WO2011111598A1 - テンタ装置及びテンタ装置内での異物除去方法並びに溶液製膜設備 - Google Patents
テンタ装置及びテンタ装置内での異物除去方法並びに溶液製膜設備 Download PDFInfo
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- WO2011111598A1 WO2011111598A1 PCT/JP2011/054891 JP2011054891W WO2011111598A1 WO 2011111598 A1 WO2011111598 A1 WO 2011111598A1 JP 2011054891 W JP2011054891 W JP 2011054891W WO 2011111598 A1 WO2011111598 A1 WO 2011111598A1
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- Prior art keywords
- film
- section
- foreign matter
- chamber
- jet
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/20—Edge clamps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0034—Polarising
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
Definitions
- the present invention relates to a tenter device that dries a film while stretching both sides of the film at a certain width-enhancing rate, and a foreign matter removing method in the tenter device.
- the present invention further relates to a solution casting apparatus including the tenter device.
- Polymer films are widely used as optical functional films because they have excellent light transmittance and flexibility and can be made light and thin.
- the cellulose ester film using cellulose acylate or the like has toughness and low birefringence in addition to the above-described properties.
- This cellulose ester film is used as a protective film and an optical compensation film for a polarizing plate, which is a constituent member of a liquid crystal display (LCD) whose market is expanding in recent years, including a photographic photosensitive film.
- LCD liquid crystal display
- One method for producing a polymer film is a solution casting method.
- a dope containing a polymer and a solvent is cast from a casting die onto a support to form a casting film.
- the cast film is peeled off from the support as a wet film.
- the wet film is conveyed in the state which hold
- the tenter the ear portion is stretched in the width direction with respect to the wet film being conveyed, and drying is performed by blowing dry air. Thereby, a film is obtained.
- edge part of a film it dries further with a drying apparatus.
- the film that has passed through the drying device is wound up by a winding device.
- Drying of the wet film in the tenter is performed by carrying both ends of the film by carrying means such as clips and pins, and blowing dry air on the running film.
- the carrying means is fixed to an endless moving body such as a chain and is circulated. For this reason, when the film is supported again by the supporting means exposed to high temperature drying air near the exit of the tenter and heated to a high temperature, foaming due to boiling of the solvent in the film may occur, leading to film cutting.
- the film is supported by a pin plate having pins.
- the supporting means is cooled by passing through a cooling duct before supporting both side ends of the film (see, for example, Patent Document 1).
- cooling ducts create new problems.
- the solvent gas evaporated from the wet film is filled.
- the plasticizer and UV agent (ultraviolet absorber) in the wet film are evaporated together with the solvent, and these are also mixed in the solvent gas.
- Such solvent gas is entrained in the cooling duct as the clip or pin plate moves.
- the solvent gas that has entered the cooling duct is liquefied or solidified by cooling the cooling duct, and adheres to the pins and the pin plate as foreign matter.
- This foreign material contains a large amount of additives such as plasticizers and UV agents added to the dope.
- a large burden is placed on the pin plate.
- the film cannot be conveyed stably.
- the solvent is recovered from the solvent gas in the tenter by condensation recovery or adsorption recovery, and the gas from which the solvent has been removed is sent back into the tenter.
- a plasticizer, a UV agent and the like are recovered in accordance with the recovery of the solvent.
- the pin tenter in addition to the foreign matter generated in the cooling duct as described above, punched debris generated when the pin is inserted into the film, burrs remaining around the pin when the pin is extracted from the film, etc. Foreign matter may also adhere and accumulate on the pin plate. Such foreign matter not only prevents the stable conveyance of the film, but also contributes to in-process contamination in the pin tenter 13, similarly to the foreign matter generated in the cooling duct as described above. At the same time, when these foreign substances are mixed in the film, the quality of the film may be affected.
- An object of the present invention is to provide a tenter device that removes foreign matter that hinders film transport and stabilizes film transport, a method for removing foreign matter in the tenter device, and a solution casting apparatus.
- the tenter device of the present invention includes a supporting member, a circulation moving unit, a stretching / drying unit, a chamber, a jet wind blowing unit, and a foreign matter discharging unit.
- the supporting member supports both end portions of the film being conveyed.
- the circulation moving unit circulates and moves the carrying member between the carrying section and the release section.
- the carrying section is a section in which the carrying member carries the film.
- the release section is a section in which the support member releases the support of the film.
- the stretching / drying section stretches the film in the carrying section with a constant widening ratio and dries by blowing dry air. The stretching is performed by gradually shifting the support member in the direction in which the film is widened.
- a chamber covers the carrier member in the release section.
- the jet air blowing unit removes foreign matter adhering to the carrying member by blowing jet air against the carrying member passing through the chamber.
- the foreign matter discharge unit discharges the foreign matter out of the chamber.
- the foreign matter discharge portion is provided on the upstream side suction chamber provided on the upstream side with respect to the moving direction of the support member and on the downstream side with respect to the jet wind spray portion.
- the foreign matter is sucked into the downstream suction chamber, and the sucked foreign matter is discharged out of the chamber together with the jet wind through a discharge nozzle attached to the upstream suction chamber and the downstream suction chamber. It is preferable.
- the upstream suction chamber and the downstream suction chamber are preferably in a negative pressure state.
- the tenter device preferably includes a jet wind circulation unit, a jet wind escape unit, and a control unit.
- the jet wind circulation unit circulates the jet wind by collecting the jet wind blown to the support member in the chamber and returning the collected jet wind to the chamber.
- the jet wind escape section allows a part of the collected jet wind to escape.
- the control unit controls the temperature of the jet wind blown to the support member by adjusting the amount of jet wind released by the jet wind escape section.
- the solution casting apparatus of the present invention includes a support and a tenter device.
- the dope is cast on the support to form a cast film.
- the dope includes a polymer, a solvent, and an additive.
- the tenter device stretches the wet film, which is the cast film peeled off from the support, in the width direction and dries it by blowing dry air to form a film.
- the tenter device includes a support member, a circulation moving unit, a chamber, a jet wind blowing unit, and a foreign matter discharging unit.
- the supporting member supports both end portions of the film being conveyed.
- the circulation moving unit circulates and moves the carrying member between the carrying section and the release section.
- the carrying section is a section in which the carrying member carries the film.
- the release section is a section in which the support member releases the support of the film.
- a chamber covers the carrier member in the release section.
- the jet air blowing unit removes foreign matter from the carrying member by blowing jet air against the carrying member passing through the chamber.
- the foreign matter discharge unit discharges the foreign matter together with the jet wind to the outside of the chamber.
- the foreign substances include those in which the additive is liquefied or solidified.
- the foreign matter includes at least one of debris and burrs that are generated when the carrying of the carrying member is started or released.
- the tenter device preferably includes a separation unit and a downward inclined pipe.
- the separation unit separates the foreign matter and the jet wind.
- the downward inclined pipe is provided so as to be gradually lowered from the foreign matter discharge portion toward the separation portion, and sends the foreign matter from the foreign matter discharge portion to the separation portion.
- the tenter device preferably includes a jet wind circulation unit, a jet wind escape unit, and a control unit.
- the jet wind circulation unit circulates the jet wind by collecting the jet wind blown to the support member in the chamber and returning the collected jet wind to the chamber.
- the jet wind escape section allows a part of the collected jet wind to escape.
- the control unit controls the temperature of the jet wind blown to the support member by adjusting the amount of jet wind released by the jet wind escape section.
- the control unit controls the temperature of the jet air so that the temperature exceeds the melting point of the additive and is less than the heat resistance temperature of various devices in the tenter device.
- the temperature of the jet air is preferably 49 ° C. or higher and controlled to 120 ° C. or lower, which is the heat resistance temperature of various devices in the tenter device.
- the tenter device is preferably a pin tenter having a pin and a pin plate in which a large number of the pins are planted as the carrying member.
- the foreign matter removing method in the tenter apparatus of the present invention includes a circulation movement step, a stretching / drying step, a jet wind blowing step, and a foreign matter discharging step.
- the circulating movement step circulates the carrying member between the carrying section and the release section.
- the carrying section is a section in which both end portions of the film being conveyed are carried by the carrying member.
- the release section is a section in which the support of the film by the support member is released.
- the stretching / drying step the film in the carrying section is stretched at a constant widening rate and dried by blowing dry air. The stretching is performed by gradually shifting the supporting member in the direction in which the film is widened.
- the jet wind blowing step removes foreign matter adhering to the carrying member by blowing jet air to the carrying member passing through the chamber in the chamber covering the carrying member in the release section.
- the foreign matter discharge step the foreign matter is discharged out of the chamber.
- FIG. 6 is a sectional view taken along line VI-VI in FIG. 3.
- FIG. 4 is a sectional view taken along line VII-VII in FIG. 3.
- FIG. 4 is a sectional view taken along line VIII-VIII in FIG.
- FIG. 4 is a sectional view taken along line IX-IX in FIG. 3. It is sectional drawing which shows the rail in a 1st cooling area, a rail cover, and a pin carrier.
- the solution casting apparatus 10 includes a casting chamber 11, a transition part 12, a pin tenter 13, a clip tenter 14, an ear clip device 15, a drying device 16, a cooling device 17, a winding device.
- the casting chamber 11 is provided with a feed block 21, a casting drum 22, a casting die 23, a stripping roller 26, a condenser (condenser) 27, and a recovery device 28.
- the dope from the dope production facility 20 is fed into the feed block 21.
- the casting drum 22 is a support on which the dope is cast.
- the casting die 23 casts the dope onto the casting drum 22.
- the stripping roller 26 strips the casting film 24 on the casting drum 22 as a wet film 25.
- the condenser 27 condenses and liquefies the solvent gas evaporated from the casting film 24 and the wet film 25.
- the recovery device 28 recovers the liquefied solvent.
- a heat transfer medium supply device (not shown) is connected to the casting drum 22. By supplying the heat transfer medium into the heat transfer medium supply device, the surface temperature of the casting drum 22 is adjusted to a desired temperature. Further, a temperature adjusting device 30 for adjusting the internal temperature is attached to the casting chamber 11.
- a dope channel is formed inside the feed block 21.
- a decompression chamber 32 is attached to the casting die 23.
- the decompression chamber 32 decompresses the dope flow (hereinafter referred to as “bead”) from the discharge port of the casting die 23 to the casting drum 22 to stabilize the contact of the bead with the casting drum 22.
- Bead the dope flow
- a jacket (not shown) is attached to the decompression chamber 32, and the decompression chamber 32 is adjusted to a desired temperature.
- a large number of rollers 35 are installed in the crossover section 12. These rollers 35 convey the wet film 25 peeled off from the casting drum 22 to the pin tenter 13.
- the transport direction of the wet film 25 is referred to as the A direction.
- a blower 36 is provided above the conveyance path of the wet film 25. The blower 36 blows dry air on the wet film 25 to promote drying of the wet film 25.
- the pin tenter 13 is inserted into and held by a pin at an ear portion of the wet film 25, and the wet film 25 is conveyed while the ear portion is held.
- the width of the wet film 25 is expanded at a constant widening ratio by extending the ear portion in the width direction.
- drying air is sent to the wet film 25 from the drying ducts 52 and 53 (see FIG. 3), and is heated to a desired temperature, thereby promoting drying.
- the drying air circulation device 60 adsorbs and recovers the solvent and plasticizer from the drying air sent from the drying ducts 52 and 53, and returns the dried air after the adsorption recovery to the drying ducts 52 and 53.
- the clip tenter 14 is provided downstream of the pin tenter 13, grips and conveys the ear portion of the wet film 25 coming out of the pin tenter 13 and performs drying.
- the wet film 25 is dried by blowing the dry wind while extending the ear portion in the width direction.
- the film 37 is obtained.
- the clip tenter is provided as necessary and may be omitted.
- the film 37 exiting the pin tenter 13 is sent to the drying device 16.
- the ear clip device 15 cuts the ear portion of the film 37 that has come out of the clip tenter 14.
- a crusher 66 is connected to the ear clip device 15, and the crusher 66 crushes the ear portion of the film 37 into chips. Then, the film 37 from which the ears have been cut is sent to the drying device 16.
- a large number of rollers 67 are provided inside the drying device 16, and the film 37 is dried while being conveyed by the rollers 67.
- the solvent gas generated from the film 37 in the drying device 16 is adsorbed and recovered by an adsorption recovery device 69 provided outside the drying device 16.
- the gas from which the solvent has been removed by the adsorption recovery is returned to the drying device 16 again.
- the film 37 exiting the drying device 16 is sent to the cooling device 17 where it is cooled to approximately room temperature.
- the ear clip device may also be provided at the outlet of the pin tenter 13 so that the ear portion is cut and then sent to the clip tenter.
- the winding device 18 includes a core 70, and the film 37 exiting the cooling device 17 is wound around the core 70 in a roll shape.
- the winding device 18 includes a press roller 71.
- the press roller 71 winds the film 37 while adjusting the winding pressure.
- the pin tenter 13 carries the wet film 25 in the A direction in a state in which both end portions (ear portions) 25a of the wet film 25 are carried, and the width direction (hereinafter referred to as “ In the “B direction”) at a predetermined stretching rate.
- the pin tenter 13 includes a brush roller 40 for inserting a pin, a dust removing device 42, a rail 44, sprockets 46 to 48, drying ducts 52 and 53, a rail cover (duct) 54, and a pin carrier 58. .
- the brush roller 40 is provided on the inlet 13a side of the pin tenter 13, and the pin 72 (see FIG. 4) is inserted into the ear portion 25a of the wet film 25 that has entered the pin tenter 13 to its root portion.
- the dust removing device 42 is provided on the outlet 13b side of the pin tenter 13 and removes dust and the like on the ear portion 25a by suction.
- the rails 44 are installed on both sides of the transport path of the wet film 25.
- the rail 44 has its width and widening pattern determined according to the stretch ratio of the wet film 25, and the stretched state of the rail 44 is shown exaggerated. Moreover, the widening pattern is also an example, and various widening patterns may be employed in consideration of the optical characteristics of the film.
- the rail 44 is composed of a pair of rails 44a and 44b arranged in the vertical direction.
- the sprockets 46 and 47 are provided on the inlet 13 a side of the pin tenter 13.
- the sprocket 48 is provided on the outlet 13 b side of the pin tenter 13.
- the pin carrier 58 for carrying the pin 72 and the pin plate in which many pins 72 are planted travels along the rail 44.
- the sprockets 46 and 47 rotate.
- the drying duct 52 is installed above the conveyance path of the wet film 25.
- the drying duct 53 is installed below the conveyance path of the wet film 25.
- the drying duct 52 blows dry air on the upper surface of the wet film 25. Further, the drying duct 53 blows dry air on the lower surface of the wet film 25.
- the temperature of the drying air in the drying ducts 52 and 53 is set to a predetermined temperature in the range of 40 ° C. or more and 200 ° C. or less. Thereby, drying of the wet film 25 is promoted, and the solvent gas evaporates from the wet film 25.
- the rail cover 54 covers a part of the rails 44 a and 44 b and the pin carrier 58.
- a rail 44a is attached to the upper surface inside the rail cover 54, and a rail 44b is attached to the lower surface thereof.
- the pin carrier 58 is disposed between the rail 44a and the rail 44b.
- a slit 54 a is formed in the rail cover 54 along the traveling direction of the pin carrier 58.
- the slit 54a is covered with a wind shielding member 75, which will be described later, so that inert gas and cooling air sent into the rail cover 54 do not escape.
- the rail cover 54 near the position where the sprocket 46 is installed has a slit 54b for the sprocket 46 to enter.
- the pin carrier 58 includes a pin 72, a pin plate 73, a carrier body 74, a wind shielding member 75, and guide rollers 76 to 79.
- the pin 72 and the pin plate 73 constitute a support member.
- a large number of pins 72 are planted on the pin plate 73 at predetermined intervals.
- the pin plate 73 is fixed to the wind shield 75 a of the wind shield member 75.
- a protrusion 74 a for supporting the wind shielding member 75 is formed on the side surface of the carrier body 74.
- a wind shield member 75 is fixed to the protrusion 74a.
- a meshing groove 74 b that meshes with the teeth of the sprockets 46, 47, 48 is formed at the center of the lower surface of the carrier body 74.
- the wind shield member 75 is fixed to the protrusion 74 a of the carrier body 74 through the slit 54 a of the rail cover 54.
- the wind shield 75 includes a wind shield 75a extending in the vertical and horizontal directions so as to cover the slit 54a.
- the wind shield 75a covers the slit 54a of the rail cover 54.
- the wind shield 75 a prevents dry air containing solvent gas evaporated from the wet film 25 from entering the rail cover 54. Further, the wind shield 75a prevents the steam from entering the rail cover 54 when the pins 72 and the pin plate 73 are subjected to steam cleaning in a steam cleaning area 82 (see FIG. 7) described later.
- the guide roller 76 and the guide roller 77 are provided on the upper surface of the carrier body 74 so as to be separated from each other by the width of the rail 44a.
- the guide roller 78 and the guide roller 79 are provided on the lower surface of the carrier body 74 so as to be separated by the width of the rail 44b.
- a connecting bracket for connecting the carrier bodies 74 to each other is provided at the front end portion and the rear end portion of each carrier body 74 in the traveling direction.
- a connecting pin is attached to the connecting bracket in the horizontal direction. Therefore, since each carrier main body 74 is connected via the connecting pin, it can run and move in the vertical plane as shown in FIG.
- the pin carrier may be formed using a chain.
- the pin tenter 13 includes a gas purge area 81, a steam cleaning area 82, a jet wind cleaning area 83, a first cooling area along the traveling direction of the pin carrier 58 from which the wet film 25 is released. 84, a second cooling area 86 is provided.
- Most of the foreign matters removed by the cleaning in the steam cleaning area 82 and the jet wind cleaning area 83 contain components contained in the solvent gas evaporated from the wet film 25.
- Components contained in the solvent gas include liquefied additives such as plasticizers such as TPP (triphenyl phosphate), BDP (biphenyl diphenyl phosphate) and polyester, and UV agents such as benzotriazole materials.
- the foreign matters include those in which the optical property adjusting agent is liquefied or solidified. By removing such foreign matter, there is no pin carrier 58 obstructing the conveyance of the wet film. At the same time, in-process contamination in the pin tenter 13 can be prevented, and foreign matter can be prevented from entering the wet film 25.
- an air supply nozzle 90 and an intake exhaust pipe 91 are attached to the rail cover 54 located in the gas purge area 81.
- the blowout hole of the nozzle 90 and the intake hole of the discharge pipe 91 are directed to the inside of the rail cover 54, respectively.
- a nitrogen gas supply unit 94, a suction device 95, and a filter 96 are installed in the gas purge area 81.
- the nitrogen gas supply unit 94 is connected to the nozzle 90.
- the suction device 95 is connected to the discharge pipe 91.
- the suction device 95 is connected to the nitrogen gas supply unit 94 via the filter 96.
- nitrogen gas is supplied from the nitrogen gas supply unit 94 to the nozzle 90.
- the nitrogen gas is supplied into the rail cover 54 through the blowout hole of the nozzle 90.
- the suction device 95 sucks in gas from the pressurized rail cover 54 through the suction hole of the discharge pipe 91 and sucks foreign matter accumulated in the rail cover 54.
- the filter 96 removes foreign substances from the gas sucked by the suction device 95.
- the nitrogen gas from which the foreign matter has been removed is sent to the nitrogen gas supply unit 94.
- the area where the holding of the ear portion 25a of the wet film 25 is released is an area where the concentration of the solvent gas is particularly high in the pin tenter 13 as well. Accordingly, by increasing the pressure inside the rail cover 54 by supplying nitrogen gas, the solvent gas can be prevented from entering the rail cover 54. Even if solvent gas enters the rail cover 54 and the solvent gas is liquefied or solidified and adheres to the guide rollers 76 to 79 as foreign matter, such foreign matter is removed by blowing nitrogen gas. . Furthermore, since the removed foreign matter is discharged out of the rail cover 54 by the suction device 95, there is no object that obstructs the travel of the pin carrier 58 in the rail cover 54. As a result, the pin carrier 58 can stably travel along the rail 44.
- the discharge pipe 91 may be provided away from the nozzle 90 in the traveling direction of the pin carrier 58. In this case, by setting the discharge position away from the position of the nozzle 90, it is possible to efficiently set the pressure in the rail cover 54 higher than that of the tenter chamber.
- a plurality of nozzles 90 and discharge pipes 91 may be provided in the gas purge area 81 at an appropriate pitch in the traveling direction of the pin carrier 58.
- nozzles 120a to 120c for spraying steam are installed in the steam cleaning area 82.
- the outlet hole of the nozzle 120 a is directed in the direction of the pin 72 and the pin plate 73.
- the blowout holes of the nozzles 120b and 120c are directed toward the rails 44a and 44b, the carrier body 74, and the guide rollers 76 to 79.
- a steam supply unit 122 is installed in the steam cleaning area 82.
- the steam supply unit 122 is connected to the nozzles 120a to 120c.
- jet wind is blown from the nozzles 203 and 204 arranged in the chamber 202 to the pins 72 and the pin plate 73.
- jet air By blowing jet air in the chamber 202, foreign matters such as punch debris and burrs are removed from the pins 72 and the pin plate 73. Further, the foreign matter accumulated in the chamber 202 is discharged out of the chamber 202 by the exhaust nozzle 240 (see FIG. 9).
- Jet air is supplied from a blower 205 outside the casing 200 via a supply pipe 206.
- the supply pipe 206 connects between the blower 205 and the chamber 202.
- an escape wind pipe 208 for attaching a part of the jet wind from the supply pipe 206 and releasing it into the casing 200 is attached.
- a three-way valve 209 that adjusts the amount of jet air that escapes to the escape wind pipe 208 is attached.
- the centrifuge 212 is provided at a position lower than the chamber 202, and the suction pipe 210 connecting them is inclined so as to gradually become lower from the chamber 202 toward the centrifuge 212.
- the foreign matters flowing in the suction pipe 210 include not only solid materials such as punched debris but also liquefied materials in which TPP or the like has been liquefied. Therefore, by setting the suction pipe 210 to a downward slope, the liquefied or solidified foreign matter can be reliably sent to the centrifuge 212 without clogging in the middle of the suction pipe 210.
- the centrifuge 212 separates foreign matter and jet air sent from the suction pipe 210.
- the centrifuge 212 is of a cyclone type, and feeds foreign matter and jet air from the suction pipe 210 along the inner peripheral surface of the cylindrical main body 214. Since the foreign matter is heavier than the jet wind, each time it turns in the cylindrical main body 214, it gradually falls in a spiral shape by its own weight. Thereby, the foreign substance and the jet wind are separated.
- the fallen foreign matter is sent to the collection unit 216 via a hopper 215 attached to the lower part of the cylindrical main body 214.
- the jet wind separated from the foreign matter is sent to the blower 205 via the pipe 218.
- the TPP can be reused by filtering.
- the chamber 202 is provided with a temperature sensor 219 for measuring the internal temperature.
- the controller 220 controls the opening degree of the three-way valve 209 based on the temperature in the chamber 202 measured by the temperature sensor 219.
- the opening degree by controlling the amount of jet air sent to the escape air pipe 208, the temperature of the jet air coming out of the nozzles 203 and 204 in the chamber 202 can be adjusted. Accordingly, not only the temperature of the jet wind but also the temperature in the chamber 202 can be adjusted only by escaping a part of the jet wind to the wind pipe 208, so that there is an additional cost such as installation of a heater or a cooling cooler. Does not need to take.
- the temperature of the jet wind is adjusted so that the temperature exceeds the melting point of the TPP and is lower than the heat resistance temperature of the casing 200, the nozzles 203, 204, the chamber 202, and other devices. It is preferable.
- the melting point of TPP is 49 ° C.
- the heat-resistant temperature of the device is 120 ° C.
- the chamber 202 includes a jet wind blowing unit 230, an upstream side intake chamber 231, and a downstream side intake chamber 232.
- the jet wind blowing unit 230 blows jet wind against the pins 72 and the pin plate 73.
- the upstream side intake chamber 231 is provided on the upstream side of the jet wind blowing unit 230 with respect to the moving direction P of the pin and the pin plate.
- the downstream side intake chamber 232 is provided on the downstream side of the jet wind blowing unit 230.
- the jet wind blowing unit 230 includes ducts 235 and 236 and a plurality of nozzles 203a to 203e and 204a to 204e. Ducts 235 and 236 are fed with jet air from blower 205.
- the plurality of nozzles 203a to 203e and 204a to 204e are provided on the lower surfaces of the ducts 235 and 236 and the upper surface of the duct, and blow the jet air in the ducts 235 and 236 toward the pin 72 and the pin plate 73.
- the plurality of nozzles 203a to 203e, 204a to 204e are provided at regular intervals along the moving direction P of the pin 72 and the pin plate 73.
- the nozzles 203 a and 204 a closest to the upstream side intake chamber 231 are provided so that the jet wind blows out substantially along the moving direction P of the pin 72 and the pin plate 73.
- the other nozzles 203b to 203e and 204b to 204e are provided so that the jet wind blows in the direction Q substantially opposite to the moving direction P of the pin 72 and the pin plate 73.
- the wind speed of the jet air blown from the nozzles 203a to 203e, 204a to 204e is preferably 10 m / min or more.
- the jet wind was blown along the moving direction P by blowing the jet wind from the nozzles 203b to 203e, 204b to 204e in the direction Q almost opposite to the moving direction P of the pin 72 and the pin plate 73.
- the impact force when the pin 72 and the pin plate 73 and the jet wind collide with each other is larger than that.
- the foreign material adhering to the pin 72 and the pin plate 73 can be easily removed.
- the jet air in the P direction which is the counter wind with respect to the jet air in the Q direction is used as the most upstream nozzle 203a. 204a, the momentum of the jet wind in the Q direction is weakened. Therefore, there is no possibility that the jet wind and the foreign matter contained in the jet wind will go out of the chamber 202 beyond the upstream side intake chamber 231.
- An exhaust nozzle 240 is attached to the upstream side intake chamber 231. By exhausting the gas in the upstream intake chamber 231 by the exhaust nozzle 240, the upstream intake chamber 231 is in a negative pressure state.
- An exhaust nozzle 242 similar to the upstream intake chamber 231 is also attached to the downstream intake chamber 232, and the downstream intake chamber 232 is in a negative pressure state by the exhaust nozzle 242.
- the upstream side intake chamber 231 and the downstream side intake chamber 232 are in a negative pressure state, the foreign matter removed from the pin 72 and the pin plate 73 by the jet wind blowing unit 230 is removed from the upstream side intake chamber 231 or the downstream side.
- the air is sucked into the side intake chamber 232.
- the foreign matter sucked into the upstream side intake chamber 231 or the downstream side intake chamber 232 is sent to the suction pipe 210 via the exhaust nozzles 240 and 242.
- the pins 72 and the pin plate 73 are covered with a pin cover 130 in the first cooling area 84.
- a supply hole 130 a is formed on the side surface of the pin cover 130.
- An air supply nozzle 132 is attached to the rail cover 54 located in the first cooling area 84. The blowout hole of the nozzle 132 is directed to the inside of the rail cover 54.
- a cooling air supply unit 134 is installed in the first cooling area 84, and the cooling air supply unit 134 is connected to the supply hole 130a.
- cooling air is supplied from the cooling air supply unit 134 so that the temperature inside the rail cover 54 and the whole inside of the pin cover 130 in the first cooling area 84 is substantially uniform.
- the temperature of the cooling air is set to a predetermined temperature of, for example, ⁇ 30 ° C. or higher and + 30 ° C. or lower.
- the temperature of the inside of the rail cover 54 and the whole inside of the pin cover 130 becomes below the melting point of TPP, that is, below 50 ° C. Accordingly, when TPP evaporated together with the solvent from the wet film 25 enters the first cooling area 84 with the movement of the pin carrier 58 or the pin plate 73, the TPP or the like is moved to the pin 72, the pin carrier 58, or the like. It will be deposited.
- the second cooling area 86 only the pins 72 and the pin plate 73 are cooled by cooling air. Since the configuration of the second cooling area 86 is the same as that of the first cooling area 84 except that no pin cover is installed, the description thereof is omitted. In the second cooling area 86, the surface temperature of the pin 72 and the pin plate 73 becomes 35 ° C. or more and 50 ° C. or less by performing cooling subsequent to the first cooling area 84. By setting the temperature of the pin 72 within the above range, the pin 72 can easily pass through the ear portion 25a.
- the wet film was transported without being inverted between the start of holding the ear of the wet film and the release.
- the present invention is not limited to this, and a multi-stage conveyance system that conveys the wet film while inverting it a plurality of times may be employed.
- the present invention is applied to the pin tenter in the present embodiment.
- the present invention is not limited to this, and the present invention can also be applied to a clip tenter.
- the pin tenter of the present invention was introduced into the solution casting equipment, the present invention is not limited to this, and the present invention may be implemented in a web manufacturing equipment for producing webs other than films.
- the width of the film 37 manufactured in this embodiment is preferably 1400 mm or more and 2500 mm or less. In addition, even if it is a case where the width
- the thickness of the film 37 manufactured in the above embodiment is preferably 20 ⁇ m or more and 100 ⁇ m or less, more preferably 20 ⁇ m or more and 80 ⁇ m or less, and most preferably 30 ⁇ m or more and 70 ⁇ m or less.
- the present invention is also effective when a cast film having a multilayer structure is formed.
- a known method such as casting a desired number of dopes simultaneously or sequentially may be used, and there is no particular limitation.
- co-casting, peeling method, stretching, drying conditions of each process, handling method, curling, winding method after flatness correction, solvent recovery method, film The recovery method is described in detail in paragraphs [0617] to [0889] of JP-A-2005-104148, and the inventions relating to these descriptions can also be applied to the present invention.
- the performance of the completed film, the degree of curling, the thickness, and the measuring methods thereof are described in paragraphs [1073] to [1087] of JP-A-2005-104148.
- the invention can also be applied to the present invention.
- a surface treatment it is preferable to apply a surface treatment to at least one surface of the completed film because the degree of adhesion with an optical member such as a polarizing plate can be increased.
- the surface treatment include vacuum glow discharge treatment, atmospheric pressure plasma discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, flame treatment, acid treatment, alkali treatment, etc., and at least one of these treatments is performed. Is preferred.
- a completed film When a completed film is used as a base and a desired functional layer is provided on both sides or one side, it can be used as various functional films.
- the functional layer include an antistatic layer, a cured resin layer, an antireflection layer, an easy adhesion layer, an antiglare layer, and an optical compensation layer.
- an antireflection layer when an antireflection layer is provided, an antireflection film capable of preventing light reflection and providing high image quality can be obtained.
- the functional layer and the forming method are described in detail in paragraphs [0890] to [1072] of JP-A-2005-104148, and the inventions relating to these descriptions can also be applied to the present invention. it can.
- TN type for example, TN type, STN type, VA type, OCB type, reflective type and the like described in paragraphs [1088] to [1265] of JP-A-2005-104148 For use in liquid crystal display devices.
- cellulose ester As the dope raw material because a highly transparent film can be obtained.
- the cellulose ester include lower fatty acid esters of cellulose such as cellulose triacetate, cellulose acetate propionate, and cellulose acylate butyrate.
- a cellulose acylate from the height of transparency, and it is preferable to use a triacetyl cellulose (TAC).
- TAC triacetyl cellulose
- the dope used in the above embodiment includes triacetyl cellulose (TAC) as a polymer.
- TAC triacetyl cellulose
- 90% by mass or more of TAC is preferably particles having a size of 0.1 to 4 mm.
- the cellulose acylate preferably has a degree of substitution with an acyl group for a hydroxyl group of cellulose that satisfies all of the following formulas (a) to (c) in order to obtain a film with higher transparency.
- a and B in the following formula represent the substitution degree of the acyl group with respect to the hydrogen atom in the hydroxyl group of cellulose. Specifically, A is the substitution degree of the acetyl group, and B has 3 to 22 carbon atoms. The degree of substitution of the acyl group. (A) 2.5 ⁇ A + B ⁇ 3.0 (B) 0 ⁇ A ⁇ 3.0 (C) 0 ⁇ B ⁇ 2.9
- the ⁇ -1,4-bonded glucose unit constituting cellulose has free hydroxyl groups at the 2nd, 3rd and 6th positions.
- Cellulose acylate is a polymer obtained by esterifying some or all of these hydroxyl groups with an acyl group having 2 or more carbon atoms.
- the degree of acyl substitution means the ratio of the esterification of the hydroxyl group of cellulose for each of the 2-position, 3-position and 6-position. The degree of substitution is 1 in the case of 100% esterification.
- the total degree of acylation substitution that is, the value of DS2 + DS3 + DS6 is preferably 2.00 to 3.00, more preferably 2.22 to 2.90, and particularly preferably 2.40 to 2.88. Further, the value of DS6 / (DS2 + DS3 + DS6) is preferably 0.28 or more, more preferably 0.30 or more, and particularly preferably 0.31 to 0.34.
- DS2 is a ratio in which the hydrogen of the hydroxyl group at the 2-position in the glucose unit is substituted with an acyl group
- DS3 is a ratio in which the hydrogen of the hydroxyl group at the 3-position in the glucose unit is substituted with an acyl group
- DS6 is the ratio in which the hydrogen of the 6-position hydroxyl group is replaced by an acyl group in the glucose unit.
- acyl group Only one type of acyl group may be used for cellulose acylate, or two or more types of acyl groups may be used. When two or more kinds of acyl groups are used, it is preferable that one of them is an acetyl group.
- the sum of the degree of substitution of hydroxyl groups at the 2nd, 3rd and 6th positions by acetyl groups is DSA, and the sum of the degree of substitution of the hydroxyl groups at the 2nd, 3rd and 6th positions by acyl groups other than acetyl groups
- DSA + DSB is preferably 2.22 to 2.90, and particularly preferably 2.40 to 2.88.
- DSB is preferably 0.30 or more, particularly preferably 0.7 or more. Further, 20% or more of DSB is preferably a substituent at the 6-position hydroxyl group, more preferably 25% or more, further preferably 30% or more, and particularly preferably 33% or more. Furthermore, the value of DSA + DSB at the 6-position of cellulose acylate is 0.75 or more, more preferably 0.80 or more, and particularly preferably cellulose acylate of 0.85 or more. When such cellulose acylate is used, a dope having excellent solubility can be prepared. In the case of using the cellulose acylate as described above, when a non-chlorinated solvent is used, a dope having very excellent solubility, low viscosity, and excellent filterability can be prepared. .
- Cellulose which is a raw material for cellulose acylate, may be obtained from either linter cotton or pulp cotton.
- the acyl group having 2 or more carbon atoms of cellulose acylate may be an aliphatic group or an aryl group, and is not particularly limited.
- cellulose alkylcarbonyl ester, alkenylcarbonyl ester, aromatic carbonyl ester, aromatic alkylcarbonyl ester and the like can be mentioned. Further, each may have a substituted group.
- Preferred examples of these include propionyl group, butanoyl group, pentanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, hexadecanoyl group, octadecanoyl group, iso-butanoyl group , T-butanoyl group, cyclohexanecarbonyl group, oleoyl group, benzoyl group, naphthylcarbonyl group, cinnamoyl group and the like.
- a propionyl group, a butanoyl group, a dodecanoyl group, an octadecanoyl group, a t-butanoyl group, an oleoyl group, a benzoyl group, a naphthylcarbonyl group, a cinnamoyl group, and the like are more preferable, and a propionyl group and a butanoyl group are particularly preferable. .
- the solvent used as the dope raw material is preferably an organic compound that can dissolve the polymer used.
- the dope means a mixture obtained by dissolving or dispersing the polymer in a solvent, and therefore a solvent having low solubility with the polymer can also be used.
- Solvents that can be suitably used include, for example, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene, and alcohols such as methanol, ethanol, n-propanol, n-butanol, and diethylene glycol.
- Ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate, ethyl acetate and propyl acetate, ethers such as tetrahydrofuran and methyl cellosolve, and the like.
- Two or more kinds of solvents may be selected from these solvents and mixed solvents may be used.
- use of dichloromethane is preferable because a dope having excellent solubility can be obtained and the solvent in the cast film can be evaporated in a short time to form a film.
- halogenated hydrocarbon those having 1 to 7 carbon atoms are preferably used.
- dichloromethane has 1 to 5 carbon atoms. It is preferable to use one of these alcohols or a mixture of several alcohols.
- the alcohol content is preferably 2 to 25% by weight, more preferably 5 to 20% by weight, based on the entire solvent.
- Specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, etc. Among them, it is preferable to use methanol, ethanol, n-butanol, or a mixture thereof.
- ethers having 4 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, and esters having 3 to 12 carbon atoms are preferable, and these are preferably used by being appropriately mixed.
- These compounds may have a cyclic structure, and compounds having two or more functional groups of ether, ketone, and ester, that is, any of —O—, —CO—, and —COO— may also be used as the solvent.
- the solvent may have another functional group such as an alcoholic hydroxyl group.
- the carbon number should just be in the prescription
- the dope may be added with various known additives such as a plasticizer, an ultraviolet absorber (UV agent), a deterioration inhibitor, a slipping agent, and a peeling accelerator.
- a plasticizer such as triphenyl phosphate and biphenyldiphenyl phosphate, phthalate plasticizers such as diethyl phthalate, and various known plasticizers such as polyester polyurethane elastomers are used. be able to.
- a silicon dioxide derivative is preferably used.
- the silicon dioxide derivative in the present invention includes silicon dioxide and a silicone resin having a three-dimensional network structure.
- an alkylated surface Fine particles that have been subjected to a hydrophobic treatment such as an alkylation treatment have excellent dispersibility in a solvent, so that a dope can be prepared without agglomeration of the fine particles, and a film can be produced. It is possible to produce a film with few state defects and high transparency.
- the fine particles whose surface is alkylated for example, Aerosil R805 (manufactured by Nippon Aerosil Co., Ltd.) which is commercially available as a silicon dioxide derivative having an octyl group introduced on its surface can be used.
- the fine particle content relative to the solid content of the dope is preferably 0.2% or less.
- the average particle diameter is preferably 1.0 ⁇ m or less, more preferably 0.3 to 1.0 ⁇ m, and particularly preferably 0.4 to 0 so that the fine particles do not hinder the passage of light. .8 ⁇ m.
- the ratio of containing TAC is 5 to 40% by weight with respect to the total amount of the dope after mixing the solvent and additives. More preferably, the proportion containing TAC is 15 to 30% by weight, particularly preferably 17 to 25% by weight.
- the proportion of the additive (mainly plasticizer) is preferably 1 to 20% by weight based on the entire solid content including the polymer and other additives contained in the dope.
- JP-A-2005 JP-A-2005.
- -104148 describes in detail in paragraphs [0196] to [0516], and these descriptions can also be applied to the present invention.
- it is a method for producing a dope using TAC.
- materials, raw materials, methods for dissolving and adding additives, filtration methods, defoaming and the like are also disclosed in JP-A-2005-104148 [0517]. It is described in detail from paragraph to [0616] paragraph, and these descriptions can also be applied to the present invention.
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Abstract
Description
(a) 2.5≦A+B≦3.0
(b) 0≦A≦3.0
(c) 0≦B≦2.9
Claims (12)
- テンタ装置は、以下を備える:
搬送中のフィルムの両側端部を担持する担持部材;
担持区間と解放区間との間で前記担持部材を循環移動させる循環移動部であり、前記担持区間は前記担持部材が前記フィルムの担持を行う区間である、前記解放区間は前記担持部材が前記フィルムの担持を解放する区間である;
前記担持区間におけるフィルムを一定の拡幅率で延伸するとともに乾燥風を吹付けることによって乾燥させる延伸・乾燥部であり、前記フィルムが拡幅する方向に前記担持部材を徐々にずらしておくことにより前記延伸を行う;
前記解放区間における前記担持部材を覆うチャンバ;
前記チャンバ内を通過する前記担持部材に対してジェット風を吹き付けることによって、前記担持部材に付着した異物を除去するジェット風吹付部;及び、
前記異物を前記チャンバ外へと排出する異物排出部。 - 請求の範囲第1項記載のテンタ装置において、前記異物排出部は、前記担持部材の移動方向に対して前記ジェット風吹付部よりも上流側に設けられた上流側吸引室と、前記ジェット風吹付部よりも下流側に設けられた下流側吸引室とにおいて、前記異物を吸引し、吸引した異物を、前記上流側吸引室及び下流側吸引室に取り付けられた排出ノズルを介して、前記ジェット風とともに前記チャンバ外に排出する。
- 請求の範囲第2項記載のテンタ装置において、前記上流側吸引室及び下流側吸引室は負圧状態となっている。
- 請求の範囲第1項記載のテンタ装置は備える:
前記チャンバ内で前記担持部材に吹き付けられたジェット風を回収し、回収したジェット風を前記チャンバにまで戻すことによって、ジェット風を循環させるジェット風循環部;
回収したジェット風の一部を逃がすジェット風逃がし部;及び、
前記ジェット風逃がし部によって逃がすジェット風の風量を調節することによって、前記担持部材に吹き付けるジェット風の温度を制御する制御部。 - 支持体とテンタ装置とを備える溶液製膜設備であって、前記支持体はドープが流延されて流延膜が形成される、前記ドープはポリマーと溶媒と添加剤とを含む、前記テンタ装置は前記支持体から剥ぎ取られた前記流延膜である湿潤フィルムを、幅方向に延伸するとともに乾燥風の吹き付けで乾燥してフィルムにする、前記テンタ装置は、以下を含む:
搬送中のフィルムの両側端部を担持する担持部材;
担持区間と解放区間との間で前記担持部材を循環移動させる循環移動部であり、前記担持区間は前記担持部材が前記フィルムの担持を行う区間である、前記解放区間は前記担持部材が前記フィルムの担持を解放する区間である;
前記解放区間における前記担持部材を覆うチャンバ;
前記チャンバ内を通過する前記担持部材に対してジェット風を吹き付けることによって、前記担持部材から異物を除去するジェット風吹付部;及び、
前記ジェット風とともに前記異物を前記チャンバ外へと排出する異物排出部。 - 請求の範囲第5項記載の溶液製膜設備において、前記異物は前記添加剤が液化又は固化したものを含む。
- 請求の範囲第5項記載の溶液製膜設備において、前記異物は前記担持部材の担持を開始又は解放したときに発生するカスとバリとの少なくともいずれか一方を含む。
- 請求の範囲第5項記載の溶液製膜設備において、前記テンタ装置は以下を含む:
前記異物と前記ジェット風とを分離する分離部;及び、
前記異物排出部から前記分離部に向かって徐々に低くなるように設けられ、前記異物排出部からの異物を前記分離部にまで送る下り傾斜配管。 - 請求の範囲第5項記載の溶液製膜設備において、前記テンタ装置は以下を含む:
前記チャンバ内で前記担持部材に吹き付けられたジェット風を回収し、回収したジェット風を前記チャンバにまで戻すことによって、ジェット風を循環させるジェット風循環部;
回収したジェット風の一部を逃がすジェット風逃がし部;及び、
前記ジェット風逃がし部によって逃がすジェット風の風量を調節することによって、前記担持部材に吹き付けるジェット風の温度を制御する制御部であり、前記制御部は、前記添加剤の融点を超える温度であって、前記テンタ装置内の各種機器の耐熱温度未満の範囲に、前記ジェット風の温度を制御する。 - 請求の範囲第9項記載の溶液製膜設備において、前記ジェット風の温度は、49℃以上であって、前記テンタ装置内の各種機器の耐熱温度の120℃以下に制御される。
- 請求の範囲第5項記載の溶液製膜設備において、前記テンタ装置は、前記担持部材として、ピンとこのピンが多数植えつけられたピンプレートとを有するピンテンタである。
- テンタ装置内での異物除去方法は、以下のステップを備える:
担持区間と解放区間との間で前記担持部材を循環移動させること、前記担持区間は搬送中のフィルムの両側端部を担持部材により担持する区間である、前記解放区間は前記担持部材による前記フィルムの担持を解放した区間である;
前記担持区間におけるフィルムを一定の拡幅率で延伸するとともに、乾燥風を吹付けることによって乾燥させること、前記延伸は前記フィルムが拡幅する方向に前記担持部材を徐々にずらしていくことにより行う;
前記解放区間における前記担持部材を覆うチャンバにおいて、前記チャンバ内を通過する担持部材に対してジェット風を吹き付けることによって、前記担持部材に付着した異物を除去すること;及び、
前記異物を前記チャンバ外へと排出すること。
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KR1020127023419A KR101587316B1 (ko) | 2010-03-10 | 2011-03-03 | 텐터 장치 및 텐터 장치 내에서의 이물질 제거 방법 그리고 용액 제막 설비 |
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JPH1177719A (ja) * | 1997-09-12 | 1999-03-23 | Konica Corp | セルローストリアセテートフィルムの製造装置及び製造方法 |
JPH11156937A (ja) * | 1997-11-26 | 1999-06-15 | Unitika Ltd | 同時二軸延伸機のリンク汚れ除去装置 |
JP2003025422A (ja) * | 2001-07-17 | 2003-01-29 | Mitsubishi Heavy Ind Ltd | テンタオーブン装置 |
JP2008265294A (ja) * | 2007-03-29 | 2008-11-06 | Fujifilm Corp | フィルム乾燥方法及び装置並びに溶液製膜方法 |
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JP2011183724A (ja) | 2011-09-22 |
CN102791466B (zh) | 2015-11-25 |
JP5479165B2 (ja) | 2014-04-23 |
KR20130006611A (ko) | 2013-01-17 |
KR101587316B1 (ko) | 2016-02-02 |
CN102791466A (zh) | 2012-11-21 |
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