WO2017056580A1 - Method for producing polarizing film, polarizing film, and polarizing plate - Google Patents

Method for producing polarizing film, polarizing film, and polarizing plate Download PDF

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Publication number
WO2017056580A1
WO2017056580A1 PCT/JP2016/068186 JP2016068186W WO2017056580A1 WO 2017056580 A1 WO2017056580 A1 WO 2017056580A1 JP 2016068186 W JP2016068186 W JP 2016068186W WO 2017056580 A1 WO2017056580 A1 WO 2017056580A1
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Prior art keywords
film
polarizing film
polarizing
producing
polyvinyl alcohol
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PCT/JP2016/068186
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French (fr)
Japanese (ja)
Inventor
枝澤 敏行
早川 誠一郎
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日本合成化学工業株式会社
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Priority to JP2016541456A priority Critical patent/JP6733543B2/en
Publication of WO2017056580A1 publication Critical patent/WO2017056580A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details

Definitions

  • the present invention relates to a method for producing a polarizing film, a polarizing film and a polarizing plate used in a liquid crystal display device (hereinafter sometimes abbreviated as LCD), and more specifically, a polyvinyl alcohol film as a raw material.
  • the present invention relates to a method for producing a polarizing film dyed with iodine, a polarizing film produced by the production method, and a polarizing plate using the polarizing film.
  • LCDs are used in portable information terminals, liquid crystal televisions, desktop electronic calculators, electronic watches, personal computers, word processors, automobile and machine instruments, etc., and polarizing plates are used in this LCD.
  • the polarizing plate one in which a protective film such as triacetyl cellulose is laminated on one side or both sides of a polarizing film made of a polyvinyl alcohol film to which iodine or a dichroic dye is adsorbed and oriented is brightly used.
  • a polarizing plate having a high transmittance and a high degree of polarization is required.
  • the polarizing film described above for example, is obtained by swelling a polyvinyl alcohol film with water (including warm water), dyeing with iodine, stretching to arrange iodine molecules, and boric acid to maintain the stretched state. It is produced by crosslinking with a crosslinking agent such as This manufacturing process is continuously performed while unwinding the polyvinyl alcohol film from the roll and transporting it in the horizontal direction using a winder or a nip roll.
  • the film absorbs water or dehydrates and curls, and folds and wrinkles occur at the end in the width direction of the film. There was a problem that it could not be manufactured. In particular, when the film is thin, there is a problem that the film breaks due to such folds and wrinkles and the production is interrupted. Furthermore, such a defect at the edge also affects the inside of the polarizing film, thereby degrading the polarizing performance of the entire polarizing film, making it difficult to uniformly attach the polarizing plate to the liquid crystal cell, and the color of the liquid crystal display image. It was the cause of unevenness and white spots.
  • JP 2006-189560 A Japanese Patent Laid-Open No. 7-247378
  • Patent Document 1 can avoid creases and wrinkles in the drying process
  • the film may be folded or wrinkled in any of the steps of water swelling, dyeing, stretching, and boric acid crosslinking before the drying process. If it occurs, there is a problem that it cannot be transported to the drying process in the first place.
  • Patent Document 2 can avoid folding and wrinkles in water, it cannot prevent folding and wrinkles that occur in the air. Therefore, the present invention aims to solve the problem of folding and wrinkles in the entire manufacturing process of the polarizing film, and to manufacture a polarizing film with high productivity and little polarization unevenness.
  • Method for producing polarizing film 1) A method for producing a polarizing film comprising a step of unwinding a polyvinyl alcohol film from a roll and transferring it horizontally, 2) a water swelling step, 3) a dyeing step, 4) a stretching step, and 5) a boric acid crosslinking step. There, Before and / or after any of the steps 2) to 4), a gas is blown to both ends of the film in the width direction under the following condition a to prevent curling of the film: Production method. Condition a) The angle ⁇ 1 formed between the gas blowing direction and the film surface is 5 to 80 °.
  • a polarizing plate comprising a protective film provided on at least one surface of the polarizing film of the present invention.
  • the “film width direction” is generally a direction substantially perpendicular to the longitudinal direction of the belt-like film.
  • the direction is substantially perpendicular to the film transfer direction, and typically the distance between both edges of the film is the shortest.
  • the width direction of the film is referred to as “TD direction”
  • the transfer direction of the film is referred to as “MD direction”.
  • the polyvinyl alcohol film is also simply referred to as “film”.
  • a wide, long and thin polarizing film can be produced with high productivity, and a polarizing film having a uniform degree of polarization from the center to the end of the polarizing film can be obtained. Furthermore, it is possible to easily produce a wide, long and thin polarizing plate, and to reduce color unevenness and white spots in a liquid crystal display image.
  • FIG. 1 is a diagram schematically showing locations of air blowing in 1) a raw fabric unwinding step, 2) a water swelling step, and 3) a dyeing step.
  • FIG. 2 is a diagram schematically showing the distance A between the liquid level of the water swelling tank and the roll a and the distance B between the roll a and the roll b between 2) the water swelling process and 3) the dyeing process.
  • FIG. 3A is a diagram showing a spraying mode when a liquid is sprayed on the surface of a polyvinyl alcohol film (PVA film).
  • FIG. 3B is a diagram showing a spraying mode when a liquid is sprayed on the back surface of a polyvinyl alcohol film (PVA film).
  • FIG. 4 is a diagram showing an angle ⁇ 1 formed by the blowing direction and the surface of the film when air is blown onto the front or back surface of the polyvinyl alcohol film.
  • FIG. 5 shows the angle ⁇ 2 formed between the direction when the blowing direction is perpendicularly projected onto the surface of the polyvinyl alcohol film and the transfer direction of the polyvinyl alcohol film when air is blown onto the front or back surface of the polyvinyl alcohol film.
  • FIG. FIG. 6 shows the angle ⁇ 1 formed between the blowing direction and the surface of the film when air is blown on the front or back surface of the polyvinyl alcohol film, and the direction when the blowing direction is vertically projected onto the surface of the polyvinyl alcohol film. It is a figure which shows angle (theta) 2 which makes with the transfer direction of an alcoholic film.
  • FIG. 7 is a diagram showing an example of a spraying mode when air is sprayed on a polyvinyl alcohol film.
  • a step of unwinding a polyvinyl alcohol film from a roll and transferring it horizontally 2) a water swelling step, 3) a dyeing step, 4) a stretching step, and 5) boric acid
  • a polarizing film is manufactured through a crosslinking step.
  • 1) The process which unwinds a polyvinyl alcohol-type film from a roll and transfers it to a horizontal direction is also called 1) original fabric unwinding process below.
  • the polyvinyl alcohol film used in the above 1) raw roll unwinding step is a film obtained by forming a polyvinyl alcohol resin into a film and wound up on a roll.
  • polyvinyl alcohol resin used for the polyvinyl alcohol film an unmodified polyvinyl alcohol resin, that is, a resin produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate is usually used.
  • the polyvinyl alcohol film used in the present invention is not necessarily limited thereto, and can be copolymerized with vinyl acetate and a small amount (for example, 10 mol% or less, preferably 5 mol% or less) of vinyl acetate.
  • a polyvinyl alcohol-based resin obtained by saponifying a copolymer with a component can also be used.
  • components copolymerizable with vinyl acetate include unsaturated carboxylic acids (including salts, esters, amides, nitriles, etc.), and olefins having 2 to 30 carbon atoms (eg, ethylene, propylene, n-butene). , Isobutene, etc.), vinyl ethers, unsaturated sulfonates and the like.
  • the modified polyvinyl alcohol-type resin obtained by chemically modifying the hydroxyl group after saponification can also be used.
  • a polyvinyl alcohol resin having a 1,2-diol structure in the side chain can be used as the polyvinyl alcohol resin.
  • a polyvinyl alcohol resin having a 1,2-diol structure in the side chain includes, for example, (i) a method for saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene, and (ii) acetic acid.
  • the weight average molecular weight of the polyvinyl alcohol resin is preferably 100,000 to 300,000, particularly preferably 110,000 to 280,000, and more preferably 120,000 to 260,000 from the viewpoint of optical performance and stretchability.
  • the average saponification degree of the polyvinyl alcohol-based resin is usually preferably 98 mol% or more, particularly preferably 99 mol% or more, more preferably 99.5 mol% or more, particularly preferably from the viewpoint of optical performance. It is 99.8 mol% or more.
  • polyvinyl alcohol resin used in the present invention two or more kinds having different modified species, modified amount, weight average molecular weight, average saponification degree, etc. may be used in combination.
  • the polyvinyl alcohol film used in the present invention prepares a polyvinyl alcohol resin aqueous solution using the above polyvinyl alcohol resin, and discharges and flows the aqueous solution to a cast mold such as a cast drum, a cast belt, and a cast resin film. It is manufactured by rolling and forming a film, winding it on a roll after drying.
  • polyvinyl alcohol-based resin aqueous solutions include plastics commonly used such as glycerin, diglycerin, triglycerin, ethylene glycol, triethylene glycol, polyethylene glycol, and trimethylol propane as necessary. It is preferable from the viewpoint of film forming property to contain an agent and a nonionic, anionic, and / or cationic surfactant.
  • the resin concentration of the aqueous polyvinyl alcohol resin solution is preferably 10 to 60% by weight, particularly preferably 15 to 55% by weight, and further preferably 20 to 50% by weight.
  • the temperature of the aqueous polyvinyl alcohol resin solution when discharged into a cast mold is preferably 80 to 100 ° C., particularly preferably 85 to 98 ° C.
  • the discharge rate of the aqueous polyvinyl alcohol resin solution discharged into the cast mold is preferably 0.1 to 5 m / min, particularly preferably 0.2 to 4 m / min, and more preferably 0.3 to 3 m. / Min.
  • the surface temperature of a cast mold such as a cast drum is preferably 40 to 99 ° C, particularly preferably 60 to 95 ° C.
  • the film formed in the cast mold is dried by conveying the film while the front surface and the back surface of the film are alternately brought into contact with the outer peripheral portions of a plurality of heat rolls. After drying with a hot roll, the film may be heat treated. The heat treatment is preferably performed at 60 to 150 ° C., particularly preferably 80 to 130 ° C. Before winding the film on a roll, both ends of the film may be cut off with slits.
  • the thickness of the polyvinyl alcohol film is preferably 5 to 60 ⁇ m from the viewpoint of thinning the polarizing film, more preferably 5 to 30 ⁇ m from the viewpoint of further thinning, from the viewpoint of avoiding breakage. Particularly preferably, the thickness is 10 to 30 ⁇ m.
  • the width of the polyvinyl alcohol film is preferably 3 m or more, more preferably 4 m or more from the viewpoint of increasing the area, and particularly preferably 4 to 6 m from the viewpoint of avoiding breakage.
  • the length of a polyvinyl alcohol-type film is 4 km or more, More preferably, it is 4.5 km or more from the point of enlargement, Preferably it is 5 km or more.
  • the upper limit of the length of the film is preferably 50 km or less, particularly preferably 40 km or less, and further preferably 30 km or less from the viewpoint of avoiding breakage.
  • the gas is sprayed from the viewpoint of avoiding breakage, 2) after the water swelling step, and / or 3) dyeing step.
  • the water swelling step particularly preferably 2) after the water swelling step, more preferably 2) within the range of 10 seconds after the water swelling step.
  • the surface of the film to be sprayed is not particularly limited, and can be sprayed on the front surface, the back surface, and both surfaces.
  • a polyvinyl alcohol film as a raw material is obtained by discharging and flowing an aqueous solution of a polyvinyl alcohol resin into a cast mold such as a cast belt and continuously drying the film. In such drying, the states on both sides are often not exactly the same, and the moisture on one side is often low or the degree of crystallinity is high.
  • the surface with little moisture absorbs water and tends to stretch, the film tends to curl on the opposite surface side in the 2) water swelling process and 3) dyeing process in the production of the polarizing film. In such a case, in the present invention, it is effective to spray gas on both ends on the opposite surface side in the curl direction.
  • the gas to be blown includes gases such as air, nitrogen, oxygen, water vapor, and inert gas.
  • gases such as air, nitrogen, oxygen, water vapor, and inert gas.
  • air or water vapor is preferable in that it does not adversely affect the performance of the polarizing film, and air is more preferable in terms of simplicity of equipment.
  • the temperature is preferably 10 to 50 ° C., particularly preferably 20 to 40 ° C.
  • the water swelling step is 10 to 45 ° C., preferably 20 to 35 ° C. for 0.1 to 10 minutes, preferably 0.5 to 5 in terms of controlling the degree of swelling of the polyvinyl alcohol film. Dipped in water for a minute.
  • the water may contain a small amount of an iodide compound, an additive such as a surfactant, alcohol and the like.
  • a polyvinyl alcohol film wound on a roll is unwound from the roll and transferred in the horizontal direction.
  • the water swelling of the polyvinyl alcohol film is performed by the water swelling step. Thereafter, the polyvinyl alcohol film pulled up from the water swelling tank is transferred to a dyeing tank through a roll, and 3) the polyvinyl alcohol film is dyed in a dyeing step.
  • the air is blown onto both ends of the film, as described above, between 2) the water swelling process and 3) the dyeing process. Breaks and wrinkles are most likely to occur between these processes, and once the films are stuck together with the breaks or wrinkles, they are not easily peeled off.
  • the processes 2) and 3) are the first processes for manufacturing the polarizing film, so the influence on the subsequent processes is significant.
  • the specific position of spraying is, for example, 2) Immediately after coming out of the water swelling tank in the water swelling step and immediately after the first roll a.
  • the position and direction of spraying are schematically shown by arrows in FIG.
  • the distance A until the film exits the water swelling tank in 2) the water swelling step and comes into contact with the first roll a is 1 m or less. This is a case where the distance B from the roll a to the roll b just before the dyeing tank is 1 m or less. If the distance A is too long, there is a tendency for folds and wrinkles to increase.
  • the distance A from the water swelling tank to the roll a represents the shortest distance from the liquid surface of the water swelling tank to the roll a, and the distance B from the first roll a to the roll b just before the dyeing tank is the same as that of the roll a. This represents the shortest distance between the roll b.
  • the tension between the rolls in the series of steps is preferably 1 to 100 N / m. If the tension between the rolls is too large, it tends to break, and conversely if it is too small, it tends to increase creases and wrinkles. Furthermore, the transfer speed of the film from 2) the water swelling process to 3) the dyeing process is preferably 1 m / min or more, particularly preferably 1.5 m / min or more, more preferably 2 m from the viewpoint of productivity. / Min or more.
  • nozzles are not particularly limited, and known nozzles such as point discharge nozzles, line discharge nozzles, and surface discharge nozzles can be used, but point discharge is preferable from the viewpoint of controlling the spray position.
  • a plurality of the same types of nozzles may be installed, or a plurality of types of nozzles may be combined.
  • the position of the nozzle is preferably from the point of avoiding the breakage of the film until the film comes out of the water swelling tank in the water swelling step and comes into contact with the transport roll a.
  • the distance from the outlet of the water swelling tank to the nozzle is within 1 m from the viewpoint of avoiding wrinkles of the film, and more preferably, within 0.5 m from the transport roll a to the nozzle from the viewpoint of film flatness. Is the distance.
  • the distance from the outlet of the water swelling tank to the nozzle and the distance from the transport roll a to the nozzle each represent the shortest distance.
  • the distance between the nozzle and the film surface is preferably 1 to 100 mm in terms of avoiding film breakage, and particularly preferably 2 to 50 mm in terms of avoiding film wrinkles. is there.
  • the distance between the nozzle and the film surface represents the shortest distance, and specifically represents the distance between the nozzle and the film surface in a direction perpendicular to the film surface.
  • the spraying flow velocity and the spraying angle are important in terms of curling prevention effects.
  • the spraying flow rate is preferably 0.1 to 10 m / sec. Particularly preferred is 0.2 to 5 m / sec, and even more preferred is 0.3 to 3 m / sec. If the flow rate is too slow, the effect of preventing curling tends to decrease, and if the flow rate is too fast, the film tends to swell.
  • the air blowing direction When the air blowing direction is vertically projected onto the film surface, in other words, when the film surface is viewed in a direction perpendicular to the film surface, the air blowing direction is the film width direction (TD direction) or the film transport direction (MD Direction). Therefore, preferably, the air blowing angle includes not only the angle ⁇ 1 formed by the air blowing direction and the film surface, but also the direction when the air blowing direction is vertically projected on the film surface and the film transport direction. The angle ⁇ 2 formed with the (MD direction) is included (see FIGS. 4 to 6). In FIG.
  • the film transport direction is the x-axis
  • the film width direction is the y-axis
  • the direction perpendicular to the film surface is the z-axis
  • the film surface is the xy surface
  • the surface is perpendicular to the film surface.
  • the plane parallel to the width direction is the yz plane
  • the plane perpendicular to the film plane and parallel to the film transfer direction is the xz plane.
  • the angle ⁇ 1 formed by the air blowing direction and the film surface is preferably 5 to 80 °, particularly preferably 10 to 70 °, and further preferably 20 to 60 °. If the spray angle ⁇ 1 is too low, the effect of preventing curling tends to decrease, and if it is too high, the film tends to be swelled.
  • the angle ⁇ 2 formed by the direction when the air blowing direction is vertically projected onto the film surface and the film transport direction (MD direction) is preferably 5 to 175 °, particularly preferably 20 to 90 °. More preferably, it is 30 to 60 °.
  • the spray angle ⁇ 2 is too low, the effect of preventing curling tends to decrease, and if it is too high, wrinkles tend to occur on the film.
  • the flow velocity and the spray angle of the spraying may be the same for all nozzles or may be different for each nozzle.
  • the spraying flow rate is gradually set lower from the upstream side to the downstream side in the film transfer direction (MD direction), or the spraying angle ⁇ 1 is gradually lowered. A method is mentioned.
  • the conditions described above are preferable for the nozzle used, the arrangement of the nozzles, the spraying flow rate, and the spraying angle.
  • the polyvinyl alcohol film is transferred to the following 3) dyeing step and 4) stretching step in a state where there is no break or wrinkle.
  • the polarizing film of the present invention is 1) after the unwinding step, 2) the water swelling step, 3) the dyeing step, 4) the stretching step, 5) the boric acid crosslinking step, and if necessary, the washing step and the drying step. It is manufactured through processes such as Such manufacturing steps are not necessarily performed in the order of 2) to 5), and a plurality of steps may be appropriately combined.
  • 2) the stretching process may be performed simultaneously with 2) the water swelling process, 2) after the water swelling process, 3) the stretching process may be performed with the dyeing process, and 2) the water swelling process.
  • 3) After the dyeing step, 5) The boric acid crosslinking step and 4) the stretching step may be performed, 2) the water swelling step, 3) the dyeing step, and 5) the boric acid crosslinking step.
  • a stretching process may be performed.
  • the dyeing step is performed by bringing the film into contact with a liquid containing iodine or a dichroic dye.
  • a liquid containing iodine or a dichroic dye usually, an iodine-potassium iodide aqueous solution is used.
  • the iodine concentration is suitably 0.1-2 g / L, and the potassium iodide concentration is 1-100 g / L.
  • the dyeing time is practically about 30 to 500 seconds.
  • the temperature of the treatment bath is preferably 5 to 50 ° C.
  • the aqueous solution may contain a small amount of an organic solvent compatible with water in addition to the aqueous solvent.
  • any means such as dipping, coating, spraying and the like can be applied.
  • the stretching step is a step of stretching 3 to 10 times in a uniaxial direction, and it is particularly preferable to stretch 3.5 to 6 times.
  • the film may be slightly stretched (stretching to prevent shrinkage in the width direction or more) in a direction perpendicular to the stretching direction.
  • the temperature during stretching is preferably selected from a temperature range of 30 to 170 ° C.
  • the draw ratio may be finally set within the above range, and the drawing operation may be performed not only in one stage but also in any stage of the manufacturing process.
  • the boric acid crosslinking step is performed using a boron compound such as boric acid or borax.
  • the boron compound is used in the form of an aqueous solution or a water-organic solvent mixture at a concentration of about 10 to 100 g / L, and it is desirable to allow a small amount of potassium iodide to coexist in the solution from the viewpoint of stabilizing the polarization performance.
  • the treatment temperature is preferably about 30 to 70 ° C., and the treatment time is preferably about 0.1 to 20 minutes.
  • the film may be washed.
  • the precipitate generated on the surface of the film can be removed by the washing treatment.
  • the cleaning treatment is performed, for example, by immersing a polyvinyl alcohol film in an aqueous iodide solution such as water or potassium iodide.
  • an aqueous potassium iodide solution the concentration of potassium iodide may be about 1 to 80 g / L.
  • the temperature during the washing treatment is usually 5 to 50 ° C., preferably 10 to 45 ° C.
  • the treatment time is usually 1 to 300 seconds, preferably 10 to 240 seconds.
  • the drying step may be performed in the atmosphere at 40 to 80 ° C. for 1 to 10 minutes.
  • the polarization degree of the polarizing film thus obtained is preferably 99.8% or more, more preferably 99.9% or more. If the degree of polarization is too low, there is a tendency that the contrast in the liquid crystal display cannot be secured.
  • the degree of polarization is generally the light transmittance (H 11 ) measured at the wavelength ⁇ in the state where two polarizing films are overlapped so that their orientation directions are the same direction, and the two polarizing films. It is calculated according to the following equation from the light transmittance (H 1 ) measured at the wavelength ⁇ in a state where the films are superposed so that the orientation directions are orthogonal to each other. [(H 11 ⁇ H 1 ) / (H 11 + H 1 )] 1/2
  • the single transmittance of the polarizing film of the present invention is preferably 42% or more. If the single transmittance is too low, it tends to be impossible to achieve high brightness of the liquid crystal display.
  • the single transmittance is a value obtained by measuring the light transmittance of a single polarizing film using a spectrophotometer.
  • the width of the polarizing film of the present invention is preferably 1 m or more, preferably 1.3 m or more from the viewpoint of increasing the area, and particularly preferably 1.5 m or more from the viewpoint of further increasing the area. From the viewpoint of avoiding breakage, it is more preferably 1.5 to 2.5 m.
  • the thickness of the polarizing film of the present invention is preferably 15 ⁇ m or less, particularly preferably 10 ⁇ m or less from the viewpoint of further thinning, more preferably 2 to 9 ⁇ m, particularly preferably from the viewpoint of avoiding breakage. Is 3 to 8 ⁇ m.
  • the polarizing film of the present invention Since the polarizing film of the present invention thus obtained has little polarization unevenness, it is suitable for producing a high-performance polarizing plate.
  • the manufacturing method which manufactures a polarizing plate from the polarizing film of this invention is demonstrated.
  • the polarizing film of the present invention is bonded to one side or both sides of an optically isotropic resin film as a protective film via an adhesive to form a polarizing plate.
  • protective films include films of cellulose triacetate, cellulose diacetate, polycarbonate, polymethyl methacrylate, cycloolefin polymer, cycloolefin copolymer, polystyrene, polyethersulfone, polyarylene ester, poly-4-methylpentene, polyphenylene oxide, and the like. Or a sheet
  • the bonding method is performed by a known method. For example, after a liquid adhesive composition is uniformly applied to a polarizing film, a protective film, or both, the two are bonded and pressure-bonded, and heating or active energy is applied. This is done by irradiating a line.
  • a curable resin such as urethane resin, acrylic resin, urea resin or the like is applied to one side or both sides of the protective film and cured to obtain a polarizing plate.
  • the polarizing film and polarizing plate obtained by the present invention are excellent in polarization performance, such as portable information terminals, personal computers, televisions, projectors, signage, electronic desk calculators, electronic watches, word processors, electronic paper, game machines, videos, cameras. , Photo albums, thermometers, audio, liquid crystal display devices such as automobile and machinery instruments, sunglasses, anti-glare glasses, stereoscopic glasses, wearable displays, reflection for display elements (CRT, LCD, organic EL, electronic paper, etc.) It is preferably used for a prevention layer, an optical communication device, a medical device, a building material, a toy and the like.
  • polarization degree (%) was measured as follows.
  • the polarization degree of the obtained polarizing film at the central part and both ends (each 10 cm from the end) in the width direction was measured using RETS-1100A manufactured by Otsuka Electronics Co., Ltd.
  • Example 1 Manufacture of polyvinyl alcohol film
  • Polyvinyl alcohol resin with a weight average molecular weight of 142,000, saponification degree of 99.8 mol%, 1000 kg of water, 2500 kg of water and 100 kg of glycerin as a plasticizer are added, and the temperature is raised to 140 ° C. with stirring to adjust the resin concentration to 25% by weight.
  • the temperature is raised to 140 ° C. with stirring to adjust the resin concentration to 25% by weight.
  • the polyvinyl alcohol-based resin aqueous solution is supplied to a twin-screw extruder having a vent and defoamed, and then the aqueous solution temperature is set to 95 ° C., and a cast drum having a surface temperature of 90 ° C. from the T-type slit die discharge port, The film was cast by casting at a discharge speed of 0.6 m / min. Next, the obtained film was dried with a plurality of hot rolls, subjected to heat treatment at 120 ° C. for 3 minutes using a floating dryer, and cut into a 4 m width with a slit.
  • Nozzle Adjust hose made by MISUMI Nozzle position: 1 m from the outlet of the water swelling tank Nozzle position (height): 5mm from the top of the film Spraying flow velocity: 3m / sec Spraying angle ⁇ 1: 30 ° Spray angle ⁇ 2: 45 °
  • the obtained film was stretched in the transfer direction while being immersed and dyed in an aqueous solution composed of 0.9 g / L of iodine and 30 g / L of potassium iodide (0.5 minutes at 28 ° C., 1.6 times stretching ratio). ) [3) Dyeing step]. Next, it was immersed in an aqueous solution having a composition of boric acid 25 g / L and potassium iodide 30 g / L, and uniaxially stretched in the transport direction while crosslinking with boric acid (55 ° C. for 1 minute, stretch ratio 2.0 times) [5] Boric acid crosslinking step].
  • the film was washed with an aqueous potassium iodide solution and dried to obtain a polarizing film having a total draw ratio of 5.4 times (width 1.8 m, thickness 7 ⁇ m).
  • the obtained polarizing film was not broken or wrinkled, and no breakage occurred over a length of 12 km.
  • Table 1 shows the polarization characteristics of the obtained polarizing film.
  • a triacetyl cellulose film (TAC film) with a thickness of 40 ⁇ m was bonded to both surfaces of the obtained polarizing film using a polyvinyl alcohol-based aqueous solution as an adhesive, and dried at 50 ° C. to obtain a polarizing plate. Polarization unevenness was not observed in the obtained polarizing plate.
  • Example 2 a polarizing film was obtained in the same manner as in Example 1 except that the air blowing angle ⁇ 1 was set to 60 °. About the obtained polarizing film, evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1. Further, a polarizing plate was obtained in the same manner as in Example 1. Polarization unevenness was not observed in the obtained polarizing plate.
  • Example 3 a polarizing film was obtained in the same manner as in Example 1 except that the air blowing angle ⁇ 2 was set to 135 °. About the obtained polarizing film, evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1. Further, a polarizing plate was obtained in the same manner as in Example 1. Polarization unevenness was not observed in the obtained polarizing plate.
  • Example 4 In Example 1, a polarizing film was obtained in the same manner as in Example 1 except that water vapor was blown instead of air. About the obtained polarizing film, evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1. Further, a polarizing plate was obtained in the same manner as in Example 1. Polarization unevenness was not observed in the obtained polarizing plate.
  • Example 1 the production of the polarizing film was started in the same manner as in Example 1 except that the spraying was not performed. However, 2) After the water swelling step, folds and wrinkles were observed at both ends of the film, and when a polarizing film having a length of 1 km was produced, breakage occurred in the dyeing tank. Table 1 shows the polarization characteristics of the obtained part. In addition, since the fracture occurred, the polarizing plate could not be manufactured.
  • a long polarizing film can be obtained without folds or wrinkles.
  • the degree of polarization is high not only in the central part of the polarizing film but also at both ends in the width direction, a polarizing film having a uniform degree of polarization from the central part to the end part of the polarizing film can be obtained.
  • the polarizing film of the present invention is a portable information terminal, personal computer, TV, projector, signage, electronic desk calculator, electronic clock, word processor, electronic paper, game machine, video, camera, photo album, thermometer, audio, automobile and machine.
  • Liquid crystal display devices such as various instruments, sunglasses, anti-glare glasses, stereoscopic glasses, wearable displays, antireflection layers for display elements (CRT, LCD, organic EL, electronic paper, etc.), optical communication equipment, medical equipment, building materials Used for toys.
  • PVA film polyvinyl alcohol-based film ⁇ 1 (°): angle formed by spraying direction and film surface ⁇ 2 (°): direction when the spraying direction is perpendicularly projected onto the surface of the polyvinyl alcohol-based film and transfer of the polyvinyl alcohol-based film Angle formed by direction Distance A: Distance between the liquid level of the water swelling tank and roll a Distance B: Distance between roll a and roll b

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Abstract

The purpose of the invention is to produce, with excellent productivity, a polarizing film with little unevenness in polarization by solving problems related to folding and creases throughout all of the steps for producing the polarizing film. Disclosed is a method for producing a polarizing film through: (1) a step for unwinding a polyvinyl alcohol-based film from a roll and transporting the film in the horizontal direction; (2) a water-swelling step; (3) a dyeing step; (4) a drawing step; and (5) a boric acid crosslinking step. Before and/or after one of the steps (2) to (4), a gas is blown onto both edges, in the width direction, of the film according to the following condition (a), to prevent curling of the film. Condition (a): the angle θ1 formed between the gas blowing direction and the surface of the film is from 5 to 80°.

Description

偏光膜の製造方法、偏光膜及び偏光板Manufacturing method of polarizing film, polarizing film and polarizing plate
 本発明は、液晶表示装置(以下、LCDと略称することがある。)等に使用される偏光膜の製造方法、偏光膜及び偏光板に関し、さらに詳しくは、原反であるポリビニルアルコール系フィルムをヨウ素で染色した偏光膜の製造方法、その製造法により製造される偏光膜、その偏光膜を用いた偏光板に関する。 The present invention relates to a method for producing a polarizing film, a polarizing film and a polarizing plate used in a liquid crystal display device (hereinafter sometimes abbreviated as LCD), and more specifically, a polyvinyl alcohol film as a raw material. The present invention relates to a method for producing a polarizing film dyed with iodine, a polarizing film produced by the production method, and a polarizing plate using the polarizing film.
 LCDは、携帯情報端末、液晶テレビ、卓上電子計算機、電子時計、パーソナルコンピュータ、ワードプロセッサ、自動車や機械の計器類等に使用されており、このLCDには偏光板が使用されている。偏光板としては、ヨウ素又は二色性染料を吸着配向させたポリビニルアルコール系フィルムからなる偏光膜の片面又は両面に、トリアセチルセルロースなどの保護フィルムを積層したものが一般に使用されており、明るく、高いコントラストを有するLCDを提供するために、高い透過率と高い偏光度を兼ね備えた偏光板が必要とされている。 LCDs are used in portable information terminals, liquid crystal televisions, desktop electronic calculators, electronic watches, personal computers, word processors, automobile and machine instruments, etc., and polarizing plates are used in this LCD. As the polarizing plate, one in which a protective film such as triacetyl cellulose is laminated on one side or both sides of a polarizing film made of a polyvinyl alcohol film to which iodine or a dichroic dye is adsorbed and oriented is brightly used. In order to provide an LCD having a high contrast, a polarizing plate having a high transmittance and a high degree of polarization is required.
 前述した偏光膜は、例えば、ポリビニルアルコール系フィルムを水(温水を含む)で膨潤させた後、ヨウ素で染色し、ヨウ素分子を配列させるために延伸し、延伸した状態を保持するためにホウ酸などの架橋剤で架橋し、乾燥させて製造されている。かかる製造工程は、ロールからポリビニルアルコール系フィルムを巻き出して、巻き取り機やニップロールを用いて、水平方向に搬送しながら連続して行われる。 The polarizing film described above, for example, is obtained by swelling a polyvinyl alcohol film with water (including warm water), dyeing with iodine, stretching to arrange iodine molecules, and boric acid to maintain the stretched state. It is produced by crosslinking with a crosslinking agent such as This manufacturing process is continuously performed while unwinding the polyvinyl alcohol film from the roll and transporting it in the horizontal direction using a winder or a nip roll.
 しかし、水膨潤、染色、延伸、ホウ酸架橋、乾燥の製造工程において、フィルムが吸水又は脱水してカールし、フィルムの幅方向端部に折れや皺が発生するので、偏光膜を生産性良く製造できないという問題があった。特に、フィルムが薄い場合には、かかる折れや皺が起因となってフィルムが破断し、生産が中断する問題もあった。更に、かかる端部の不具合は、偏光膜の内部にも影響して、偏光膜全体の偏光性能を低下させたり、偏光板の液晶セルへの均一な装着を困難にしたり、液晶表示画像の色ムラや白抜けなどの原因となっていた。 However, in the manufacturing process of water swelling, dyeing, stretching, boric acid crosslinking, and drying, the film absorbs water or dehydrates and curls, and folds and wrinkles occur at the end in the width direction of the film. There was a problem that it could not be manufactured. In particular, when the film is thin, there is a problem that the film breaks due to such folds and wrinkles and the production is interrupted. Furthermore, such a defect at the edge also affects the inside of the polarizing film, thereby degrading the polarizing performance of the entire polarizing film, making it difficult to uniformly attach the polarizing plate to the liquid crystal cell, and the color of the liquid crystal display image. It was the cause of unevenness and white spots.
 近年、液晶テレビなどの画面の大型化に伴い、従来品よりも一段と幅広薄型の偏光膜が必要とされる中、端部の折れや皺は、撲滅せねばならない課題であった。
 かかる折れや皺を低減するために、乾燥処理でフィルムの幅方向に一定の張力をかける手法が提案されている(例えば特許文献1参照。)。また、水中走行中のフィルムの幅方向両端部にノズルから水を噴射する手法が提案されている(例えば特許文献2参照。)。
In recent years, with the enlargement of screens of liquid crystal televisions and the like, a polarizing film that is wider and thinner than conventional products is required.
In order to reduce such folds and wrinkles, a method of applying a constant tension in the width direction of the film by a drying process has been proposed (for example, see Patent Document 1). Moreover, the method of injecting water from a nozzle to the both ends of the width direction of the film currently running underwater is proposed (for example, refer to patent documents 2).
特開2006-189560号公報JP 2006-189560 A 特開平7-247378号公報Japanese Patent Laid-Open No. 7-247378
 しかしながら、上記特許文献1の開示技術では、乾燥処理工程における折れや皺を回避できるものの、乾燥工程前の水膨潤、染色、延伸、ホウ酸架橋のうちいずれかの工程でフィルムに折れや皺が発生すると、そもそも乾燥工程まで搬送できないという課題がある。
 また、上記特許文献2の開示技術では、水中での折れや皺を回避できるものの、空中で発生する折れや皺を防ぐことができない。
 そこで、本発明は、偏光膜の全製造工程において、折れや皺の問題を解決し、生産性良く偏光ムラの少ない偏光膜を製造することを目的としたものである。
However, although the disclosed technique of Patent Document 1 can avoid creases and wrinkles in the drying process, the film may be folded or wrinkled in any of the steps of water swelling, dyeing, stretching, and boric acid crosslinking before the drying process. If it occurs, there is a problem that it cannot be transported to the drying process in the first place.
Moreover, although the disclosed technique of Patent Document 2 can avoid folding and wrinkles in water, it cannot prevent folding and wrinkles that occur in the air.
Therefore, the present invention aims to solve the problem of folding and wrinkles in the entire manufacturing process of the polarizing film, and to manufacture a polarizing film with high productivity and little polarization unevenness.
 そこで、本発明では以下の態様の発明を提供する。
 〔偏光膜の製造方法〕
 1)ポリビニルアルコール系フィルムをロールから巻き出して水平方向に移送する工程、2)水膨潤工程、3)染色工程、4)延伸工程、及び5)ホウ酸架橋工程を有する偏光膜の製造方法であって、
 前記2)~4)のいずれかの工程の前及び/又は後において、前記フィルムの幅方向両端部に気体を下記条件aで吹き付けて前記フィルムのカールを防止することを特徴とする偏光膜の製造方法。
 条件a)気体の吹き付け方向と前記フィルムの面とのなす角度θ1が5~80°である。
Therefore, the present invention provides the following aspects of the invention.
[Method for producing polarizing film]
1) A method for producing a polarizing film comprising a step of unwinding a polyvinyl alcohol film from a roll and transferring it horizontally, 2) a water swelling step, 3) a dyeing step, 4) a stretching step, and 5) a boric acid crosslinking step. There,
Before and / or after any of the steps 2) to 4), a gas is blown to both ends of the film in the width direction under the following condition a to prevent curling of the film: Production method.
Condition a) The angle θ1 formed between the gas blowing direction and the film surface is 5 to 80 °.
 〔偏光膜〕
 本発明の偏光膜の製造方法により製造される偏光膜。
[Polarizing film]
The polarizing film manufactured by the manufacturing method of the polarizing film of this invention.
 〔偏光板〕
 本発明の偏光膜の少なくとも片面に保護フィルムが設けられてなることを特徴とする偏光板。
〔Polarizer〕
A polarizing plate comprising a protective film provided on at least one surface of the polarizing film of the present invention.
 本発明において、「フィルムの幅方向」とは、一般には帯状のフィルムの長手方向に対して略直交する方向である。特に、ロールから巻き出し水平方向に移送されるポリビニルアルコール系フィルムにおいては、フィルムの移送方向に対して略直交する方向であり、典型的には、フィルムの両縁間の距離が最短となるときの方向をいう。
 本発明においては、フィルムの幅方向を「TD方向」と称し、フィルムの移送方向を「MD方向」と称する。
 なお、以下では、ポリビニルアルコール系フィルムを単に「フィルム」ともいう。
In the present invention, the “film width direction” is generally a direction substantially perpendicular to the longitudinal direction of the belt-like film. In particular, in a polyvinyl alcohol film unwound from a roll and transferred in the horizontal direction, the direction is substantially perpendicular to the film transfer direction, and typically the distance between both edges of the film is the shortest. The direction.
In the present invention, the width direction of the film is referred to as “TD direction”, and the transfer direction of the film is referred to as “MD direction”.
Hereinafter, the polyvinyl alcohol film is also simply referred to as “film”.
 本発明の偏光膜の製造方法によれば、2)水膨潤工程、3)染色工程、及び4)延伸工程のいずれかの工程の前及び/又は後において、ポリビニルアルコール系フィルムの幅方向両端部に気体を所定の条件で吹き付けてフィルムのカールを防止するので、フィルム全面を平坦に保つことができ、折れや皺を回避することができる。 According to the method for producing a polarizing film of the present invention, both ends of the polyvinyl alcohol film in the width direction before and / or after any of the steps 2) water swelling step, 3) dyeing step, and 4) stretching step. Since the film is blown under a predetermined condition to prevent curling of the film, the entire surface of the film can be kept flat, and folding and wrinkles can be avoided.
 本発明の製造方法により、幅広長尺薄型の偏光膜を生産性良く製造でき、偏光膜の中央部から端部まで均一な偏光度を有する偏光膜を得ることができる。更に、幅広長尺薄型の偏光板の製造を容易にすることができ、液晶表示画像の色ムラや白抜けを低減することができる。 By the production method of the present invention, a wide, long and thin polarizing film can be produced with high productivity, and a polarizing film having a uniform degree of polarization from the center to the end of the polarizing film can be obtained. Furthermore, it is possible to easily produce a wide, long and thin polarizing plate, and to reduce color unevenness and white spots in a liquid crystal display image.
図1は1)原反巻き出し工程、2)水膨潤工程、3)染色工程における空気の吹き付け箇所を模式的に示す図である。FIG. 1 is a diagram schematically showing locations of air blowing in 1) a raw fabric unwinding step, 2) a water swelling step, and 3) a dyeing step. 図2は2)水膨潤工程と3)染色工程間における水膨潤槽の液面とロールaとの距離A、ロールa及びロールb間の距離Bを模式的に示す図である。FIG. 2 is a diagram schematically showing the distance A between the liquid level of the water swelling tank and the roll a and the distance B between the roll a and the roll b between 2) the water swelling process and 3) the dyeing process. 図3Aはポリビニルアルコール系フィルム(PVAフィルム)の表面に液体を吹き付ける場合の吹き付け態様を示す図である。FIG. 3A is a diagram showing a spraying mode when a liquid is sprayed on the surface of a polyvinyl alcohol film (PVA film). 図3Bはポリビニルアルコール系フィルム(PVAフィルム)の裏面に液体を吹き付ける場合の吹き付け態様を示す図である。FIG. 3B is a diagram showing a spraying mode when a liquid is sprayed on the back surface of a polyvinyl alcohol film (PVA film). 図4はポリビニルアルコール系フィルムの表面又は裏面に空気を吹き付けた場合において、吹き付け方向とフィルムの面とのなす角度θ1を示す図である。FIG. 4 is a diagram showing an angle θ1 formed by the blowing direction and the surface of the film when air is blown onto the front or back surface of the polyvinyl alcohol film. 図5はポリビニルアルコール系フィルムの表面又は裏面に空気を吹き付けた場合において、吹き付け方向をポリビニルアルコール系フィルムの面に垂直投影したときの方向とポリビニルアルコール系フィルムの移送方向とのなす角度θ2を示す図である。FIG. 5 shows the angle θ2 formed between the direction when the blowing direction is perpendicularly projected onto the surface of the polyvinyl alcohol film and the transfer direction of the polyvinyl alcohol film when air is blown onto the front or back surface of the polyvinyl alcohol film. FIG. 図6はポリビニルアルコール系フィルムの表面又は裏面に空気を吹き付けた場合において、吹き付け方向とフィルムの面とのなす角度θ1、及び吹き付け方向をポリビニルアルコール系フィルムの面に垂直投影したときの方向とポリビニルアルコール系フィルムの移送方向とのなす角度θ2を示す図である。FIG. 6 shows the angle θ1 formed between the blowing direction and the surface of the film when air is blown on the front or back surface of the polyvinyl alcohol film, and the direction when the blowing direction is vertically projected onto the surface of the polyvinyl alcohol film. It is a figure which shows angle (theta) 2 which makes with the transfer direction of an alcoholic film. 図7はポリビニルアルコール系フィルムに空気を吹き付ける場合の吹き付け態様の一例を示す図である。FIG. 7 is a diagram showing an example of a spraying mode when air is sprayed on a polyvinyl alcohol film.
 以下、本発明の構成につき詳細に説明するが、これらは望ましい実施態様の一例を示すものであり、本発明はこれらの内容に特定されるものではない。 Hereinafter, the configuration of the present invention will be described in detail, but these show examples of desirable embodiments, and the present invention is not limited to these contents.
 本発明の偏光膜の製造方法では、1)ポリビニルアルコール系フィルムをロールから巻き出して水平方向に移送する工程、2)水膨潤工程、3)染色工程、4)延伸工程、及び5)ホウ酸架橋工程を経て偏光膜を製造する。なお、1)ポリビニルアルコール系フィルムをロールから巻き出して水平方向に移送する工程を以下では1)原反巻き出し工程ともいう。
 上記1)原反巻き出し工程に用いられるポリビニルアルコール系フィルムは、ポリビニルアルコール系樹脂をフィルム状に製膜し、ロールに巻き取られたものである。
In the method for producing a polarizing film of the present invention, 1) a step of unwinding a polyvinyl alcohol film from a roll and transferring it horizontally, 2) a water swelling step, 3) a dyeing step, 4) a stretching step, and 5) boric acid A polarizing film is manufactured through a crosslinking step. In addition, 1) The process which unwinds a polyvinyl alcohol-type film from a roll and transfers it to a horizontal direction is also called 1) original fabric unwinding process below.
The polyvinyl alcohol film used in the above 1) raw roll unwinding step is a film obtained by forming a polyvinyl alcohol resin into a film and wound up on a roll.
 ポリビニルアルコール系フィルムに用いられるポリビニルアルコール系樹脂としては、通常、未変性のポリビニルアルコール系樹脂、即ち、酢酸ビニルを重合して得られるポリ酢酸ビニルをケン化して製造される樹脂が用いられる。本発明で用いられるポリビニルアルコール系フィルムにおいては、必ずしもこれに限定されるものではなく、酢酸ビニルと、少量(例えば、10モル%以下、好ましくは5モル%以下)の酢酸ビニルと共重合可能な成分との共重合体をケン化して得られるポリビニルアルコール系樹脂を用いることもできる。酢酸ビニルと共重合可能な成分としては、例えば、不飽和カルボン酸(例えば、塩、エステル、アミド、ニトリル等を含む)、炭素数2~30のオレフィン類(例えば、エチレン、プロピレン、n-ブテン、イソブテン等)、ビニルエーテル類、不飽和スルホン酸塩等が挙げられる。また、ケン化後の水酸基を化学修飾して得られる変性ポリビニルアルコール系樹脂を用いることもできる。 As the polyvinyl alcohol resin used for the polyvinyl alcohol film, an unmodified polyvinyl alcohol resin, that is, a resin produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate is usually used. The polyvinyl alcohol film used in the present invention is not necessarily limited thereto, and can be copolymerized with vinyl acetate and a small amount (for example, 10 mol% or less, preferably 5 mol% or less) of vinyl acetate. A polyvinyl alcohol-based resin obtained by saponifying a copolymer with a component can also be used. Examples of components copolymerizable with vinyl acetate include unsaturated carboxylic acids (including salts, esters, amides, nitriles, etc.), and olefins having 2 to 30 carbon atoms (eg, ethylene, propylene, n-butene). , Isobutene, etc.), vinyl ethers, unsaturated sulfonates and the like. Moreover, the modified polyvinyl alcohol-type resin obtained by chemically modifying the hydroxyl group after saponification can also be used.
 また、ポリビニルアルコール系樹脂として、側鎖に1,2-ジオール構造を有するポリビニルアルコール系樹脂を用いることもできる。かかる側鎖に1,2-ジオール構造を有するポリビニルアルコール系樹脂は、例えば、(i)酢酸ビニルと3,4-ジアセトキシ-1-ブテンとの共重合体をケン化する方法、(ii)酢酸ビニルとビニルエレンカーボネートとの共重合体をケン化及び脱炭酸する方法、(iii)酢酸ビニルと2,2-ジアルキル-4-ビニル-1,3-ジオキソランとの共重合体をケン化及び脱ケタール化する方法、(iv)酢酸ビニルとグリセリンモノアリルエーテルとの共重合体をケン化する方法、等により得られる。 Also, as the polyvinyl alcohol resin, a polyvinyl alcohol resin having a 1,2-diol structure in the side chain can be used. Such a polyvinyl alcohol resin having a 1,2-diol structure in the side chain includes, for example, (i) a method for saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene, and (ii) acetic acid. A method of saponifying and decarboxylating a copolymer of vinyl and vinylene carbonate; (iii) saponifying and decarboxylating a copolymer of vinyl acetate and 2,2-dialkyl-4-vinyl-1,3-dioxolane. It is obtained by a method of ketalization, (iv) a method of saponifying a copolymer of vinyl acetate and glyceryl monoallyl ether, or the like.
 ポリビニルアルコール系樹脂の重量平均分子量は、光学性能や延伸性の点で、10万~30万であることが好ましく、特に好ましくは11万~28万、更に好ましくは12万~26万である。
 ポリビニルアルコール系樹脂の平均ケン化度は、光学性能の点で、通常98モル%以上であることが好ましく、特に好ましくは99モル%以上、更に好ましくは99.5モル%以上、殊に好ましくは99.8モル%以上である。
The weight average molecular weight of the polyvinyl alcohol resin is preferably 100,000 to 300,000, particularly preferably 110,000 to 280,000, and more preferably 120,000 to 260,000 from the viewpoint of optical performance and stretchability.
The average saponification degree of the polyvinyl alcohol-based resin is usually preferably 98 mol% or more, particularly preferably 99 mol% or more, more preferably 99.5 mol% or more, particularly preferably from the viewpoint of optical performance. It is 99.8 mol% or more.
 本発明に用いるポリビニルアルコール系樹脂として、変性種、変性量、重量平均分子量、平均ケン化度などの異なる2種以上のものを併用してもよい。 As the polyvinyl alcohol resin used in the present invention, two or more kinds having different modified species, modified amount, weight average molecular weight, average saponification degree, etc. may be used in combination.
 本発明で使用されるポリビニルアルコール系フィルムは、上記のポリビニルアルコール系樹脂を用いてポリビニルアルコール系樹脂水溶液を調製し、かかる水溶液をキャストドラム、キャストベルト、キャスト樹脂フィルムなどのキャスト型に吐出及び流延して製膜し、乾燥後、ロールに巻き取ることで製造される。 The polyvinyl alcohol film used in the present invention prepares a polyvinyl alcohol resin aqueous solution using the above polyvinyl alcohol resin, and discharges and flows the aqueous solution to a cast mold such as a cast drum, a cast belt, and a cast resin film. It is manufactured by rolling and forming a film, winding it on a roll after drying.
 ポリビニルアルコール系樹脂水溶液には、ポリビニルアルコール系樹脂以外に、必要に応じて、グリセリン、ジグリセリン、トリグリセリン、エチレングリコール、トリエチレングリコール、ポリエチレングリコール、トリメチロールプロパンなどの一般的に使用される可塑剤や、ノニオン性、アニオン性、及び/またはカチオン性の界面活性剤を含有させることが、製膜性の点から好ましい。 In addition to polyvinyl alcohol-based resins, polyvinyl alcohol-based resin aqueous solutions include plastics commonly used such as glycerin, diglycerin, triglycerin, ethylene glycol, triethylene glycol, polyethylene glycol, and trimethylol propane as necessary. It is preferable from the viewpoint of film forming property to contain an agent and a nonionic, anionic, and / or cationic surfactant.
 ポリビニルアルコール系樹脂水溶液の樹脂濃度は、10~60重量%であることが好ましく、特に好ましくは15~55重量%、更に好ましくは20~50重量%である。 The resin concentration of the aqueous polyvinyl alcohol resin solution is preferably 10 to 60% by weight, particularly preferably 15 to 55% by weight, and further preferably 20 to 50% by weight.
 キャスト型に吐出する際のポリビニルアルコール系樹脂水溶液の温度は、80~100℃であることが好ましく、特に好ましくは85~98℃である。また、キャスト型に吐出されるポリビニルアルコール系樹脂水溶液の吐出速度は、0.1~5m/分であることが好ましく、特に好ましくは0.2~4m/分、更に好ましくは0.3~3m/分である。 The temperature of the aqueous polyvinyl alcohol resin solution when discharged into a cast mold is preferably 80 to 100 ° C., particularly preferably 85 to 98 ° C. The discharge rate of the aqueous polyvinyl alcohol resin solution discharged into the cast mold is preferably 0.1 to 5 m / min, particularly preferably 0.2 to 4 m / min, and more preferably 0.3 to 3 m. / Min.
 キャストドラム等のキャスト型の表面温度は、40~99℃であることが好ましく、特に好ましくは60~95℃である。
 キャスト型で製膜されたフィルムの乾燥は、フィルムの表面と裏面とを複数本の熱ロールの外周部に交互に接触させながら搬送させることにより行なわれる。熱ロールによる乾燥後、フィルムに熱処理を行ってもよい。熱処理については、60~150℃で行われることが好ましく、特には80~130℃が好ましい。
 フィルムをロールに巻き取る前に、フィルムの両端部をスリットで切り落としてもよい。
The surface temperature of a cast mold such as a cast drum is preferably 40 to 99 ° C, particularly preferably 60 to 95 ° C.
The film formed in the cast mold is dried by conveying the film while the front surface and the back surface of the film are alternately brought into contact with the outer peripheral portions of a plurality of heat rolls. After drying with a hot roll, the film may be heat treated. The heat treatment is preferably performed at 60 to 150 ° C., particularly preferably 80 to 130 ° C.
Before winding the film on a roll, both ends of the film may be cut off with slits.
 かかるポリビニルアルコール系フィルムの厚さは、偏光膜の薄型化の点から、5~60μmであることが好ましく、更なる薄型化の点から、より好ましくは5~30μmであり、破断回避の点から、特に好ましくは10~30μmである。
 また、ポリビニルアルコール系フィルムの幅は、3m以上であることが好ましく、大面積化の点からより好ましくは4m以上、破断回避の点から特に好ましくは4~6mである。
 また、ポリビニルアルコール系フィルムの長さは、4km以上であることが好ましく、大面積化の点からより好ましくは4.5km以上、好ましくは5km以上である。
 なお、フィルムの長さの上限は、破断回避の点から、好ましくは50km以下、特に好ましくは40km以下、更に好ましくは30km以下である。
The thickness of the polyvinyl alcohol film is preferably 5 to 60 μm from the viewpoint of thinning the polarizing film, more preferably 5 to 30 μm from the viewpoint of further thinning, from the viewpoint of avoiding breakage. Particularly preferably, the thickness is 10 to 30 μm.
The width of the polyvinyl alcohol film is preferably 3 m or more, more preferably 4 m or more from the viewpoint of increasing the area, and particularly preferably 4 to 6 m from the viewpoint of avoiding breakage.
Moreover, it is preferable that the length of a polyvinyl alcohol-type film is 4 km or more, More preferably, it is 4.5 km or more from the point of enlargement, Preferably it is 5 km or more.
The upper limit of the length of the film is preferably 50 km or less, particularly preferably 40 km or less, and further preferably 30 km or less from the viewpoint of avoiding breakage.
 本発明の製造方法では、上記2)水膨潤工程、3)染色工程、及び4)延伸工程のいずれかの工程の前及び/又は後において、搬送されるフィルムの幅方向両端部に気体を所定の条件で吹き付けてフィルムのカールを防止する。
 4)延伸工程の後の5)ホウ酸架橋工程後や、その後の6)乾燥工程後に、気体の吹き付けを行うことも可能であるが、かかる工程ではフィルムが架橋や乾燥により高硬度になるので折れや皺は発生し難く、吹き付けによる効果は顕著では無い。
In the production method of the present invention, before and / or after any one of the above-mentioned 2) water swelling step, 3) dyeing step, and 4) stretching step, gas is given to both ends in the width direction of the film to be conveyed. To prevent the film from curling.
4) After the stretching step 5) After the boric acid crosslinking step and after the subsequent 6) drying step, it is possible to spray the gas, but in this step, the film becomes hard due to crosslinking and drying. Folds and wrinkles are unlikely to occur and the effect of spraying is not significant.
 気体の吹き付けを行なう時期は、上記2)水膨潤工程、3)染色工程、及び4)延伸工程の中では、折れ回避の点から、2)水膨潤工程の後、及び/又は3)染色工程の後が好ましく、特に好ましくは、しわ回避の点で、2)水膨潤工程の後であり、更に好ましくは、偏光膜の平坦化の点で2)水膨潤工程の後10秒以内である。 In the above 2) water swelling step, 3) dyeing step, and 4) stretching step, the gas is sprayed from the viewpoint of avoiding breakage, 2) after the water swelling step, and / or 3) dyeing step. After the water swelling step, particularly preferably 2) after the water swelling step, more preferably 2) within the range of 10 seconds after the water swelling step.
 吹き付けを行うフィルムの面は、特に限定されず、表面、裏面、及び両面への吹き付けが可能である。一般的に、原反となるポリビニルアルコール系フィルムは、ポリビニルアルコール系樹脂の水溶液をキャストベルトなどのキャスト型に吐出及び流涎して製膜し、連続的に乾燥して得られる。かかる乾燥において、両面の状態が全く同じにはならないことが多く、片面側の水分が少なかったり、結晶化度が高かったりする場合が多い。当然のことながら、水分の少ない面が吸水して伸びやすいため、偏光膜製造における2)水膨潤工程や3)染色工程において、反対面側にフィルムがカールしやすい。かかる場合、本発明においては、カール方向である該反対面側の両端部に、気体の吹き付けを行うことが有効である。 The surface of the film to be sprayed is not particularly limited, and can be sprayed on the front surface, the back surface, and both surfaces. Generally, a polyvinyl alcohol film as a raw material is obtained by discharging and flowing an aqueous solution of a polyvinyl alcohol resin into a cast mold such as a cast belt and continuously drying the film. In such drying, the states on both sides are often not exactly the same, and the moisture on one side is often low or the degree of crystallinity is high. As a matter of course, since the surface with little moisture absorbs water and tends to stretch, the film tends to curl on the opposite surface side in the 2) water swelling process and 3) dyeing process in the production of the polarizing film. In such a case, in the present invention, it is effective to spray gas on both ends on the opposite surface side in the curl direction.
 吹き付ける気体としては、空気、窒素、酸素、水蒸気、不活性ガスなどの気体が挙げられる。これらの中では、偏光膜の性能に悪影響しない点で、空気又は水蒸気が好ましく、より好ましくは、設備の簡便さの点で、空気である。空気を用いる場合、温度は10~50℃が好ましく、特に好ましくは20~40℃である。 The gas to be blown includes gases such as air, nitrogen, oxygen, water vapor, and inert gas. Among these, air or water vapor is preferable in that it does not adversely affect the performance of the polarizing film, and air is more preferable in terms of simplicity of equipment. When air is used, the temperature is preferably 10 to 50 ° C., particularly preferably 20 to 40 ° C.
 以下に、本発明の好ましい実施形態の1つとして、2)水膨潤工程後に空気の吹き付けを行う場合を例にとって、本発明を説明する。 Hereinafter, the present invention will be described as an example of a preferred embodiment of the present invention, taking as an example the case where 2) air is blown after the water swelling step.
 一般的に、2)水膨潤工程は、ポリビニルアルコール系フィルムの膨潤度制御の点で、10~45℃、好ましくは20~35℃で、0.1~10分間、好ましくは0.5~5分間、水に浸漬して行われる。なお、水には、ヨウ化化合物、界面活性剤等の添加物、アルコール等が少量入っていてもよい。
 例えば、図1に示すように、ロールに巻かれたポリビニルアルコール系フィルムをロールから巻き出して水平方向に移送する1)原反巻き出し工程を経て、水膨潤槽へ投入されたポリビニルアルコール系フィルムは、2)水膨潤工程により、ポリビニルアルコール系フィルムの水膨潤が行なわれる。その後、水膨潤槽から引き上げられたポリビニルアルコール系フィルムは、ロールを経て染色槽へと移送され、3)染色工程にてポリビニルアルコール系フィルムの染色が行なわれる。
Generally, 2) the water swelling step is 10 to 45 ° C., preferably 20 to 35 ° C. for 0.1 to 10 minutes, preferably 0.5 to 5 in terms of controlling the degree of swelling of the polyvinyl alcohol film. Dipped in water for a minute. The water may contain a small amount of an iodide compound, an additive such as a surfactant, alcohol and the like.
For example, as shown in FIG. 1, a polyvinyl alcohol film wound on a roll is unwound from the roll and transferred in the horizontal direction. 1) A polyvinyl alcohol film fed into a water swelling tank through an unwinding step. 2) The water swelling of the polyvinyl alcohol film is performed by the water swelling step. Thereafter, the polyvinyl alcohol film pulled up from the water swelling tank is transferred to a dyeing tank through a roll, and 3) the polyvinyl alcohol film is dyed in a dyeing step.
 本発明において、フィルム両端部への空気の吹き付けは、上述したとおり、2)水膨潤工程後、3)染色工程に至るまでの工程間でフィルムに対して行われることが好ましい。かかる工程間で折れや皺が最も発生しやすく、折れや皺でフィルム同士が一旦、貼り付くと簡単には剥がれない。また、かかる工程間で折れや皺が発生した場合には、2)及び3)の工程が偏光膜製造の初工程であるので、後工程に与える影響が甚大である。吹き付けの具体的な位置は、例えば、2)水膨潤工程の水膨潤槽から出た直後、及び最初のロールaの直後が好ましい。なお、図1中の矢印にて吹き付けの位置と方向を模式的に示す。 In the present invention, it is preferable that the air is blown onto both ends of the film, as described above, between 2) the water swelling process and 3) the dyeing process. Breaks and wrinkles are most likely to occur between these processes, and once the films are stuck together with the breaks or wrinkles, they are not easily peeled off. In addition, when a crease or wrinkle occurs between the processes, the processes 2) and 3) are the first processes for manufacturing the polarizing film, so the influence on the subsequent processes is significant. The specific position of spraying is, for example, 2) Immediately after coming out of the water swelling tank in the water swelling step and immediately after the first roll a. In addition, the position and direction of spraying are schematically shown by arrows in FIG.
 本発明においては、図2に示すように、フィルムが2)水膨潤工程における水膨潤槽を出て最初のロールaに接するまでの距離Aが1m以下であることが好ましく、特に好ましくは、最初のロールaから染色槽直前のロールbまでの距離Bも1m以下である場合である。距離Aが長すぎると、折れや皺が増加する傾向がある。なお、水膨潤槽からロールaまでの距離Aは、水膨潤槽の液面からロールaまでの最短距離を表し、最初のロールaから染色槽直前のロールbまでの距離Bは、ロールaとロールbとの間の最短距離を表す。
 また、一連の工程におけるロール間の張力は、1~100N/mであることが好ましい。ロール間の張力が大きすぎると、破断しやすい傾向があり、逆に小さすぎると、折れや皺が増加する傾向がある。
 更に、2)水膨潤工程から3)染色工程に至るフィルムの移送速度は、生産性の点から、1m/分以上であることが好ましく、特に好ましくは1.5m/分以上、更に好ましくは2m/分以上である。
In the present invention, as shown in FIG. 2, it is preferable that the distance A until the film exits the water swelling tank in 2) the water swelling step and comes into contact with the first roll a is 1 m or less. This is a case where the distance B from the roll a to the roll b just before the dyeing tank is 1 m or less. If the distance A is too long, there is a tendency for folds and wrinkles to increase. The distance A from the water swelling tank to the roll a represents the shortest distance from the liquid surface of the water swelling tank to the roll a, and the distance B from the first roll a to the roll b just before the dyeing tank is the same as that of the roll a. This represents the shortest distance between the roll b.
The tension between the rolls in the series of steps is preferably 1 to 100 N / m. If the tension between the rolls is too large, it tends to break, and conversely if it is too small, it tends to increase creases and wrinkles.
Furthermore, the transfer speed of the film from 2) the water swelling process to 3) the dyeing process is preferably 1 m / min or more, particularly preferably 1.5 m / min or more, more preferably 2 m from the viewpoint of productivity. / Min or more.
 空気による吹き付けを行う場合、ノズルを用いて、フィルムの幅方向両端部の片面または両面に空気を吐出することが好ましい。このとき、図3Aに示すように、フィルムの表面に空気を吐出してもよいし、図3Bに示すように、フィルムの裏面に空気を吐出してもよいし、フィルムの両面に空気を吐出してもよい。かかるノズルとしては、特に限定されず、点吐出ノズル、線吐出ノズル、面吐出ノズルなど公知のノズルを使用することができるが、吹き付け位置の制御の点から、点吐出が好ましい。かかるノズルは、同種のものを複数個設置してもよく、複数種のものを組み合わせても良い。 When spraying with air, it is preferable to discharge air to one or both sides of the both ends in the width direction of the film using a nozzle. At this time, as shown in FIG. 3A, air may be discharged to the surface of the film, as shown in FIG. 3B, air may be discharged to the back surface of the film, or air is discharged to both surfaces of the film. May be. Such nozzles are not particularly limited, and known nozzles such as point discharge nozzles, line discharge nozzles, and surface discharge nozzles can be used, but point discharge is preferable from the viewpoint of controlling the spray position. A plurality of the same types of nozzles may be installed, or a plurality of types of nozzles may be combined.
 ノズルの位置は、図2に示すように、フィルムの折れ回避の点で、フィルムが2)水膨潤工程における水膨潤槽を出た後、搬送用のロールaに接するまでの間が好ましく、特に好ましくは、フィルムの皺回避の点で、水膨潤槽の出口からノズルまで1m以内の距離であり、更に好ましくは、フィルムの平坦性の点で、搬送用のロールaからノズルまで0.5m以内の距離である。なお、水膨潤槽の出口からノズルまでの距離、及び搬送用のロールaからノズルまでの距離は、それぞれ最短距離を表す。
 また、ノズルとフィルム面との間の距離は、フィルムの折れ回避の点で、1~100mmの距離であることが好ましく、特に好ましくは、フィルムの皺回避の点で、2~50mmの距離である。なお、ノズルとフィルム面との間の距離は最短距離を表し、具体的には、フィルム面に垂直な方向におけるノズルとフィルム面との間の距離を表す。
As shown in FIG. 2, the position of the nozzle is preferably from the point of avoiding the breakage of the film until the film comes out of the water swelling tank in the water swelling step and comes into contact with the transport roll a. Preferably, the distance from the outlet of the water swelling tank to the nozzle is within 1 m from the viewpoint of avoiding wrinkles of the film, and more preferably, within 0.5 m from the transport roll a to the nozzle from the viewpoint of film flatness. Is the distance. The distance from the outlet of the water swelling tank to the nozzle and the distance from the transport roll a to the nozzle each represent the shortest distance.
The distance between the nozzle and the film surface is preferably 1 to 100 mm in terms of avoiding film breakage, and particularly preferably 2 to 50 mm in terms of avoiding film wrinkles. is there. The distance between the nozzle and the film surface represents the shortest distance, and specifically represents the distance between the nozzle and the film surface in a direction perpendicular to the film surface.
 本発明においては、カール防止の効果の点で、吹き付けの流速と吹き付け角度が重要である。
 吹き付けの流速は、0.1~10m/秒であることが好ましい。特に好ましくは0.2~5m/秒、更に好ましくは0.3~3m/秒である。流速が遅すぎると、カール防止の効果が低下する傾向があり、流速が速すぎると、フィルムにうねりが生じやすい傾向がある。
In the present invention, the spraying flow velocity and the spraying angle are important in terms of curling prevention effects.
The spraying flow rate is preferably 0.1 to 10 m / sec. Particularly preferred is 0.2 to 5 m / sec, and even more preferred is 0.3 to 3 m / sec. If the flow rate is too slow, the effect of preventing curling tends to decrease, and if the flow rate is too fast, the film tends to swell.
 空気の吹き付け方向をフィルムの面に垂直投影したとき、言い換えればフィルム面に垂直な方向でフィルム面を見たとき、空気の吹き付け方向がフィルムの幅方向(TD方向)やフィルムの移送方向(MD方向)に平行でないことが好ましい。したがって、好ましくは、空気の吹き付けの角度には、空気の吹き付け方向とフィルムの面とのなす角度θ1のみならず、空気の吹き付け方向をフィルムの面に垂直投影したときの方向とフィルムの移送方向(MD方向)とのなす角度θ2が包含される(図4~図6を参照)。
 なお、図6においては、フィルムの移送方向をx軸、フィルムの幅方向をy軸、フィルム面に垂直な方向をz軸とし、フィルム面をxy面、フィルム面に垂直な面であってフィルムの幅方向に平行な面をyz面、フィルム面に垂直な面であってフィルムの移送方向に平行な面をxz面としている。
When the air blowing direction is vertically projected onto the film surface, in other words, when the film surface is viewed in a direction perpendicular to the film surface, the air blowing direction is the film width direction (TD direction) or the film transport direction (MD Direction). Therefore, preferably, the air blowing angle includes not only the angle θ1 formed by the air blowing direction and the film surface, but also the direction when the air blowing direction is vertically projected on the film surface and the film transport direction. The angle θ2 formed with the (MD direction) is included (see FIGS. 4 to 6).
In FIG. 6, the film transport direction is the x-axis, the film width direction is the y-axis, the direction perpendicular to the film surface is the z-axis, the film surface is the xy surface, and the surface is perpendicular to the film surface. The plane parallel to the width direction is the yz plane, and the plane perpendicular to the film plane and parallel to the film transfer direction is the xz plane.
 空気の吹き付け方向とフィルムの面とのなす角度θ1は、5~80°であることが好ましく、特に好ましくは10~70°であり、更に好ましくは20~60°である。吹き付け角度θ1が低すぎると、カール防止の効果が低下する傾向があり、高すぎると、フィルムにうねりが生じやすい傾向がある。
 また、空気の吹き付け方向をフィルムの面に垂直投影したときの方向とフィルムの移送方向(MD方向)とのなす角度θ2は、5~175°であることが好ましく、特に好ましくは20~90°であり、更に好ましくは30~60°である。吹き付け角度θ2が低すぎると、カール防止の効果が低下する傾向があり、高すぎると、フィルムに皺が生じる傾向がある。
 なお、図7に示すように、複数のノズルを用いる場合、かかる吹き付けの流速と吹き付け角度は、全てのノズルが同じであっても、ノズルごとに異なっていてもよい。ノズルごとに異なる手法としては、例えば、フィルムの移送方向(MD方向)の上流側から下流側へ向かって、吹き付け流速を徐々に低く設定したり、吹き付け角度θ1を徐々に低角度にするなどの手法が挙げられる。
The angle θ1 formed by the air blowing direction and the film surface is preferably 5 to 80 °, particularly preferably 10 to 70 °, and further preferably 20 to 60 °. If the spray angle θ1 is too low, the effect of preventing curling tends to decrease, and if it is too high, the film tends to be swelled.
In addition, the angle θ2 formed by the direction when the air blowing direction is vertically projected onto the film surface and the film transport direction (MD direction) is preferably 5 to 175 °, particularly preferably 20 to 90 °. More preferably, it is 30 to 60 °. If the spray angle θ2 is too low, the effect of preventing curling tends to decrease, and if it is too high, wrinkles tend to occur on the film.
As shown in FIG. 7, when a plurality of nozzles are used, the flow velocity and the spray angle of the spraying may be the same for all nozzles or may be different for each nozzle. As a method different for each nozzle, for example, the spraying flow rate is gradually set lower from the upstream side to the downstream side in the film transfer direction (MD direction), or the spraying angle θ1 is gradually lowered. A method is mentioned.
 空気以外の気体を使用する場合、使用されるノズル、ノズルの配置、吹き付け流速、吹き付け角度は、上述した条件が好ましい。 When using a gas other than air, the conditions described above are preferable for the nozzle used, the arrangement of the nozzles, the spraying flow rate, and the spraying angle.
 かかる手法で、ポリビニルアルコール系フィルムは、折れや皺が無い状態で、次の3)染色工程や4)延伸工程に移送される。 By such a method, the polyvinyl alcohol film is transferred to the following 3) dyeing step and 4) stretching step in a state where there is no break or wrinkle.
 本発明の偏光膜は、1)原反巻き出し工程の後、2)水膨潤工程、3)染色工程、4)延伸工程、5)ホウ酸架橋工程、必要に応じて、洗浄工程や乾燥工程などの工程を経て製造される。かかる製造工程は、2)~5)の順に必ずしも行われる必要は無く、複数の工程を適宜組み合わせてもよい。例えば、2)水膨潤工程と同時に4)延伸工程を行ってもよいし、2)水膨潤工程の後、3)染色工程と同時に4)延伸工程を行っても良いし、2)水膨潤工程と3)染色工程の後、5)ホウ酸架橋工程と同時に4)延伸工程を行ってもよいし、2)水膨潤工程、3)染色工程、5)ホウ酸架橋工程のいずれにおいても4)延伸工程を行ってもよい。 The polarizing film of the present invention is 1) after the unwinding step, 2) the water swelling step, 3) the dyeing step, 4) the stretching step, 5) the boric acid crosslinking step, and if necessary, the washing step and the drying step. It is manufactured through processes such as Such manufacturing steps are not necessarily performed in the order of 2) to 5), and a plurality of steps may be appropriately combined. For example, 2) the stretching process may be performed simultaneously with 2) the water swelling process, 2) after the water swelling process, 3) the stretching process may be performed with the dyeing process, and 2) the water swelling process. And 3) After the dyeing step, 5) The boric acid crosslinking step and 4) the stretching step may be performed, 2) the water swelling step, 3) the dyeing step, and 5) the boric acid crosslinking step. A stretching process may be performed.
 以下、2)水膨潤以降の工程に関して説明する。 Hereinafter, 2) Steps after water swelling will be described.
 3)染色工程は、フィルムにヨウ素または二色性染料を含有する液体を接触させることによって行なわれる。通常は、ヨウ素-ヨウ化カリウムの水溶液が用いられ、ヨウ素の濃度は0.1~2g/L、ヨウ化カリウムの濃度は1~100g/Lが適当である。染色時間は30~500秒程度が実用的である。処理浴の温度は5~50℃が好ましい。水溶液には、水溶媒以外に水と相溶性のある有機溶媒を少量含有させてもよい。接触手段としては浸漬、塗布、噴霧などの任意の手段が適用できる。 3) The dyeing step is performed by bringing the film into contact with a liquid containing iodine or a dichroic dye. Usually, an iodine-potassium iodide aqueous solution is used. The iodine concentration is suitably 0.1-2 g / L, and the potassium iodide concentration is 1-100 g / L. The dyeing time is practically about 30 to 500 seconds. The temperature of the treatment bath is preferably 5 to 50 ° C. The aqueous solution may contain a small amount of an organic solvent compatible with water in addition to the aqueous solvent. As the contact means, any means such as dipping, coating, spraying and the like can be applied.
 4)延伸工程は、一軸方向に好ましくは3~10倍延伸する工程であり、3.5~6倍延伸することが特に好ましい。この際、延伸方向に対して直角をなす方向にも若干の延伸(幅方向の収縮を防止する程度、又はそれ以上の延伸)を行なっても差し支えない。延伸時の温度は、30~170℃の温度範囲から選ぶのが望ましい。さらに、延伸倍率は最終的に前記範囲に設定されればよく、延伸操作は一段階のみならず、製造工程の任意の範囲の段階に実施すればよい。 4) The stretching step is a step of stretching 3 to 10 times in a uniaxial direction, and it is particularly preferable to stretch 3.5 to 6 times. At this time, the film may be slightly stretched (stretching to prevent shrinkage in the width direction or more) in a direction perpendicular to the stretching direction. The temperature during stretching is preferably selected from a temperature range of 30 to 170 ° C. Furthermore, the draw ratio may be finally set within the above range, and the drawing operation may be performed not only in one stage but also in any stage of the manufacturing process.
 5)ホウ酸架橋工程は、ホウ酸やホウ砂などのホウ素化合物を使用して行われる。ホウ素化合物は水溶液または水-有機溶媒混合液の形で濃度10~100g/L程度で用いられ、液中には少量のヨウ化カリウムを共存させるのが、偏光性能の安定化の点で望ましい。処理時の温度は30~70℃程度、処理時間は0.1~20分程度が好ましい。 5) The boric acid crosslinking step is performed using a boron compound such as boric acid or borax. The boron compound is used in the form of an aqueous solution or a water-organic solvent mixture at a concentration of about 10 to 100 g / L, and it is desirable to allow a small amount of potassium iodide to coexist in the solution from the viewpoint of stabilizing the polarization performance. The treatment temperature is preferably about 30 to 70 ° C., and the treatment time is preferably about 0.1 to 20 minutes.
 その後、前記フィルムに洗浄処理を施してもよい。洗浄処理により、フィルムの表面に発生する析出物を除去することができる。洗浄処理は、例えば、水やヨウ化カリウム等のヨウ化物水溶液にポリビニルアルコール系フィルムを浸漬することにより行う。ヨウ化カリウム水溶液を用いる場合のヨウ化カリウム濃度は1~80g/L程度でよい。洗浄処理時の温度は、通常、5~50℃、好ましくは10~45℃である。処理時間は、通常、1~300秒間、好ましくは10~240秒間である。なお、水洗浄とヨウ化カリウム水溶液による洗浄は、適宜組み合わせて行ってもよい。また、その後、前記フィルムに乾燥工程を施してもよい。
 乾燥工程は、大気中で40~80℃で1~10分間行えばよい。
Thereafter, the film may be washed. The precipitate generated on the surface of the film can be removed by the washing treatment. The cleaning treatment is performed, for example, by immersing a polyvinyl alcohol film in an aqueous iodide solution such as water or potassium iodide. When using an aqueous potassium iodide solution, the concentration of potassium iodide may be about 1 to 80 g / L. The temperature during the washing treatment is usually 5 to 50 ° C., preferably 10 to 45 ° C. The treatment time is usually 1 to 300 seconds, preferably 10 to 240 seconds. In addition, you may perform combining water washing | cleaning and washing | cleaning by potassium iodide aqueous solution suitably. Moreover, you may give a drying process to the said film after that.
The drying step may be performed in the atmosphere at 40 to 80 ° C. for 1 to 10 minutes.
 このようにして得られる偏光膜の偏光度は、好ましくは99.8%以上、より好ましくは99.9%以上である。偏光度が低すぎると液晶ディスプレイにおけるコントラストを確保することができなくなる傾向がある。
 なお、偏光度は、一般的に2枚の偏光膜を、その配向方向が同一方向になるように重ね合わせた状態で、波長λにおいて測定した光線透過率(H11)と、2枚の偏光膜を、配向方向が互いに直交する方向になる様に重ね合わせた状態で、波長λにおいて測定した光線透過率(H)より、下式にしたがって算出される。
   〔(H11-H)/(H11+H)〕1/2
The polarization degree of the polarizing film thus obtained is preferably 99.8% or more, more preferably 99.9% or more. If the degree of polarization is too low, there is a tendency that the contrast in the liquid crystal display cannot be secured.
Note that the degree of polarization is generally the light transmittance (H 11 ) measured at the wavelength λ in the state where two polarizing films are overlapped so that their orientation directions are the same direction, and the two polarizing films. It is calculated according to the following equation from the light transmittance (H 1 ) measured at the wavelength λ in a state where the films are superposed so that the orientation directions are orthogonal to each other.
[(H 11 −H 1 ) / (H 11 + H 1 )] 1/2
 さらに、本発明の偏光膜の単体透過率は、好ましくは42%以上である。かかる単体透過率が低すぎると液晶ディスプレイの高輝度化を達成できなくなる傾向がある。
 単体透過率は、分光光度計を用いて偏光膜単体の光線透過率を測定して得られる値である。
Further, the single transmittance of the polarizing film of the present invention is preferably 42% or more. If the single transmittance is too low, it tends to be impossible to achieve high brightness of the liquid crystal display.
The single transmittance is a value obtained by measuring the light transmittance of a single polarizing film using a spectrophotometer.
 本発明の偏光膜の幅は、1m以上であることが好ましく、大面積化の点からは1.3m以上であることが好ましく、更なる大面積化の点から、特に好ましくは1.5m以上、破断回避の点から、更に好ましくは1.5~2.5mである。 The width of the polarizing film of the present invention is preferably 1 m or more, preferably 1.3 m or more from the viewpoint of increasing the area, and particularly preferably 1.5 m or more from the viewpoint of further increasing the area. From the viewpoint of avoiding breakage, it is more preferably 1.5 to 2.5 m.
 また、本発明の偏光膜の厚さは、15μm以下であることが好ましく、更なる薄型化の点から特に好ましくは10μm以下であり、破断回避の点から更に好ましくは2~9μm、殊に好ましくは3~8μmである。 The thickness of the polarizing film of the present invention is preferably 15 μm or less, particularly preferably 10 μm or less from the viewpoint of further thinning, more preferably 2 to 9 μm, particularly preferably from the viewpoint of avoiding breakage. Is 3 to 8 μm.
 かくして得られる本発明の偏光膜は、偏光ムラが少ないため、高性能な偏光板を製造するのに好適である。
 以下、本発明の偏光膜から偏光板を製造する製造方法について説明する。
Since the polarizing film of the present invention thus obtained has little polarization unevenness, it is suitable for producing a high-performance polarizing plate.
Hereinafter, the manufacturing method which manufactures a polarizing plate from the polarizing film of this invention is demonstrated.
 本発明の偏光膜は、その片面または両面に、接着剤を介して、光学的に等方性な樹脂フィルムを保護フィルムとして貼合されて偏光板となる。保護フィルムとしては、例えば、セルローストリアセテート、セルロースジアセテート、ポリカーボネート、ポリメチルメタクリレート、シクロオレフィンポリマー、シクロオレフィンコポリマー、ポリスチレン、ポリエーテルスルホン、ポリアリーレンエステル、ポリ-4-メチルペンテン、ポリフェニレンオキサイドなどのフィルムまたはシートが挙げられる。 The polarizing film of the present invention is bonded to one side or both sides of an optically isotropic resin film as a protective film via an adhesive to form a polarizing plate. Examples of protective films include films of cellulose triacetate, cellulose diacetate, polycarbonate, polymethyl methacrylate, cycloolefin polymer, cycloolefin copolymer, polystyrene, polyethersulfone, polyarylene ester, poly-4-methylpentene, polyphenylene oxide, and the like. Or a sheet | seat is mentioned.
 貼合方法は、公知の手法で行われ、例えば、液状の接着剤組成物を、偏光膜、保護フィルム、あるいはその両方に均一に塗布した後、両者を貼り合わせて圧着し、加熱や活性エネルギー線を照射することで行われる。 The bonding method is performed by a known method. For example, after a liquid adhesive composition is uniformly applied to a polarizing film, a protective film, or both, the two are bonded and pressure-bonded, and heating or active energy is applied. This is done by irradiating a line.
 また、偏光膜には、薄膜化を目的として、上記保護フィルムの代わりに、その片面または両面にウレタン系樹脂、アクリル系樹脂、ウレア樹脂などの硬化性樹脂を塗布し、硬化して偏光板とすることもできる。 In addition, for the purpose of thinning the polarizing film, instead of the protective film, a curable resin such as urethane resin, acrylic resin, urea resin or the like is applied to one side or both sides of the protective film and cured to obtain a polarizing plate. You can also
 本発明により得られる偏光膜や偏光板は、偏光性能に優れており、携帯情報端末機、パソコン、テレビ、プロジェクター、サイネージ、電子卓上計算機、電子時計、ワープロ、電子ペーパー、ゲーム機、ビデオ、カメラ、フォトアルバム、温度計、オーディオ、自動車や機械類の計器類などの液晶表示装置、サングラス、防眩メガネ、立体メガネ、ウェアラブルディスプレイ、表示素子(CRT、LCD、有機EL、電子ペーパーなど)用反射防止層、光通信機器、医療機器、建築材料、玩具などに好ましく用いられる。 The polarizing film and polarizing plate obtained by the present invention are excellent in polarization performance, such as portable information terminals, personal computers, televisions, projectors, signage, electronic desk calculators, electronic watches, word processors, electronic paper, game machines, videos, cameras. , Photo albums, thermometers, audio, liquid crystal display devices such as automobile and machinery instruments, sunglasses, anti-glare glasses, stereoscopic glasses, wearable displays, reflection for display elements (CRT, LCD, organic EL, electronic paper, etc.) It is preferably used for a prevention layer, an optical communication device, a medical device, a building material, a toy and the like.
 以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
 <測定条件>
 実施例及び比較例で得られた偏光膜について下記のとおりに偏光度(%)を測定した。
 得られた偏光膜の幅方向の中央部と両端部(それぞれ端から10cmの箇所)の偏光度を、大塚電子(株)製:RETS-1100Aを用いて測定した。
<Measurement conditions>
About the polarizing film obtained by the Example and the comparative example, polarization degree (%) was measured as follows.
The polarization degree of the obtained polarizing film at the central part and both ends (each 10 cm from the end) in the width direction was measured using RETS-1100A manufactured by Otsuka Electronics Co., Ltd.
 <実施例1>
(ポリビニルアルコール系フィルムの製造)
 重量平均分子量142000、ケン化度99.8モル%のポリビニルアルコール系樹脂1000kg、水2500kg、可塑剤としてグリセリン100kgを入れ、撹拌しながら140℃まで昇温して、樹脂濃度25重量%に濃度調整を行い、均一に溶解したポリビニルアルコール系樹脂水溶液を得た。
 次に、該ポリビニルアルコール系樹脂水溶液を、ベントを有する二軸押出機に供給して脱泡した後、水溶液温度を95℃にし、T型スリットダイ吐出口から表面温度90℃のキャストドラムに、吐出速度0.6m/分で流延して製膜した。
 次いで、得られたフィルムを複数の熱ロールで乾燥し、フローティングドライヤーを用いて120℃で3分間の熱処理を行い、4m幅にスリットで切り落とした。最後に、外径17cm、内径16cm、長さ4.4mのアルミニウム製芯管に巻き取ることによって、含水率が2重量%の帯状のポリビニルアルコール系フィルム(幅4m、長さ5km、厚み15μm)が芯管に巻き付けられたフィルムロールを得た。
<Example 1>
(Manufacture of polyvinyl alcohol film)
Polyvinyl alcohol resin with a weight average molecular weight of 142,000, saponification degree of 99.8 mol%, 1000 kg of water, 2500 kg of water and 100 kg of glycerin as a plasticizer are added, and the temperature is raised to 140 ° C. with stirring to adjust the resin concentration to 25% by weight. To obtain a uniformly dissolved polyvinyl alcohol-based resin aqueous solution.
Next, the polyvinyl alcohol-based resin aqueous solution is supplied to a twin-screw extruder having a vent and defoamed, and then the aqueous solution temperature is set to 95 ° C., and a cast drum having a surface temperature of 90 ° C. from the T-type slit die discharge port, The film was cast by casting at a discharge speed of 0.6 m / min.
Next, the obtained film was dried with a plurality of hot rolls, subjected to heat treatment at 120 ° C. for 3 minutes using a floating dryer, and cut into a 4 m width with a slit. Finally, it is wound on an aluminum core tube having an outer diameter of 17 cm, an inner diameter of 16 cm, and a length of 4.4 m, thereby forming a strip-like polyvinyl alcohol film having a moisture content of 2 wt% (width 4 m, length 5 km, thickness 15 μm). A film roll wound around the core tube was obtained.
(偏光膜の製造)
 得られたポリビニルアルコール系フィルムを、ロールから巻き出して水平方向に移送しながら〔1)原反巻き出し工程〕、水膨潤槽の温水に浸漬して膨潤させながら、移送方向へ延伸した(25℃で1分間、延伸倍率1.7倍)〔2)水膨潤工程〕。
 水膨潤槽からフィルムを引き上げ、水平に配置された2つのロール間で(ロール間の距離1m、ロール間の張力20N/m)、移送速度1m/分で水平方向に搬送されるフィルムの両端部に、ノズルで上側から空気(23℃)を吹き付けてカールを防止した。かかる空気の吹き付け条件は以下のとおりである。
 ノズル:ミスミ社製アジャストホース
 ノズル位置:水膨潤槽出口から1m
 ノズル位置(高さ):フィルム上面から5mm
 吹き付け流速:3m/秒
 吹き付け角度θ1:30°
 吹き付け角度θ2:45°
(Manufacture of polarizing film)
While the obtained polyvinyl alcohol film was unwound from a roll and transferred in the horizontal direction [1) Raw roll unwinding step], the film was stretched in the transfer direction while being immersed in hot water in a water swelling tank and swollen (25 (2) Water swelling step].
The film is pulled up from the water swelling tank, and the two ends of the film are transported in the horizontal direction at a transfer speed of 1 m / min between two horizontally disposed rolls (distance between rolls 1 m, tension between rolls 20 N / m). Then, air (23 ° C.) was blown from the upper side with a nozzle to prevent curling. The air blowing conditions are as follows.
Nozzle: Adjust hose made by MISUMI Nozzle position: 1 m from the outlet of the water swelling tank
Nozzle position (height): 5mm from the top of the film
Spraying flow velocity: 3m / sec Spraying angle θ1: 30 °
Spray angle θ2: 45 °
 得られたフィルムを、ヨウ素0.9g/L、ヨウ化カリウム30g/Lよりなる水溶液中に浸漬し染色しながら、移送方向へ延伸した(28℃で0.5分間、延伸倍率1.6倍)〔3)染色工程〕。
 次いで、ホウ酸25g/L、ヨウ化カリウム30g/Lの組成の水溶液に浸漬し、ホウ酸架橋しながら、移送方向へ一軸延伸した(55℃1分、延伸倍率2.0倍)〔5)ホウ酸架橋工程〕。
 その後、ヨウ化カリウム水溶液で洗浄を行い、乾燥して総延伸倍率5.4倍の偏光膜を得た(幅1.8m、厚さ7μm)。得られた偏光膜に折れ又は皺は無く、長さ12kmにわたって破断は生じなかった。得られた偏光膜の偏光特性を表1に示す。
The obtained film was stretched in the transfer direction while being immersed and dyed in an aqueous solution composed of 0.9 g / L of iodine and 30 g / L of potassium iodide (0.5 minutes at 28 ° C., 1.6 times stretching ratio). ) [3) Dyeing step].
Next, it was immersed in an aqueous solution having a composition of boric acid 25 g / L and potassium iodide 30 g / L, and uniaxially stretched in the transport direction while crosslinking with boric acid (55 ° C. for 1 minute, stretch ratio 2.0 times) [5] Boric acid crosslinking step].
Thereafter, the film was washed with an aqueous potassium iodide solution and dried to obtain a polarizing film having a total draw ratio of 5.4 times (width 1.8 m, thickness 7 μm). The obtained polarizing film was not broken or wrinkled, and no breakage occurred over a length of 12 km. Table 1 shows the polarization characteristics of the obtained polarizing film.
(偏光板の製造)
 得られた偏光膜の両面に、厚さ40μmのトリアセチルセルロースフイルム(TACフィルム)を、ポリビニルアルコール系水溶液を接着剤として用いて貼合し、50℃で乾燥して偏光板とした。得られた偏光板に偏光ムラは観察されなかった。
(Manufacture of polarizing plates)
A triacetyl cellulose film (TAC film) with a thickness of 40 μm was bonded to both surfaces of the obtained polarizing film using a polyvinyl alcohol-based aqueous solution as an adhesive, and dried at 50 ° C. to obtain a polarizing plate. Polarization unevenness was not observed in the obtained polarizing plate.
 <実施例2>
 実施例1において、空気の吹き付け角度θ1を60°とする以外は実施例1と同様にして、偏光膜を得た。得られた偏光膜について、実施例1と同様の評価を行った。評価結果を表1に示す。更に、実施例1と同様にして偏光板を得た。得られた偏光板に偏光ムラは観察されなかった。
<Example 2>
In Example 1, a polarizing film was obtained in the same manner as in Example 1 except that the air blowing angle θ1 was set to 60 °. About the obtained polarizing film, evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1. Further, a polarizing plate was obtained in the same manner as in Example 1. Polarization unevenness was not observed in the obtained polarizing plate.
 <実施例3>
 実施例1において、空気の吹き付け角度θ2を135°とする以外は実施例1と同様にして、偏光膜を得た。得られた偏光膜について、実施例1と同様の評価を行った。評価結果を表1に示す。更に、実施例1と同様にして偏光板を得た。得られた偏光板に偏光ムラは観察されなかった。
<Example 3>
In Example 1, a polarizing film was obtained in the same manner as in Example 1 except that the air blowing angle θ2 was set to 135 °. About the obtained polarizing film, evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1. Further, a polarizing plate was obtained in the same manner as in Example 1. Polarization unevenness was not observed in the obtained polarizing plate.
 <実施例4>
 実施例1において、空気に代えて水蒸気を吹き付ける以外は実施例1と同様にして、偏光膜を得た。
 得られた偏光膜について、実施例1と同様の評価を行った。評価結果を表1に示す。更に、実施例1と同様にして偏光板を得た。得られた偏光板に偏光ムラは観察されなかった。
<Example 4>
In Example 1, a polarizing film was obtained in the same manner as in Example 1 except that water vapor was blown instead of air.
About the obtained polarizing film, evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1. Further, a polarizing plate was obtained in the same manner as in Example 1. Polarization unevenness was not observed in the obtained polarizing plate.
 <比較例1>
 実施例1において、吹き付けを行わない以外は実施例1と同様にして、偏光膜の製造を開始した。しかし、2)水膨潤工程以降、フィルムの両端部に折れや皺が観察され、長さ1kmの偏光膜を製造したところで、染色槽において破断が生じた。得られた部分の偏光特性を表1に示す。なお、破断が生じたため、偏光板の製造はできなかった。
<Comparative Example 1>
In Example 1, the production of the polarizing film was started in the same manner as in Example 1 except that the spraying was not performed. However, 2) After the water swelling step, folds and wrinkles were observed at both ends of the film, and when a polarizing film having a length of 1 km was produced, breakage occurred in the dyeing tank. Table 1 shows the polarization characteristics of the obtained part. In addition, since the fracture occurred, the polarizing plate could not be manufactured.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表1に示すように、本発明の偏光膜の製造方法によれば、折れや皺が無く、長尺の偏光膜を得ることができる。また、偏光膜の中央部のみならず、幅方向両端部においても偏光度が高いので、偏光膜の中央部から端部まで均一な偏光度を有する偏光膜を得ることができる。更に、幅広長尺薄型の偏光板の製造を容易にすることができ、液晶表示画像の色ムラや白抜けを低減することができる。 As shown in Table 1, according to the method for producing a polarizing film of the present invention, a long polarizing film can be obtained without folds or wrinkles. In addition, since the degree of polarization is high not only in the central part of the polarizing film but also at both ends in the width direction, a polarizing film having a uniform degree of polarization from the central part to the end part of the polarizing film can be obtained. Furthermore, it is possible to easily produce a wide, long and thin polarizing plate, and to reduce color unevenness and white spots in a liquid crystal display image.
 本発明の偏光膜は、携帯情報端末機、パソコン、テレビ、プロジェクター、サイネージ、電子卓上計算機、電子時計、ワープロ、電子ペーパー、ゲーム機、ビデオ、カメラ、フォトアルバム、温度計、オーディオ、自動車や機械類の計器類などの液晶表示装置、サングラス、防眩メガネ、立体メガネ、ウェアラブルディスプレイ、表示素子(CRT、LCD、有機EL、電子ペーパーなど)用反射防止層、光通信機器、医療機器、建築材料、玩具などに用いられる。 The polarizing film of the present invention is a portable information terminal, personal computer, TV, projector, signage, electronic desk calculator, electronic clock, word processor, electronic paper, game machine, video, camera, photo album, thermometer, audio, automobile and machine. Liquid crystal display devices such as various instruments, sunglasses, anti-glare glasses, stereoscopic glasses, wearable displays, antireflection layers for display elements (CRT, LCD, organic EL, electronic paper, etc.), optical communication equipment, medical equipment, building materials Used for toys.
 PVAフィルム:ポリビニルアルコール系フィルム
 θ1(°):吹き付け方向とフィルムの面とのなす角度
 θ2(°):吹き付け方向をポリビニルアルコール系フィルムの面に垂直投影したときの方向とポリビニルアルコール系フィルムの移送方向とのなす角度
 距離A:水膨潤槽の液面とロールaとの距離
 距離B:ロールaとロールbとの間の距離
PVA film: polyvinyl alcohol-based film θ1 (°): angle formed by spraying direction and film surface θ2 (°): direction when the spraying direction is perpendicularly projected onto the surface of the polyvinyl alcohol-based film and transfer of the polyvinyl alcohol-based film Angle formed by direction Distance A: Distance between the liquid level of the water swelling tank and roll a Distance B: Distance between roll a and roll b

Claims (10)

  1.  1)ポリビニルアルコール系フィルムをロールから巻き出して水平方向に移送する工程、2)水膨潤工程、3)染色工程、4)延伸工程、及び5)ホウ酸架橋工程を有する偏光膜の製造方法であって、
     前記2)~4)のいずれかの工程の前及び/又は後において、前記フィルムの幅方向両端部に気体を下記条件a)で吹き付けて前記フィルムのカールを防止することを特徴とする偏光膜の製造方法。
     条件a)気体の吹き付け方向と前記フィルムの面とのなす角度θ1が5~80°である。
    1) A method for producing a polarizing film comprising a step of unwinding a polyvinyl alcohol film from a roll and transferring it horizontally, 2) a water swelling step, 3) a dyeing step, 4) a stretching step, and 5) a boric acid crosslinking step. There,
    Before and / or after any of the steps 2) to 4), a polarizing film is characterized in that gas is blown to both end portions in the width direction of the film under the following condition a) to prevent the film from curling. Manufacturing method.
    Condition a) The angle θ1 formed between the gas blowing direction and the film surface is 5 to 80 °.
  2.  前記気体を、下記条件b)で吹き付けることを特徴とする請求項1記載の偏光膜の製造方法。
     条件b)気体の吹き付け方向を前記フィルムの面に垂直投影したときの方向と前記フィルムの移送方向とのなす角度θ2が5~175°である。
    2. The method for producing a polarizing film according to claim 1, wherein the gas is sprayed under the following condition b).
    Condition b) The angle θ2 formed by the direction in which the gas blowing direction is perpendicularly projected onto the surface of the film and the film transfer direction is 5 to 175 °.
  3.  前記気体の吹き付けが、2)水膨潤工程の後に行なわれることを特徴とする請求項1又は2記載の偏光膜の製造方法。 3. The method for producing a polarizing film according to claim 1, wherein the gas is sprayed after 2) the water swelling step.
  4.  前記気体が、空気又は水蒸気であることを特徴とする請求項1~3いずれか記載の偏光膜の製造方法。 The method for producing a polarizing film according to any one of claims 1 to 3, wherein the gas is air or water vapor.
  5.  前記気体の吹き付けが、流速0.1~10m/秒で行なわれることを特徴とする請求項1~4いずれか記載の偏光膜の製造方法。 5. The method for producing a polarizing film according to claim 1, wherein the gas is sprayed at a flow rate of 0.1 to 10 m / sec.
  6.  前記2)水膨潤工程から前記3)染色工程に至る前記フィルムの移送速度が、1m/分以上であることを特徴とする請求項1~5いずれか記載の偏光膜の製造方法。 6. The method for producing a polarizing film according to claim 1, wherein the transfer speed of the film from the 2) water swelling step to the 3) dyeing step is 1 m / min or more.
  7.  偏光膜の厚さが15μm以下であることを特徴とする請求項1~6いずれか記載の偏光膜の製造方法。 7. The method for producing a polarizing film according to claim 1, wherein the polarizing film has a thickness of 15 μm or less.
  8.  偏光膜の幅が1m以上であることを特徴とする請求項1~7いずれか記載の偏光膜の製造方法。 8. The method for producing a polarizing film according to claim 1, wherein the width of the polarizing film is 1 m or more.
  9.  請求項1~8のいずれか記載の偏光膜の製造方法により製造される偏光膜。 A polarizing film produced by the method for producing a polarizing film according to any one of claims 1 to 8.
  10.  請求項9記載の偏光膜の少なくとも片面に保護フィルムが設けられてなることを特徴とする偏光板。 A polarizing plate comprising a protective film provided on at least one side of the polarizing film according to claim 9.
PCT/JP2016/068186 2015-09-30 2016-06-17 Method for producing polarizing film, polarizing film, and polarizing plate WO2017056580A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021210542A1 (en) * 2020-04-16 2021-10-21 富士フイルム株式会社 Method for producing coating film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07247378A (en) * 1994-03-09 1995-09-26 Nippon Synthetic Chem Ind Co Ltd:The Method and apparatus for enlarging water stream width in underwater running of vinyl alcohol polymer film
JP2000147251A (en) * 1998-11-10 2000-05-26 Nitto Denko Corp Production of polarizing film and polarizing plate
JP2001315140A (en) * 2000-05-09 2001-11-13 Kuraray Co Ltd Polyvinyl alcohol polymer film, method for manufacturing the same, and polarizing film
JP2014146035A (en) * 2014-02-27 2014-08-14 Nitto Denko Corp Method for manufacturing polarizer, polarizer, polarizing plate, optical film and image display device
JP2015102615A (en) * 2013-11-22 2015-06-04 住友化学株式会社 Production method of polarizing film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07247378A (en) * 1994-03-09 1995-09-26 Nippon Synthetic Chem Ind Co Ltd:The Method and apparatus for enlarging water stream width in underwater running of vinyl alcohol polymer film
JP2000147251A (en) * 1998-11-10 2000-05-26 Nitto Denko Corp Production of polarizing film and polarizing plate
JP2001315140A (en) * 2000-05-09 2001-11-13 Kuraray Co Ltd Polyvinyl alcohol polymer film, method for manufacturing the same, and polarizing film
JP2015102615A (en) * 2013-11-22 2015-06-04 住友化学株式会社 Production method of polarizing film
JP2014146035A (en) * 2014-02-27 2014-08-14 Nitto Denko Corp Method for manufacturing polarizer, polarizer, polarizing plate, optical film and image display device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021210542A1 (en) * 2020-04-16 2021-10-21 富士フイルム株式会社 Method for producing coating film
JP7446412B2 (en) 2020-04-16 2024-03-08 富士フイルム株式会社 Coating film manufacturing method

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