. Therefore, the pressure is maintained to exclude the second and third casting liquids 51b, 51c.

The clearance CL1 is preferably at most 40 mm. The pressure loss at the outlet 81b of the casting die 81 is considered, and the clearance CL1 is particularly preferably at most 20 mm, particularly 5 mm, and more preferably 3 mm. In the case where the clearance CL1 exceeds 40 mm, it may not maintain the flow rate of the second-third casting solution liquids 51b, 51c until it is discharged from the outlet 81b, with the result that it may be difficult to control the thickness of the side portion of the casting pellet 80. Further, when the end 140a protrudes from the casting die 81 (i.e., the distance from the circumference 82b to the end 140a of the casting cylinder 82 is smaller than the outlet 81b) is less preferable. In this case, it is possible to discharge the second and third casting liquids 51b, 51c without combining the first casting liquid 51a, and thus it is difficult to form the casting pellets 80. It should be noted that the lower limit of the clearance CL1 can be determined based on the processing accuracy of the outlet 81a and the end 140a. For example, the lower limit is preferably 0.1 mm or more.

In this particular embodiment, the divider portions 140, 150 have the same thickness D1. However, the invention is not limited thereto, and the partitioning portion 140, 150 machine The thickness can vary by a predetermined range. In addition, the ends 140a, 150a have the same clearance for the outlet 81b. However, the invention is not limited thereto, and the gaps of the ends 140a, 150a may be different.

In the above specific embodiment, the drive casting controller 79 performs the flow rate of the side coating liquid and the adjustment of the feed. However, the present invention is not limited thereto, and the casting controller may have a function of offsetting the partition portion, such as a gap between the end of the partition portion and the exit of the casting die.

In the above specific embodiment, the side portions of the casting pellet 80 form the two side edge portions of the film 57, and the thickness of the side edge portion is adjusted so that the stability of the casting pellet 80 can be increased, and the wet film 55 is self-casting cylinder 82. The stripping force of the circumference 82b. However, the present invention is not limited thereto, and the thickness of the side portion can be adjusted so that the transfer force after peeling can be increased. Further, the film 57 produced by the film production line 32 has predetermined optical properties when the additives of the respective first-third casting coating liquids 51a to 51c can be appropriately selected. For example, an additive for increasing the optical properties of the film is added to the first casting solution 51a, and additives for increasing the peeling force and the post-peeling transfer property are added to the second and third casting coating liquids 51b, 51c. Thus, it is possible to manufacture a film excellent in optical properties with high productivity.

If the second and third casting coating liquids 51b, 51c are suitable for recycling with the additive, it is possible to easily reuse the chips obtained by crushing the film fragments using the edge cutting device 65 and the crusher 95. The additive suitable for recycling is not particularly limited as long as it is easily recycled by a known recycling method. Specifically, the additive can be easily removed from the dissolved liquid 28 using, for example, the filtering devices 20, 22.

In the above specific embodiment, the outlets 135a of the channels 135, 145, Each of 145a is formed on the contact faces 130b, 131b. However, the outlets 135a, 145a may be formed on the contact faces 130a, 131a.

Further, the contact faces 130b, 131b are formed such that the coating liquid passage 81c can be continuously widened on the outlet 81b side. However, the invention is not limited thereto and may be almost fixed.

In this particular embodiment, channel 136 is formed in inner frame plate 130. However, the invention is not limited thereto. The passage 135 can be formed using a member having the partition portion 140 and a member having the contact surface 130b.

The cast pellets 80 are sometimes partially cured. In this case, the cured foreign material is sometimes contained in the film, which causes defects such as a decrease in optical properties. In addition, the casting is poor when the foreign material is attached to the outlet 81b. If the casting is carried out under such conditions, the film produced has streaks on its surface, i.e., surface defects. Therefore, in order to prevent partial solidification of the casting pellets 80, it is preferred to supply a solution (not shown) on both sides of the outlet 81b. In this case, it uses a liquid which can dissolve the solid material in the first-third casting solution 51a-51c. The liquid is, for example, a mixed solvent of 86.5 parts by weight of methylene chloride, 13 parts by weight of a lip, and 0.5 part by weight of n-butanol, and is preferably supplied to the side edge of the casting pellet 80 and the gas between the slits - Liquid interface. Further, the solution is preferably a good solvent component and a poor solvent component of the cast coating liquid polymer.

It should be noted that the pulsation rate of the pump for supplying the liquid is preferably at most 5%. The solution can be used as the second and third casting liquids 51b, 51c. This prevents defects caused by splashing of the solution and prevents defects and surface unevenness caused by foreign materials.

In addition, the poor solvent in the second and third casting liquids 51b, 51c will be formed. The weight percentage of the fraction is defined as HCe, which will be defined as HCc in the first cast coating liquid 51a. The HCe/HCc value is preferably in the range of 1.05 to 3. The two side edges of the cast film thus can be easily gelled, and thus the peeling force is increased. It should be noted that the HCc value is the weight percentage of the solvent in the first casting solution 51a of the poor solvent component, and the HCe value is the weight percentage of the solvent in the second and third casting coatings 51b, 51c of the poor solvent component. It should be noted that the present invention is also applicable when the HCc is 0% by weight.

The judgment that the solvent component is a good solvent component or a poor solvent component can be carried out as follows. The ingredients and the polymer are mixed such that the weight percentage of the polymer to the total weight may be 5% by weight. In this case, if a part of the polymer is insoluble in the solvent and remains in the mixture, the solvent component is a poor solvent component. If the polymer is completely dissolved, the ingredients are good solvent components.

Each of the first to third casting coating liquids 51a to 51c contains a polymer and a solvent, and further contains an additive if necessary. The first to third cast coating liquids 51a to 51c may be the same or different. In the case where the first to third casting liquids 51a to 51c are the same, they independently control the flow rates of the first to third casting liquids 51a to 51c. However, the invention is not limited thereto. For example, the flow rates of the first to third casting liquids 51a to 51c are controlled in accordance with the respective contents of the first to third casting liquids 51a to 51c. Therefore, the polymer contained in the first casting solution 51a may be the same as or different from the second and third casting coatings 51b, 51c. Further, the polymer contained in the second casting solution 51b may be the same as or different from the third casting solution 51c. The solvent and additives contained in the first to third casting liquids 51a to 51c may be the same or different.

The solvent contains a good solvent component as a solvent component of the soluble polymer. A good solvent component can be a mixture of a variety of materials that are determined to be good solvent components. Things. Further, the solvent may contain a good solvent component and a poor solvent component. The poor solvent component can be a mixture of a plurality of materials which are determined to be poor solvent components. It should be noted that a detailed explanation of the good solvent component and the poor solvent component is performed later.

The elongational viscosity of the second casting solution 51b is preferably higher than that of the first casting solution 51a. In this case, the side portions of the casting pellets 80 become stable, and as a result, the vibration of the casting pellets 80 caused by the disorder of the atmosphere (such as the air flowing into the decompressing chamber 165) and the vibration of the propellers are prevented. The elongational viscosity of the first casting solution 51a is referred to as ηc, and the elongational viscosity of the second casting solution 51b is referred to as ηe. The value of ηe/ηc is preferably more than 1 and a maximum of 3.

In order to make the elongational viscosity of the second casting solution 51b higher than the elongational viscosity of the first casting solution 51a, the solvent content of the poor solvent component in the second casting solution 51b is preferably higher than that of the poor solvent component to the first flow. The content of the solvent in the extended coating liquid 51a. Further, it is preferable that the content of the polymer in the second casting solution 51b is lower than the content of the polymer in the first casting solution 51a. In this case, it reduces damage caused by bottlenecks. It is compensated for when the polymer content is reduced and the elongation viscosity is lowered. This can increase the elongational viscosity of the second casting solution 51b. Therefore, it is designed to minimize the damage caused by the bottleneck and stabilize the casting pellets 80.

The conditions of the second casting solution 51b (the elongation viscosity, the content of the polymer, and the content of the poor solvent component, etc.) can be directly applied to the third casting solution 51c. It should be noted that the elongational viscosity, the content of the polymer, and the content of the poor solvent component between the second and third casting liquids 51b, 51c may be the same or different.

Each of the first - third casting solution coating extending 51a-51c of the viscosity μ ₀ zero shear viscosity of 3 times as large, and the zero shear viscosity μ ₀ line by the standard method JIS K 7199 obtained by measurement.

(good solvent)

If the polymer is deuterated cellulose, the preferred solvent component to be used is preferably an aromatic hydrocarbon (e.g., benzene, toluene, etc.), a halogenated hydrocarbon (e.g., dichloromethane, chlorobenzene, etc.), an ester (e.g., methyl acetate, acetic acid). Ethyl ester, propyl acetate, etc., and ethers (for example, tetrahydrofuran, methyl siatone, etc.).

(poor solvent)

If the polymer is deuterated cellulose, the poor solvent component to be used is preferably an alcohol (e.g., methanol, ethanol, n-propanol, n-butanol, diethylene glycol, etc.), and a ketone (e.g., acetone, methyl ethyl ketone, etc.).

It should be noted that even if the polymer is not deuterated cellulose, the solvent of the coating liquid remains the same. The poor solvent component and the good solvent component are the solvent components determined by the above method.

In this particular embodiment, the divider portions 140, 150 have acutely angled ends 140a, 150a, and the tops of the ends 140a, 150a are located in the center of the respective divider portions 140, 150 in the direction TD. However, the invention is not limited thereto. A detailed explanation thereof will be made below with reference to Figs. 6-8 of the second to fourth embodiments. It should be noted that the same numbers are applied to the same members and parts, and the explanation thereof is omitted.

In Fig. 6, the casting die 281 is composed of the lips 120, 121 and the side plates 122, 123, and has an inlet 81a through which the first casting coating liquid 51a is fed from the line 71a to the casting die 281, And self-casting die 281 emissions The first to third casting liquids 51a to 51c become the outlet 81b of the casting pellets 80. The casting die 281 has inner frame plates 230, 231 disposed on both sides of the coating liquid passage 81c in the direction TD. The inner frame plate 230 has contact faces 230a, 230b for contacting the first-third casting solution liquids 51a-51c. The inner frame plate 231 has contact faces 231a, 231b for contacting the first to third casting liquids 51a to 51c. The contact faces 230b, 231b tend to contact the faces 230a, 231a such that the coating liquid passage 81c can be widened from the inlet 81a to the outlet 81b.

A channel 235 and a channel 136 are formed in each of the inner frame plate 230 and the side plate 122. Channel 136 connects line 71b to channel 235. Channel 235 has a width W1 and a channel 136 is connected to slit 126. The outlet 235a of the passage 235 is formed on the contact surface 230b. The inner frame plate 230 has a partition portion 240 for partitioning the passage 235 and the coating liquid passage 81c. The partition portion 240 has an end 240a having an acute angle. The passage 235 gradually widens toward the outlet 235a on the outlet 81b side. Further end 240a has a clearance CL1 for outlet 81b.

In Fig. 7, the casting die 381 is composed of the lips 120, 121 and the side plates 122, 123, and has an inlet through which the first casting coating liquid 51a is fed from the line 71a to the casting die 381, and The first-third cast coating liquids 51a to 51c are discharged from the casting die 381 to become the outlet 81b of the casting pellets 80. The casting die 381 has inner frame plates 330 and 331 which are disposed on both sides of the coating liquid passage 81c in the direction TD. The inner frame plate 330 has contact faces 330a, 330b for contacting the first-third casting solution liquids 51a-51c. The inner frame plate 331 has contact faces 331a, 331b for contacting the first to third casting liquids 51a to 51c. The contact faces 330a, 331a are formed such that the width of the coating liquid passage 81c can be almost constant. The contact faces 330b, 331b tend to contact the faces 330a, 330b, so that the coating liquid passage 81c can be widened at the lower side of the figure.

A channel 335 and a channel 136 are formed in each of the inner frame plate 330 and the side plate 122. Channel 136 connects line 71b to channel 335. Channel 335 has a width W1 and a channel 136 is connected to slit 126. The outlet 335a of the passage 335 is formed on the contact surface 330b. The inner frame plate 330 has a partition portion 340 for partitioning the passage 335 from the coating liquid passage 81c. The partition portion 340 has an end 340a having an acute angle. The passage 335 is gradually widened on the side of the outlet 81b. Further end 340a has a clearance CL1 for outlet 81b. The thickness of the partition portions 240, 250 in the direction TD is preferably at most 2 mm.

In Fig. 8, the casting die 481 is composed of the lips 120, 121 and the side plates 122, 123, and has an inlet through which the first casting coating liquid 51a is fed from the line 71a to the casting die 481, and The first to third casting liquids 51a to 51c are discharged from the casting die 481 to become the outlet 81b of the casting pellets 80. The casting die 481 has inner frame plates 430 and 431 which are disposed on both sides of the coating liquid passage 81c in the direction TD.

The inner frame plate 430 has a partition portion 440 for partitioning the passage 135 from the coating liquid passage 81c. The partition portion 440 has an end 440a having an acute angle. The end 440a has a clearance CL1 to the outlet 81b. The contact surface 444 is formed by the end 440a of the partition portion 440 toward the upstream side of the passage 135, and the contact surface 445 is formed by the end 440a of the partition portion 440 toward the upstream side of the coating liquid passage 81c. The inner frame plate 431 has a partition portion 450 for partitioning the passage 145 from the coating liquid passage 81c. The partition portion 450 has an end 450a having an acute angle. The end 450a has a clearance CL1 to the outlet 81b. The contact surface 454 is formed by the end 450a of the partition portion 450 toward the upstream side of the channel 145, and the contact surface 455 is The end 450a of the partition portion 450 is formed toward the upstream side of the coating liquid passage 81c.

The contact faces 444, 445, 454, 455 are preferably coated with a polymer or the like. The polymer is, for example, Teflon (registered trademark) or the like. The thickness of the coating formed on the contact faces 444, 445, 454, 455 is suitably determined in accordance with the conditions of the process. Further, the thickness fluctuation of the casting pellet 80 in the direction TD is related to the fluctuation of the flow velocity in the direction TD after the first-third casting coating liquids 51a-51c are combined. If the flow rates of the first-third casting coating liquids 51a-51c after bonding are low, the casting grains 80 are thin. If the flow rate is high, the casting pellets 80 are thick. If the coating of the contact faces 444, 445, 454, 455 of the inner frame plates 430, 431 is made of a polymer, the flow rate non-uniformity of the first-third casting coating liquids 51a-51c in the direction TD after bonding is lowered. . Therefore, the thickness fluctuation of the casting grains in the direction TD is lowered to cause the casting die 481 to cast the first to third casting liquids 51a to 51c. As a result, the film produced has no or minimal thickness unevenness in the direction TD.

The solution casting method of the present invention has a casting method for casting a multiple coating liquid, such as a co-casting method and a sequential casting method. The feed zone can be attached to the casting die in a co-casting process, such a specific embodiment, or a multi-manifold casting die (not shown) can be used. In the production of a film having a multilayer structure, it casts a multicoat liquid onto a support to form a cast film having a first layer (uppermost layer) and a second layer (lower layer). Then, in the film to be produced, at least one of the thickness of the first layer and the thickness of the opposite lowermost layer is preferably in the range of 0.5% to 30% of the total film thickness. In addition, it is designed to carry out a co-current delay, and the coating liquid with a higher viscosity is sandwiched by a coating liquid having a lower viscosity. Specifically, it is preferred that the coating liquid for forming the surface layer has a lower viscosity than the coating liquid for forming the layer sandwiched by the surface layer. In addition, a co-current delay is designed, which is preferably in the die seam (or In the coating liquid between the lip and the support, the composition of the alcohol is higher in the outer coating than in the inner coating.

Japanese Patent Publication No. 2005-104148 details the structure of a casting die, a decompression chamber, a support, and the like in [0617] to [0889], and further relates to co-casting, stripping, stretching, and drying of each program. Conditions, treatment methods, crimping, winding method after correcting planarity, solvent recovery method, and film recovery method. The description is applicable to the present invention.

[Properties and measurement methods] (curl degree and thickness)

Japanese Patent Publication No. 2005-104148 describes the properties of the wound cellulose film and its measuring method in [0112] to [0139]. This property and measurement method can be applied to the present invention.

[surface treatment]

The deuterated cellulose film is preferably used in several ways after being surface treated on at least one surface. The preferred surface treatments are vacuum glow discharge, plasma discharge at atmospheric pressure, UV light irradiation, corona discharge, flame treatment, acid treatment, and alkali treatment. It is further preferred to utilize one of these surface treatments.

[functional layer] (antistatic, hardening, anti-reflective, easy to adhere and anti-glare layer)

The deuterated cellulose film can have an undercoat layer on at least one surface and can be used in several ways.

It is preferred to use a deuterated cellulose film as a base film to which at least one of the functional layers can be provided. Preferred functional layers are an antistatic layer, a cured resin layer, an antireflection layer, an easy adhesion layer, an antiglare layer, and an optical compensation layer.

The conditions and methods for forming the functional layer are described in detail in [0890] to [1087] of Japanese Patent Publication No. 2005-104148, which is applicable to the present invention. The film thus produced can have several functions and properties

These functional layers are preferably at least one surfactant in the range of from 0.1 mg/m2 to 1000 mg/m2. Further, the functional layer is preferably at least one plastic agent in the range of from 0.1 mg/m2 to 1000 mg/m2. The functional layer is preferably at least one matting agent in the range of from 0.1 mg/m2 to 1000 mg/m2. The functional layer is preferably at least one antistatic agent in the range of from 1 mg/m2 to 1000 mg/m2.

(various uses)

The produced cellulose halide film can be effectively used as a protective film for a polarizing filter. In the polarizing filter, it adheres the deuterated cellulose film to the polarizer. It usually adheres two polarizing filters to the liquid crystal layer to make a liquid crystal display. It should be noted that the arrangement of the liquid crystal layer and the polarizing filter is not limited thereto, and several known arrangements are possible. Japanese Patent Publication No. 2005-104148 discloses TN type, STN type, VA type, OCB type, reflective type, and other types of liquid crystal displays. This description is applicable to the present invention. Further, this publication No. 2005-104148 describes a cellulose oxide film having an optically anisotropic layer and having antireflection and antiglare functions. Further, since it is a biaxially deuterated cellulose film having appropriate optical properties, the film produced can be used as an optical compensation film. Further, this optical compensation film can be used as a protective film for a polarizing filter. The detailed description is [1088] to [1265] of Announcement No. 2005-104148.

In the method of forming a polymer film of the present invention, the formed bismuth fiber The optical film has excellent optical properties. The TAC film can be used as a protective film for a polarizing filter, a base film of a photosensitive material, or the like. Further, in order to improve the viewing angle dependence of a liquid crystal display (for a television or the like), the produced film can also be used for an optical compensation film. In particular, the film produced is effectively used when it is also used as a protective film for a polarizing filter. Therefore, the film is used not only for the TN mode such as the look-ahead mode, but also for the IPS mode, the OCB mode, the VA mode, and the like. Furthermore, it is possible to form the polarizing filter as a protective element as a structural element.

Furthermore, the invention is not limited to the manufacture of optical films, but is also suitable for the manufacture of any film by solution casting method. For example, the present invention is suitable for producing a solid electrolyte membrane as a proton conductive material for a fuel cell. It should be noted that the polymer used in the present invention is not limited to deuterated cellulose, but may be any known polymer.

[experiment]

The experiment of the present invention has been completed, which is explained below. Five film manufacturing examples were carried out in the experiment. Examples 1-12 are examples of the invention, and Comparative Examples 1-12 are a comparison of Examples 1-12. Example 1 is explained in detail, and the same explanation is omitted in the explanation of Examples 2-12 and Comparative Examples 1-12.

[Example 1]

Example 1 will now be explained. The composition used to prepare the coating liquid for film production is as follows: <solid compound>

<solvent A>

As described above, the solvent for coating liquid contains the first and second solvent components. The solid component is appropriately added to the solvent to obtain a coating liquid 11. It should be noted that the obtained coating liquid 11 had a solid content of 19.3% by weight. Then, the coating liquid 11 was filtered using a filter (#63LB, manufactured by Toyo Roshi Kaisha, Ltd.), and further filtered using a sintered metal filter (06N, porous diameter: 10 μm, manufactured by Nippon Seisen, Co., Ltd.). Further, the coating liquid 11 is filtered using a sieve filter and then stored in the raw material tank 30.

<cellulose triacetate> Depending on the cellulose triacetate used in this experiment, the residual acetic acid content is 0.1% by weight, the Ca content is 58 ppm, the Mg content is 42 ppm, the Fe content is 0.5 ppm, the free acetic acid is 40 ppm, and the sulfate ion content. It is 15 ppm. The degree of acetylation at the 6th position was 0.91, and the percentage of the acetamidine group at the 6th position to the entire acetamidine group was 32.5%. The acetone extract was 8% by weight, and the ratio of the weight average molecular weight to the number average molecular weight was 2.5. In addition, the yellowing index is 1.7, the haze value is 0.08, and the transparency is 93.5%. This cellulose triacetate is synthesized from cellulose as a material derived from cotton, and is referred to as cotton TAC in the following explanation.

Film 57 is made using film line 32. Each gear pump 73a-73c increases the primary side pressure and uses a variable flow motor to feedback control the primary coating liquid 48 Feed to the upstream side of the pump so that the primary side pressure can be a predetermined value. The main coating liquid 48 is thus fed into the lines 71a-73a. As for the efficiency of the gear pumps 73a-73c, the volumetric efficiency is at most 99.2%, and the fluctuation percentage of the discharge volume is at most 0.5%. In addition, the discharge pressure is 1.5 Mpa. The casting controller 79 drives and controls the gear pumps 73a-73c to feed the primary coating liquid 48 to the static mixers 75a-75c. Filtration of the primary coating liquid 48 is performed in the filtering devices 74a-74c.

The mixed additive is fed into the lines 71a-71c in an additive supply line. The mixture of the additive additive and the primary coating liquid 48 is then agitated by static mixers 75a-75c.

The casting die 81 includes lips 120, 121, side plates 122, 123, and inner frame plates 130, 131, and these members of the casting die 81 are formed of stainless steel having a volume change percentage of 0.002%. As for the trimming accuracy of the contact faces 120a, 120b, 121a-121d, 130a, 130b, 131a, 131b of the lips 120, 121 and the inner frame plates 130, 131, the surface roughness is at most 1 micrometer and linearity in any direction It is up to 1 micron/m. During the casting, it controls the flow rates of the respective first to third casting liquids 51a to 51c and adjusts the slit widths SW1, SW2 so that the thickness of the dried film 57 can be 80 μm. At the inlet of the casing (not shown) of the casting die 81, the temperature of the heat transfer medium was controlled to 36 ° C so that the temperature of the first to third casting liquids 51a to 51c can be controlled to 36 °C. The width W1 of the passages 135, 145 is 5 mm, and the clearance CL1 between the end 140a and the outlet 81b and between the end 140a and the outlet 81b is 2 mm. Further, each of the thicknesses D1 of the partition portions 140, 150 is 2 mm.

In this experiment, the size and size of the lips 120, 121 and the inner frame plates 130, 131 were measured using a microscope having a resolution of 1 micron.

The temperature of the casting die 81 and the lines 71a-71c was controlled to 36 °C during the film production. The casting die 81 is of a coating type in which a heat bolt for adjusting the thickness of the film is disposed at a pitch of 20 mm. Thus, the thickness of the film (or the thickness of the discharged casting solution) is automatically controlled by the heat bolt. The heat bolt shape can be set based on the flow rate of the gear pump 73a-73c corresponding to the preset program. The feedback control can be accomplished by the control program based on the shape of the infrared thickness meter (not shown) disposed in the film production line 32. It is controlled so that the film thickness difference between two points (each separated by 50 mm) can be up to 1 μm, and the film thickness in the width direction is the maximum except for the two side edge portions (20 mm in the width direction of the film to be produced) The difference from the minimum can be up to 3 microns/meter. In addition, the average film thickness can be controlled to ±1.5%.

The main side (i.e., the upstream side) of the casting die 81 has a decompression chamber 165. The decompression rate of the decompression chamber 165 is controlled in accordance with the casting speed so that a pressure difference in the range of 1 Pa to 5000 Pa occurs between the upstream and downstream sides of the coating liquid particles of the discharged casting liquid above the casting cylinder 82. At this time, the pressure difference between the two sides of the coating liquid is determined, so that the length of the coating liquid can be 20 mm to 50 mm. In addition, a jacket (not shown) is attached to allow the internal temperature of the decompression chamber to be fixed, and a temperature transfer medium for controlling the temperature of the jacket to 35 ° C is supplied to the inside of the jacket. In addition, there is a labyrinth seal (not shown) on the upstream and downstream sides of the coating liquid.

The materials of the lips 120, 121, the side plates 122, 123, and the inner frame plates 130, 131 are stainless steel, and the coefficient of thermal expansion is at most 2 × 10 ^-5 (°C ^-1 ). In the forced corrosion test of the electrolyte solution, the corrosion resistance was almost the same as that of SUS316. In addition, the material used for the casting die 81 has sufficient corrosion resistance so that no pitting (or etchback) occurs at the gas-liquid interface, even if the material is immersed in a mixed liquid of dichloromethane, methanol and water. Three months in the middle. The dressing accuracy of each of the casting molds 81 on the contact surface of the casting solution 51 is a surface roughness of at most 1 μm, the linearity in any direction is at most 1 μm/m, and the slit clearance is adjusted to a line of 1.5 mm. Sex. Depending on the edge of the contact portion of the lip end of the casting die 81, R is at most 50 microns in width. Further, the shear rate in the casting die 81 is controlled in the range of 1 to 5000 times per second. Further, WC coating is performed on the lip end of the casting die 81 by a melt extrusion method to provide a hardened layer.

The casting cylinder 82 is a stainless steel cylinder having a width of 3.0 meters. The surface of the casting can 82 is polished such that the surface roughness can be a maximum of 0.05 microns. The material is SUS316, which has sufficient corrosion resistance and strength. The thickness unevenness of all the casting cylinders 82 is at most 0.5% of the predetermined value. The shaft 82a is driven under the control of the casting controller 79 to rotate the casting cylinder 82. The casting speed, that is, the moving speed of the circumference 82b in the rotational direction Z1, is in the range of 50 m/min to 200 m/min. Further, control is performed such that the speed variation of the casting drum 82 is at most 0.5% of the predetermined value. It detects the position of the side end and controls the position of the belt in the width direction so that the casting drum 82 is reduced to 1.5 mm after one round of travel. Further, below the casting die 81, the positional change in the vertical direction between the lip end of the casting die 81 and the casting cylinder 82 is 200 μm. The casting cylinder 82 is disposed in a casting chamber 62 including an air pressure control device (not shown).

This experiment supplies the heat transfer medium to the casting can 82 so that the temperature T1 of the circumference 82b can be controlled. It supplies the heat transfer medium (water) to the casting cylinder 82 at a temperature ranging from -10 °C to 10 °C. The surface temperature of the middle portion of the casting cylinder 82 just before the casting is 0 ° C, and the temperature difference between the two sides of the casting cylinder 82 is Up to 6 ° C. It should be noted that the number of pinholes (at least 30 microns in diameter) is zero, the number of pinholes (at least 10 microns in diameter and less than 30 microns) is at most one per square meter, and the number of pinholes (less than 10 microns in diameter) Up to 2 per square meter.

It should be noted that the oxygen concentration in the dry atmosphere on the casting can 82 was maintained at 5 vol% by replacing the air with nitrogen. In order to maintain the oxygen concentration at 5% by volume, it replaces the dry air of the atmosphere with nitrogen. The solvent vapor in the casting chamber 62 is recovered by setting the outlet temperature of the condenser 87 to -3 °C. The static fluctuations near the casting die 81 are reduced to a maximum of ±1 Pa.

The first to third casting liquids 51a to 51c are flown from the casting die 81 on the casting cylinder 82, and a coating liquid 80 is formed between the die outlet 81a and the circumference 82b. Further, a solution of dichloromethane (50% by weight) and methanol (50% by weight) was supplied to the side edges of the coating liquid granules at a fixed flow rate. The decompression chamber 165 thus decompresses the back side of the casting pellet 80, and the discharged coating liquid forms a casting film 53 on the casting cylinder 82. The casting film 53 is then cooled. When the casting film 53 has a self-supporting property, the casting film 53 is peeled from the casting cylinder 82 into a wet film 55 supported by the peeling roller 83. In order to reduce the peeling trouble, it controls the peeling speed (the pulling of the peeling roller 83) to the percentage of the speed of the casting drum 82 to be 100.1% to 110%. The solvent vapor generated in the evaporation is condensed into a liquid state at -3 ° C by means of a condenser 87, and is recovered by a recovery unit 88. The water content of the recovered solvent was adjusted to a maximum of 0.5%. Further, the air from which the solvent component is removed is again heated and reused as dry air. The wet film 55 is carried by the path roller 63 to the pin tenter 64. 60 ° C of dry air from the blower was fed to the wet film 55 above the path roller 63.

In the pin tenter 64, it borrows to hold the two side edge portions of the wet film 55, and transports the wet film 55 sequentially through the temperature zone. The wet film 55 is subjected to predetermined drying during transportation of the pin tenter 64 so that the residual solvent content is at most 5% by weight. The wet film 55 is then fed from the pin tenter 64 to the edge cutting device 65 to form the film 57.

The solvent vapor evaporated in the pin tenter 64 is condensed and liquefied at -3 ° C by a condenser (not shown) to recover the solvent. The water content of the recovered solvent was then adjusted to a maximum of 0.5% by weight.

Within 30 seconds of leaving the pin tenter 64, it cuts off the two side edge portions in the edge cutting device 65. In this experiment, 50 mm of each side portion of the film 57 in the width direction was measured as a side edge portion, which was cut by an NT cutter of the edge cutting device 65. The cut side portion is sent to the crusher 95 by applying a blower from a blower (not shown) and crushed into pieces of about 80 square millimeters. The chips were reused as a raw material for the TAC frame for coating liquid production. Before drying in a drying chamber 66 at a high temperature, it is preheated in a preheating chamber (not shown) that supplies a 100 ° C blow.

The film 57 is dried at a high temperature in the drying chamber 66, and is divided into four regions. A blower having a temperature of 120 ° C, 130 ° C, 130 ° C, and 130 ° C was fed into the area from the upstream side by a blower (not shown). The transport tension of each of the rolls 100 to the film 57 was 100 N/m. The drying was carried out for 5 minutes so that the residual solvent content may be 0.3% by weight. The overlapping angle of the rolls 4 is 80° and 190°. The roller 100 is made of aluminum or carbon steel. It is hard chrome coated on the surface. The surface of the roll 100 is a flat corrugation or sandblasted by, for example, matting. During the rotation of the roll, the fluctuation of the film 57 is within 50 microns. The rotation of the roller is 50 micro Mine. In addition, the roll 100 was lowered to a maximum of 0.5 mm at a tension of 100 N/m.

The solvent vapor contained in the dry air is removed using an adsorption device 101 in which an adsorbent is used. The adsorbent is activated carbon and the desorption is carried out using dry nitrogen. The recovered solvent can be used as a solvent for preparing a coating liquid after the water content is at most 0.3% by weight. Dry air contains not only solvent vapor, but also plasticizers, UV absorbers, and high-boiling materials. Therefore, it is removed using a cooling removal cooler and a front adsorber. So use dry air again. The adsorption and desorption conditions are set such that the content of VOC (volatile organic compound) in the exhaust gas is at most 10 ppm. Further, in all of the vapor solvents, the solvent content recovered by the condensation method was 90% by weight, and most of the remaining solvent vapor was recovered by adsorption.

The dried film 57 is transported to a first moisture control chamber (not shown). It has a dry air fed at 110 ° C in the interval between the drying chamber 66 and the first moisture control chamber. Air having a temperature of 50 ° C and a dew point of 20 ° C was fed into the first moisture control chamber. Further, the film 57 is transported to a second moisture control chamber (not shown) in which the curl of the film 57 is lowered. It applies air at a temperature of 90 ° C and a humidity of 70% to the film 57 in the second moisture control chamber.

After the moisture adjustment, the film 57 was cooled to 30 ° C in the cooling chamber 67, and then edge cutting was performed. A forced neutralization device (or neutralization rod) 104 is provided such that the charged electrostatic potential of the film during transport can range from -3 kV to +3 kV. Further, film rolling is performed on each side surface of the film 57 by the embossing roll 105. The knurl width is 10 mm and the knurling pressure is set such that the maximum thickness averages up to 12 microns greater than the average thickness.

The film 57 was transported to the winding chamber 68, and its internal temperature and humidity were maintained at 28 ° C and 70%, respectively. In addition, a forced neutralization device (not shown) is provided so that the charged electrostatic potential of the film can range from -1.5 kV to +1.5 kV. The film 57 is wound by the pressing roller 108 to wind the film 57 in the casting chamber.

[Example 2]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the film 57 can be 70 μm. Other conditions are the same as in Example 1.

[Example 3]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the film 57 can be 60 μm. Other conditions are the same as in Example 1.

[Example 4]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the film 57 can be 55 μm. Other conditions are the same as in Example 1.

[Example 5]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the film 57 can be 50 μm. Other conditions are the same as in Example 1.

[Example 6]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the film 57 can be 40 μm. Other conditions are the same as in Example 1.

[Comparative Example 1-6]

The inner frame plates 130, 131 are replaced with the leading inner frame plates without the passages 135, 145. The other conditions of Comparative Examples 1-6 were the same as those of Examples 1-6.

[Film judgment]

In the example of the above experiment, the film judgment was made regarding the thickness unevenness due to the trapping of the trapped air and the instability of the cast grain. The judgment was completed in the following manner, which was the same for Examples 1-6 and Comparative Examples 1-6. The results of the film judgment are shown in Table 1.

1. Regarding the peeling trouble (PD): When the cast film 53 is peeled off from the circumference 82b, whether or not the portion of the cast film 53 is observed by the naked eye remains on the circumference 82b. The judgment is as follows: A. The portion of the casting film 53 does not remain; E. The residual portion of the casting film 53.

2. Regarding thickness unevenness (TU): The film thickness of the obtained film was measured at 25 ° C and 60 RH% using an electronic micrometer (manufactured by Anritsu Corporation) at 5 points on the film. Then, the relative standard deviation is calculated from the average value and the standard deviation of the measured values as follows: RSD (%) = (standard deviation / average value) × 100 Based on the RSD value, the thickness unevenness is judged as follows: A. The thickness unevenness is smaller than 10%, and the thickness uniformity is excellent; E. The thickness unevenness is 10% or more, and the thickness unevenness is too large.

3. Regarding Manufacturing Applicability (PA): Measuring the time taken to adjust the thickness of the side portion of the casting pellet 80 T1. The manufacturing suitability is expressed as a percentage of the advance time of the prior art used to adjust the side thickness at time T1. The judgment is made as follows.

A. Time T1 is less than 20% of the lead time; B. Time T1 is at least 20% of the lead time and less than 100%; E. Time is at least 100% of the lead time.

[Example 7]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the central portion of the film 57 can be 80 μm, and the thickness Df2 of the two side edge portions can be It is in the range of 80 microns to 160 microns. Other conditions are the same as in Example 1.

[Example 8]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the central portion of the film 57 can be 70 μm, and the thickness Df2 of the two side edge portions can be It is in the range of 70 microns to 140 microns. Other conditions are the same as in Example 1.

[Example 9]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the central portion of the film 57 can be 60 μm, and the thickness Df2 of the two side edge portions can be It is in the range of 60 microns to 120 microns. Other conditions are the same as in Example 1.

[Example 10]

The flow conditions of the first-third casting solution liquids 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the central portion of the film 57 can be 55 μm, and the thickness Df2 of the two side edge portions can be It is in the range of 55 microns to 110 microns. Other conditions are the same as in Example 1.

[Example 11]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the central portion of the film 57 can be 50 μm, and the thickness Df2 of the two side edge portions can be It is in the range of 50 microns to 100 microns. Other conditions are the same as in Example 1.

[Example 12]

The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the central portion of the film 57 can be 40 μm, and the thickness Df2 of the two side edge portions can be It is in the range of 40 microns to 80 microns. Other conditions are the same as in Example 1.

[Comparative Example 7-12]

The inner frame plates 130, 131 are replaced with the leading inner frame plates without the passages 135, 145. The other conditions of Comparative Examples 7-12 were the same as in Examples 7-12.

Examples 7-12 did not suffer from stripping troubles and thickness non-uniformities. However in comparison In Comparative Example 7-12, it was impossible to control the thickness of the side portion to a predetermined value, and peeling trouble or thickness unevenness occurred.

As is clear from Table 1, in Examples 1-6 and Comparative Examples 1-6, since the casting die of the present invention was used, it was found to reduce the thickness unevenness and the occurrence of the peeling trouble. Particularly when it is designed to produce a film having a thickness Df1 of less than 60 μm, the effect of the present invention is very large. Further, since the flow rate of the casting liquid for forming the side portion and the flow rate of the casting liquid for forming the intermediate portion are independently controlled, it takes a shorter time T1 than the prior art to adjust the thickness of the side portion. Further, in Examples 7 to 12 and Comparative Examples 7 to 12, the thickness of the side portion was at least the same as the thickness of the intermediate portion to be at most 2 times larger, and no thickness unevenness and peeling trouble occurred. Such adjustment of the side thickness becomes easy.

[Example 13]

The explanation of Example 13 is now carried out. The compound of Example 1 was added to a mixed solvent of the following composition to obtain a main coating liquid of the second component: <Solvent B>

The main coating liquid 48 is replaced with the main coating liquid of the second component to obtain second and third casting coating liquids 51b, 51c. The flow conditions of the first-third casting solution 51a-51c fed by the gear pumps 73a-73c are changed so that the thickness Df1 of the film 57 can be 80 μm, and the thickness Df2 of the two side edge portions can be 80 μm. . Other conditions are the same as in Example 1.

[Examples 14-18]

The flow conditions of the first-third casting solution liquids 51a-51c fed by the gear pumps 73a-73c are changed so that the thicknesses Df1 and Df2 may be predetermined values. Other conditions are the same as in Example 13. The values of the thicknesses Df1 and Df2 are shown in Table 2.

[Comparative Examples 13-18]

The inner frame plates 130, 131 are replaced with the leading inner frame plates without the passages 135, 145. The main coating liquid 48 is used to prepare the second and third casting coating liquids 51b, 51c instead of using the main coating liquid of the second component. The other conditions of Comparative Examples 13-18 were the same as in Examples 13-18. The values of the thicknesses Df1 and Df2 are shown in Table 2.

Table 2-18 and Table 2 of Comparative Examples 13-18 show the HCe/HCc value, the thickness Df1 of the intermediate portion, and the thickness Df2 of the side portion of the film. The HCe/HCc value is described as the content of the solvent in the second and third casting coating liquids 51b and 51c, and the content of the poor solvent component in the first casting coating liquid 51a is described as HCc. The content ratio. It also shows the judgment of stripping trouble (PD), thickness non-uniformity (TU), and manufacturing suitability (PA).

[Example 19-24]

The solid compound of Example 1 was added to the mixed solvent C (mixed solvent C was different from the mixed solvents A and B) to obtain a main coating liquid 48 of the third component. The main coating liquid 48 of the third component is used to prepare the first casting coating liquid 51a.

Then, the solid compound of Example 1 was added to the mixed solvent D (mixed solvent D was different from the mixed solvents A, B and C) to obtain a main coating liquid of the fourth component. The main coating liquid 48 of the fourth component is used to prepare the second casting coating liquids 51b, 51c.

The elongation viscosity of the main coating liquid of the third component is described as ηc, and the main coating liquid is used for the first casting coating liquid 51a, and the elongation viscosity of the main coating liquid of the fourth component is described as ηe, and this main The coating liquid is used for the second and third casting liquids 51b, 51c. The elongational viscosity was measured and the ηe/ηc value was 1.5. Then, the first casting solution 51a obtained from the main coating liquid of the third component and the second and third casting coating liquids 51b and 51c obtained from the main coating liquid of the fourth component are used for film production. The flow conditions of the first-third casting solution liquids 51a-51c fed by the gear pumps 73a-73c are changed so that the thicknesses Df1 and Df2 may be predetermined values. Other conditions are the same as in Example 13. The values of the thicknesses Df1 and Df2 are shown in Table 3.

[Comparative Examples 19-24]

The inner frame plates 130, 131 are replaced with the leading inner frame plates without the passages 135, 145. The main coating liquid of the third component is used to prepare the first to third casting coating liquids 51a to 51c. The other conditions of Comparative Examples 19-24 were the same as Examples 19-24. The values of the thicknesses Df1 and Df2 are shown in Table 3.

Table η according to Examples 19-24 and Comparative Examples 19-24 shows ηe/ηc values, The thickness Df1 of the intermediate portion and the thickness Df2 of the side portion of the film. The ηe/ηc value is a content ratio when the elongational viscosity of each of the second and third casting liquids 51b and 51c is ηc and the elongational viscosity of the first coating liquid 51a is ηe. It also shows the judgment of stripping trouble (PD), thickness non-uniformity (TU), and manufacturing suitability (PA).

[Example 25-30]

The solid compound of Example 1 was added to the mixed solvent E (mixed solvent C was different from the mixed solvents A, B, C, and D) to obtain a main coating liquid 48 of the fifth component. The main coating liquid of the fifth component is used to prepare the first casting coating liquid 51a.

Then, the solid compound of Example 1 was added to the mixed solvent F (mixed solvent C was different from the mixed solvents A, B, C, D, and E) to obtain a main coating liquid 48 of the sixth component. The main coating liquid 48 of the fourth component is used to prepare the second casting coating liquids 51b to 51c.

Then, the first casting solution 51a obtained from the main coating liquid of the fifth component And the second and third casting liquids 51b, 51c obtained from the main coating liquid of the sixth component are used for film production. The flow conditions of the first-third casting solution liquids 51a-51c fed by the gear pumps 73a-73c are changed so that the thicknesses Df1 and Df2 may be predetermined values. Other conditions are the same as in Example 13. The values of the thicknesses Df1 and Df2 are shown in Table 4.

[Comparative Example 25-30]

The inner frame plates 130, 131 are replaced with the leading inner frame plates without the passages 135, 145. The main coating liquid of the third component is used to prepare the first to third casting coating liquids 51a to 51c. The other conditions of Comparative Examples 25-30 were the same as in Examples 25-30. The values of the thicknesses Df1 and Df2 are shown in Table 4.

The PCe/PCc, HCe/Hcc, Df1, and Df2 values are shown in accordance with Tables 25-30 and Tables 4-30 of Comparative Examples 25-30. Here, the PCe value is the concentration of the polymer in the first coating liquid 51a, and the PCc value is the concentration of the polymer in the second and third coating liquids 51b, 51c. It also shows the judgment of stripping trouble (PD), thickness non-uniformity (TU), and manufacturing suitability (PA).

In the inner frame plates 430, 431 of the casting die 481, the contact faces 444, 445, 454, 455 are coated with Teflon. In the film production, other conditions were the same as in Example 1. The relative standard deviation (RSD) of Example 1 was larger than the other according to the obtained film.

Therefore, in the solution casting method and the solution casting apparatus of the present invention, since the thickness of the side portion of the casting pellet is independently controlled with respect to the intermediate portion, the film and the wide film can be efficiently produced.

Various changes and modifications are possible in the present invention, and it should be understood that they are within the scope of the present invention.

10‧‧‧ Coating liquid production line

11‧‧‧Solvent tank

13‧‧‧ mixing tank

14‧‧‧Addition funnel

15‧‧‧Additive tank

18‧‧‧ heating device

19‧‧‧ Temperature Controller

20‧‧‧Filter device

21‧‧‧Flashing device

22‧‧‧Filter device

23‧‧‧Recycling device

24‧‧‧Refining device

25,26‧‧‧ pump

28‧‧‧Soluble liquid

30‧‧‧Material tank

30a‧‧‧Motor

30b‧‧‧Agitator

30c‧‧‧ coat

32‧‧‧ film production line

35,36‧‧‧ valve

37‧‧‧ coat

38‧‧‧Motor

39‧‧‧First stirrer

40‧‧‧Motor

41‧‧‧Second stirrer

44‧‧‧ mixed liquid

46‧‧‧Valves

48‧‧‧Main coating liquid

50‧‧‧film manufacturing method

51‧‧‧Casting coating

51a, 51b, 51c‧‧‧First casting solution

52‧‧‧Casting coating method

53‧‧‧cast film

54‧‧‧Casting procedure

55‧‧‧ Wet film

56‧‧‧ stripping procedure

57‧‧‧film

58‧‧‧Drying procedure

61‧‧‧Solution supply unit

62‧‧‧Casting room

63‧‧‧path roller

64‧‧‧ pin tenter

65‧‧‧Edge cutting device

66‧‧‧Drying room

67‧‧‧Cooling room

68‧‧‧Winding room

71a, 71b, 71c‧‧‧ pipeline

73a, 73b, 73c‧‧‧ gear pump

74, 74a, 74b, 74c‧‧‧ filter unit

75a, 75b, 75c‧‧‧ static mixer

79‧‧‧cast controller

80‧‧‧coating liquid

81‧‧‧casting mode

81a‧‧‧模入口

81b‧‧‧Export

81c‧‧‧coating channel

82‧‧‧Casting

82a‧‧‧Axis

82b‧‧‧Circle

83‧‧‧ peeling roller

86‧‧‧temperature controller

87‧‧‧Condenser

88‧‧‧Recycling device

89‧‧‧Heat transfer medium circulator

90‧‧‧Decompression chamber

95‧‧‧ crusher

97‧‧‧Clip type tenter

100‧‧‧roll

101‧‧‧Adsorption device

104‧‧‧Forced neutralization device (or neutralization rod)

105‧‧‧Rolling Roller

107‧‧‧Rolling shaft

108‧‧‧Compression roller

120‧‧‧ Lips

120a, 120b‧‧‧ contact surface

121‧‧‧ Lips

121a, 121, 121c, 121d‧‧‧ contact surface

122,123‧‧‧ side panels

125‧‧‧Management

126‧‧‧ stitching

130‧‧‧ inner frame board

130a, 130b‧‧‧ contact surface

131‧‧‧ inner frame board

131a, 131b‧‧‧ contact surface

135‧‧‧ channel

135a‧‧‧Export

136‧‧‧ channel

140‧‧‧Separated section

140a‧‧‧

145‧‧‧ channel

145a‧‧‧Export

146‧‧‧ channel

150‧‧‧Separated section

150a‧‧‧

160‧‧‧temperature controller

165‧‧Decompression chamber

230‧‧‧ inner frame board

230a, 230b‧‧‧ contact surface

231‧‧‧ inner frame board

231a, 231b‧‧‧ contact surface

235‧‧‧ channel

235a‧‧ Export

240‧‧‧Separated section

240a‧‧‧

281‧‧‧casting die

330‧‧‧ inner frame board

330a, 330‧‧‧ contact surface

331‧‧‧ inner frame board

331a, 331b‧‧‧ contact surface

335‧‧‧ channel

335a‧‧‧Export

340‧‧‧Separated section

340a‧‧‧

381‧‧‧casting die

430,431‧‧‧ inner frame board

440‧‧‧Separated section

440a‧‧‧

444,445‧‧‧Contact surface

450‧‧‧Separated section

450a‧‧‧

454, 455 ‧ ‧ contact surface

481‧‧‧casting die

Z1‧‧‧ direction of rotation

SW1, SW2‧‧‧ slit width

V‧‧‧ line

TD‧‧ direction

CL1‧‧‧ clearance

W1‧‧‧Width

D1‧‧‧ thickness

The above objects and advantages of the present invention will become apparent to those skilled in the <RTIgt;

1 is a schematic view of a coating liquid production line for manufacturing a main coating liquid; FIG. 2 is a flow chart for manufacturing a film from a main coating liquid; and FIG. 3 is a schematic view of a film production line for manufacturing a film from a main coating liquid. Fig. 4 is a cross-sectional view showing a first embodiment of a casting die in a film production line; Fig. 5 is a plan view of a casting die taken along line V-V of Fig. 4; and Fig. 6 is a drawing in a film production line Fig. 7 is a cross-sectional view showing a third embodiment of a casting die in a film production line; and Fig. 8 is a view showing a fourth embodiment of a casting die in a film production line Surface map.

51a, 51b, 51c‧‧‧First casting solution

71a, 71b, 71c‧‧‧ pipeline

80‧‧‧coating liquid

81‧‧‧casting mode

81a‧‧‧模入口

81b‧‧‧Export

81c‧‧‧coating channel

121 lip

122,123‧‧‧ side panels

125‧‧‧Management

126‧‧‧ stitching

130‧‧‧ inner frame board

130a, 130b‧‧‧ contact surface

131‧‧‧ inner frame board

131a, 131b‧‧‧ contact surface

135‧‧‧ channel

135a‧‧‧Export

136‧‧‧ channel

140‧‧‧Separated section

140a‧‧‧

145‧‧‧ channel

145a‧‧‧Export

146‧‧‧ channel

150‧‧‧Separated section

150a‧‧‧

TD‧‧ direction

CL1‧‧‧ clearance

W1‧‧‧Width

D1‧‧‧ thickness

Claims (16)

A coating liquid application method for forming a casting film on a moving support, the casting film is intended to be dried into a polymer film, and the coating liquid application method comprises the following steps: (1) preparing a self-casting mold to the support a side coating liquid of a side portion of the granule, the casting mold discharges the side coating liquid through a slit extending in a width direction of the struts; (2) preparing a middle portion between the side portions of the granule The intermediate coating liquid; (3) combining the side coating liquid flow and the intermediate coating liquid flow in the casting mold, the casting mold having a partition member having a slit so that the partition member can form the side coating liquid flow a side flow passage, and an intermediate flow passage for the intermediate coating liquid flow, wherein a downstream end of the partition member is disposed upstream of the slit, so that the side coating liquid and the intermediate coating liquid can be combined before flowing out from the slit; and (4) The side coating liquid and the intermediate coating liquid are co-applied, wherein the casting mold has an outlet, and the distance from the outlet to the downstream end is in the range of 0.1 mm to 3 mm. The coating liquid application method of claim 1, wherein the side flow passage has a width W1 of at least 0.1 mm in a longitudinal direction of the slit. The coating liquid application method of claim 1, wherein the side coating liquid is supplied to the side flow passage by a side feeding device for feeding the side coating liquid. For example, the application method of the coating liquid according to item 3 of the patent application scope, Wherein the intermediate coating liquid is supplied to the intermediate flow passage by an intermediate feeding device for feeding the intermediate coating liquid; and the side feeding device is independently controlled in the side flow passage using the side feeding device The flow rate between the side coating liquid flowing and the intermediate coating liquid flowing in the intermediate flow passage. The coating liquid application method of claim 1, wherein the intermediate coating liquid, the first side coating liquid to be supplied to one of the side flow passages, and the second side coating liquid to be supplied to the other side flow passage are coated The liquid is the same. The coating liquid application method according to claim 1, wherein the side coating liquid has an elongation viscosity higher than that of the intermediate coating liquid. The coating liquid application method according to claim 6, wherein if the elongation viscosity of the side coating liquid is ηe and the tensile viscosity of the intermediate coating liquid is ηc, the ηe/ηc value is at most 3. The method for applying a coating liquid according to claim 6, wherein each of the intermediate coating liquid and the solvent of the side coating liquid contains a good solvent component and a poor solvent component; and the poor solvent component of the solvent in the side coating liquid The content is higher than the content of the solvent in the intermediate coating liquid of the poor solvent component. The coating liquid application method of claim 8, wherein the content of the polymer in the side coating liquid is lower than the content of the polymer in the intermediate coating liquid. The coating liquid application method according to claim 1, wherein the partition member has at least one contact surface for contacting the intermediate coating liquid and one of the side coating liquids, and the contact surface is coated with a polymer compound. A coating method for applying a coating liquid onto a moving support to manufacture a polymer film a liquid casting method comprising the steps of: (1) preparing a side coating liquid for a self-casting mold to a side portion of the constituent particles of the support, the casting mold discharging the side through a slit extending in a width direction of the support body a coating liquid; (2) preparing an intermediate coating liquid for constituting an intermediate portion between the sides of the pellet; (3) combining the side coating liquid flow and the intermediate coating liquid flow in the casting mold, The casting die has a partition member having a slit such that the partition member can form the side liquid flow side flow passage and the intermediate coating liquid flow intermediate flow passage, and the downstream end of the partition member is disposed upstream of the slit So that the side coating liquid and the intermediate coating liquid can be combined before flowing out from the slit; (4) co-applying the side coating liquid and the intermediate coating liquid to form a casting film; (5) having a self-casting film in the casting film After the properties are removed, the cast film is stripped from the support into the polymer film; and (6) the polymer film is dried, wherein the casting die has an outlet, and the distance from the outlet to the downstream end is Range of 0.1 mm to 3 mm. A casting unit for applying a coating liquid to form particles on a moving support, comprising: a casting die for discharging the coating liquid, the casting die having a side coating liquid for supplying a side coating layer a side inlet, an intermediate inlet for supplying an intermediate coating liquid to form an intermediate portion between the sides, for the side coating liquid and the a groove for flowing the intermediate coating liquid, a slit for jointly discharging the side coating liquid and the intermediate coating liquid, and a manifold for retaining the intermediate coating liquid; a partition member disposed in the groove, the partition member The groove is partitioned into a side flow passage for the side coating liquid flow, and an intermediate flow passage for the intermediate coating liquid flow, and the downstream end of the partition member has a slit having an acute angle, and the slit is disposed 0.1 mm to 40 mm from the upstream side of the slit And a feeding device for feeding the side coating liquid to the side inlet, wherein the casting die has an outlet, and the distance from the outlet to the downstream end is in the range of 0.1 mm to 3 mm. The casting unit of claim 12, wherein the side flow passage has a width in the longitudinal direction of the slit of at least 0.1 mm. The casting unit of claim 12, wherein the side coating liquid is supplied to the side flow passage by a side feeding device for feeding the side coating liquid. The casting unit of claim 14, wherein the intermediate coating liquid is supplied to the intermediate flow passage by an intermediate feeding device for feeding the intermediate coating liquid; and the side feeding device and the middle are used therein The feeding device independently controls the flow rate of the side coating liquid flowing in the side flow passage and the intermediate coating liquid flowing in the intermediate flow passage. The casting unit of claim 14, wherein the partition member has at least one contact surface for contacting the intermediate coating liquid and one of the side coating liquids, and the contact surface is coated with a polymer compound.