Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
  • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
  • B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
  • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

• the present invention is a polyvinyl alcohol film that has excellent dyeability, a high degree of polarization, and can be a material for forming a polarizing film with little color unevenness, a polarizing film and a polarizing plate using the polyvinyl alcohol film,
• the present invention relates to a method for producing the polyvinyl alcohol film.
• a polyvinyl alcohol film has been used in many applications as a film having excellent transparency, and one of its useful applications is a polarizing film.
• the polarizing film is used as a basic component of a liquid crystal display, and in recent years, its use has been expanded to equipment that requires high quality and high reliability.
• a polarizing film having excellent optical characteristics is required as the screens of liquid crystal televisions, multifunctional portable terminals, and the like increase in brightness, definition, area, and thickness.
• the specific requirement is further improvement of the degree of polarization and elimination of color unevenness.
• a polyvinyl alcohol film is manufactured by a continuous casting method using an aqueous solution of a polyvinyl alcohol resin as a material. Specifically, first, an aqueous solution of a polyvinyl alcohol-based resin is cast on a cast mold such as a cast drum or an endless belt to form a film, and then the formed film is peeled off from the cast mold. While being conveyed in the flow direction (MD) using a nip roll or the like, it is produced by drying using a hot roll or a floating dryer. In the said conveyance process, since the film formed into a film is pulled
• MD flow direction
• a polarizing film is obtained by first swelling a polyvinyl alcohol film, which is a raw material, with water (including warm water), then dyeing with a dichroic dye such as iodine, and then stretching. It is manufactured by. What is important in the swelling step is to swell the polyvinyl alcohol film quickly in the thickness direction, and to uniformly swell the polyvinyl alcohol film so that the dye can smoothly enter the film in the dyeing step. That is.
• the said extending process is a process of extending
• MD flow direction
• the case where the order of the stretching process and the dyeing process is opposite to the above is also carried out. That is, this is a case where a polyvinyl alcohol film which is a raw fabric is first swollen with water (including warm water), then stretched, and then dyed with a dichroic dye such as iodine.
• a dichroic dye such as iodine.
• the important thing for improving the polarizing performance of the polarizing film is that the original polyvinyl alcohol film exhibits good swelling in the thickness direction and good stretchability in the flow direction (MD). It is to show.
• a polyvinyl alcohol film which is an original fabric, has also been reduced in thickness in order to reduce the thickness of the polarizing film.
• the thin polyvinyl alcohol-based film has a productivity problem such that it is broken by stretching when the polarizing film is produced.
• a method of improving the swelling property of the polyvinyl alcohol film for example, a method of adding a polyhydric alcohol as a water swelling aid to a polyvinyl alcohol resin (see, for example, Patent Document 1) has been proposed.
• a method of improving the stretchability of the polyvinyl alcohol film for example, a method of specifying the ratio of the speed of the cast drum when forming the film and the final winding speed of the polyvinyl alcohol film (for example, Patent Document 2), a method of floating a film after film formation with a cast drum (for example, refer to Patent Document 3), and a method for controlling the tension in a film forming film drying process (for example, Patent Document 4).
• a method of controlling the birefringence of the skin layer and the core layer within a specific range has been proposed (for example, see Patent Document 5).
• Patent Document 1 is insufficient in improving the swelling property, and the methods of Patent Documents 2 to 5 do not provide stretchability during the production of a polarizing film. Insufficient improvement.
• Patent Document 2 specifies the degree of stretching (stretching) in the flow direction (MD) when producing a polyvinyl alcohol film, but also considers stretching in the width direction (TD). Otherwise, it is insufficient to improve the stretchability during the production of the polarizing film.
• Patent Document 3 can uniformly dry the formed film, the orientation of the polymer cannot be controlled, and is insufficient to improve the swelling property and stretchability during the production of the polarizing film. is there.
• Patent Document 4 although the film thickness of the polyvinyl alcohol film can be made uniform, the orientation of the polymer cannot be controlled, and the swelling property and stretchability during the production of the polarizing film can be improved. Insufficient.
• Patent Document 5 Although a high polyvinyl alcohol film having a thickness of about 75 ⁇ m used in the examples can exhibit high stretchability, the birefringence of the skin layer and the core layer can be specified. Therefore, it is difficult to cope with further thinning of the polarizing film, and in the thin polyvinyl alcohol film having a film thickness of 60 ⁇ m or less, it is difficult to cope with the polarizing film. Insufficient to improve swelling and stretchability.
• the present invention has a good balance between swelling and stretchability during the production of the polarizing film under such a background, does not cause breakage during the production of the thin polarizing film, exhibits high polarization performance, and has a color.
• a polyvinyl alcohol film capable of obtaining a polarizing film with little unevenness a polarizing film and a polarizing plate using the polyvinyl alcohol film, and a method for producing the polyvinyl alcohol film.
• the inventors of the present invention have made the birefringence of both sides of the film close to each other in the polyvinyl alcohol film, and the birefringence inside the film is more than the birefringence of both sides of the film. If the birefringence on both sides of the film is made smaller and larger than before, the balance between swelling and stretchability during the production of the polarizing film is excellent, and there is no breakage during the production of the thin polarizing film, and high polarization performance is exhibited. It was also found that a polarizing film with little color unevenness can be obtained.
• the present invention is a long polyvinyl alcohol film having a thickness of 5 to 60 ⁇ m, wherein the birefringence in the length direction (MD) of the first surface of the film is ⁇ n MDA ,
• the birefringence in the length direction (MD) of the surface is ⁇ n MDB
• the birefringence in the center in the thickness direction of the film is ⁇ n MDC
• all of the following formulas (A) to (C) are satisfied.
• the first gist is a polyvinyl alcohol film. 1.0 ⁇ ⁇ n MDA / ⁇ n MDB ⁇ 1.5 (A) ⁇ n MDB ⁇ n MDC ⁇ 0.2 ⁇ 10 ⁇ 3 (B) ⁇ n MDA ⁇ 3.0 ⁇ 10 ⁇ 3 (C)
• the second gist of the present invention is a polarizing film in which the polyvinyl alcohol film is used.
• a third gist is a polarizing plate comprising the polarizing film and a protective film provided on at least one surface of the polarizing film.
• ⁇ n MDA is the birefringence index in the flow direction (MD) of the first surface of the polyvinyl alcohol film
• ⁇ n MDB is the second surface of the polyvinyl alcohol film.
• ⁇ n MDC represents the birefringence at the center in the thickness direction of the polyvinyl alcohol film.
• the polyvinyl alcohol film of the present invention satisfies all of the above formulas (A) to (C), it is excellent in swelling property and stretchability at the time of producing a polarizing film. It is possible to prevent breakage even when used in the production of the above. Furthermore, when the polyvinyl alcohol film is used, a polarizing film having high polarization performance and little color unevenness can be obtained.
• the birefringence in the width direction (TD) perpendicular to the length direction (MD) of the first surface of the polyvinyl alcohol film is ⁇ n TDA
• the length direction (MD of the second surface of the film is MD
• ⁇ n TDB if at least one of the following formulas (D) and (E) is satisfied, A polarizing film excellent in performance and performance can be obtained.
• the polyvinyl alcohol film has a thickness of 5 to 45 ⁇ m, the swellability and stretchability during the production of the polarizing film are further improved, and a polarizing film with further improved performance can be obtained.
• the above-mentioned polyvinyl alcohol film is used for the polarizing film of the present invention, it exhibits high polarization performance and has little color unevenness.
• the polarizing film of the present invention uses the polarizing film, it exhibits high polarization performance and has little color unevenness.
• the manufacturing method of the polyvinyl-alcohol-type film of this invention is continuous drying and continuous with respect to the film forming process by the continuous casting method, conveying the film formed into the flow direction (MD). And a drying / stretching step for performing proper stretching, the production conditions in each of these steps are combined, and the polyvinyl alcohol film of the present invention having a specific birefringence can be obtained.
• the drying / stretching step when the film formed is stretched 1.05 to 1.3 times in the width direction (TD), the birefringence is suitable, and the swellability during the production of the polarizing film and A polyvinyl alcohol film superior in stretchability can be obtained.
• the film formed above is temporarily stretched in the width direction (TD) to exceed 1.3 times, and the final stretching ratio in the width direction is 1.3 times or less.
• TD width direction
• the stress applied to the film formed can be relaxed. Therefore, even if the formed film is thin, the film can be prevented from breaking.
• the polyvinyl alcohol film of the present invention is a long polyvinyl alcohol film having a thickness of 5 to 60 ⁇ m, and the birefringence in the length direction (MD) of the first surface (one surface) of the film is ⁇ n.
• MDA the birefringence in the length direction (MD) of the second surface (the other side) of the film
• ⁇ n MDC the birefringence in the center in the thickness direction of the film
• the thickness of the polyvinyl alcohol film of the present invention is required to be 5 to 60 ⁇ m, preferably 5 to 50 ⁇ m from the viewpoint of thinning the polarizing film, and particularly preferably 5 to 5 ⁇ m from the viewpoint of avoiding breakage. It is 45 ⁇ m, more preferably 10 to 40 ⁇ m. If the thickness is too thin, it tends to break during the production of the polarizing film described later, which is not preferred. If it is too thick, the tension required for stretching increases, which is not preferred.
• a value obtained by dividing the birefringence in the length direction (MD) of the first surface by the birefringence in the length direction (MD) of the second surface ( ⁇ n MDA / ⁇ n MDB )
• ⁇ n MDA / ⁇ n MDB a value obtained by dividing the birefringence in the length direction (MD) of the first surface by the birefringence in the length direction (MD) of the second surface
• ⁇ n MDA / ⁇ n MDB the difference in physical properties between both surfaces of the polyvinyl alcohol film will increase, and the polyvinyl alcohol film will be easily broken in water, so the object of the present invention cannot be achieved.
• the larger one is ⁇ n MDA and the smaller one is ⁇ n MDB .
• the difference ( ⁇ n MDB ⁇ n MDC ) between the birefringence of one side of the film on the side having the smaller birefringence and the birefringence at the center in the thickness direction of the film is ⁇ n MDB ⁇ n MDC ⁇ 0.2 ⁇ 10 ⁇ 3 , preferably ⁇ n MDB ⁇ n MDC ⁇ 0.3 ⁇ 10 ⁇ 3 , particularly preferably ⁇ n MDB ⁇ n MDC ⁇ 0.4 ⁇ 10 ⁇ 3 . If the value of ⁇ n MDB ⁇ n MDC is too small, the stretchability of the polyvinyl alcohol film deteriorates, and the object of the present invention cannot be achieved.
• the upper limit of ⁇ n MDB ⁇ n MDC is normally 10 ⁇ 10 ⁇ 3 (preferably 9.0 ⁇ 10 ⁇ 3 ). If the value of ⁇ n MDB ⁇ n MDC is too large, the production of a polarizing film described later is performed. Sometimes the film is partially clouded and tends to be uneven.
• the birefringence ( ⁇ n MDA ) of one side of the film on the side having the higher birefringence must be ⁇ n MDA ⁇ 3.0 ⁇ 10 ⁇ 3 , and preferably ⁇ n MDA ⁇ 3.2 ⁇ 10. ⁇ 3 , particularly preferably ⁇ n MDA ⁇ 3.5 ⁇ 10 ⁇ 3 , more preferably ⁇ n MDA ⁇ 4.0 ⁇ 10 ⁇ 3 . If the value of ⁇ n MDA is too small, the film tends to break during the production of the polarizing film described later, and the object of the present invention cannot be achieved.
• the upper limit of ⁇ n MDA is usually 10 ⁇ 10 ⁇ 3 (preferably 9.0 ⁇ 10 ⁇ 3 ). If the value of ⁇ n MDA is too large, the stretching tension necessary for manufacturing a polarizing film described later becomes high. It tends to be too much.
• the film formed with the cast mold is peeled from the cast mold. Then, a method of stretching in the width direction (TD) is preferable.
• the conditions in the other steps are appropriately adjusted according to the stretching conditions in the width direction (TD) (stretching ratio, atmospheric temperature during stretching, stretching time, etc.).
• the conditions include, for example, the chemical structure of the polyvinyl alcohol-based resin that is the material for forming the polyvinyl alcohol-based film, the type and amount of plasticizer, the film-forming conditions for the film (such as the cast mold temperature), and the film-forming.
• the drying conditions (temperature, time) for drying the formed film, the transport speed in the flow direction (MD) of the formed film, and the like can be mentioned.
• the formulas (A) to (C) are controlled by combining at least one of these conditions and the stretching condition in the width direction (TD).
• the values of ⁇ n MDA , ⁇ n MDB , and ⁇ n MDC in the present invention are measured, for example, by the following method.
• the measurement positions of ⁇ n MDA , ⁇ n MDB , and ⁇ n MDC are within a 50 mm ⁇ 50 mm region of the polyvinyl alcohol film.
• MD flow direction
• the slice piece is tilted, placed on the slide glass with the slice surface facing upward, and sealed with a cover glass and tricresyl phosphate (refractive index 1.557), and two-dimensional photoelasticity Retardation is measured using an evaluation system “PA-micro” (manufactured by Photonic Lattice).
• the obtained retardation distribution data in the thickness direction of the slice piece is divided by the thickness of the slice piece of 10 ⁇ m to obtain the birefringence distribution in the thickness direction of the slice piece, and the maximum birefringence in the vicinity of both sides of the slice piece
• the values are set to birefringence ⁇ n MDA and ⁇ n MDB on both sides of the slice piece, respectively.
• the larger value is set as ⁇ n MDA and the smaller value is set as ⁇ n MDB .
• the birefringence ⁇ n MDC at the center of the slice piece in the thickness direction is used.
• the polyvinyl alcohol film of the present invention further has a birefringence index ⁇ n TDA in the width direction (TD) perpendicular to the flow direction (MD) of the first surface of the film, and the second surface of the film.
• ⁇ n TDA birefringence index
• the birefringence in the width direction (TD) perpendicular to the flow direction (MD) is ⁇ n TDB , satisfying at least one of the following formulas (D) and (E) It is preferable in that it can be reduced.
• ⁇ n MDA / ⁇ n TDA ⁇ 1.0 (D) ⁇ n MDB / ⁇ n TDB ⁇ 1.0 (E)
• the slice piece is tilted, placed on the slide glass with the slice surface facing upward, and sealed with a cover glass and tricresyl phosphate (refractive index 1.557), and two-dimensional photoelasticity Retardation is measured using an evaluation system “PA-micro” (manufactured by Photonic Lattice).
• PA-micro evaluation system
• a line segment X perpendicular to the surface of the original polyvinyl alcohol film is drawn across the slice piece, and the line segment is drawn. Line analysis is performed on X to obtain retardation distribution data in the thickness direction of the slice piece.
• the observation is performed using an objective lens 40 times, and the average value of the retardation is adopted with the line width set to 3 pixels.
• the obtained retardation distribution data in the thickness direction of the slice piece is divided by the thickness of the slice piece of 10 ⁇ m to obtain the birefringence distribution in the thickness direction of the slice piece, and the maximum birefringence in the vicinity of both sides of the slice piece
• the values are set to birefringence ⁇ n TDA and ⁇ n TDB on both sides of the slice piece, respectively. At this time, the larger value is set as ⁇ n TDA and the smaller value is set as ⁇ n TDB .
• the manufacturing method of the polyvinyl alcohol-type film of this invention is demonstrated in order of a process.
• the polyvinyl alcohol resin used in the present invention and the polyvinyl alcohol resin aqueous solution will be described.
• the polyvinyl alcohol resin constituting the polyvinyl alcohol film is usually an unmodified polyvinyl alcohol resin, that is, a resin produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. Used. If necessary, a resin obtained by saponifying a copolymer of vinyl acetate and a small amount (usually 10 mol% or less, preferably 5 mol% or less) of a copolymerizable component with vinyl acetate may be used. it can.
• 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. These may be used alone or in combination of two or more. Moreover, 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.
• the polyvinyl alcohol resin having a 1,2-diol structure in the side chain is, for example, (i) a method of saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene, and (ii) acetic acid.
• (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 glycerol monoallyl ether, or the like.
• 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. If the weight average molecular weight is too small, when the polyvinyl alcohol resin is used as an optical film, sufficient optical performance tends to be difficult to obtain, and if too large, it is difficult to stretch the polyvinyl alcohol film during the production of the polarizing film. Tend to be.
• the weight average molecular weight of the polyvinyl alcohol resin is a weight average molecular weight measured by GPC-MALS method.
• the average saponification degree of the polyvinyl alcohol resin used in the present invention is usually preferably 98 mol% or more, particularly preferably 99 mol% or more, more preferably 99.5 mol% or more, and particularly preferably 99.mol%. It is 8 mol% or more.
• the average saponification degree in the present invention is measured according to JIS K 6726.
• 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-based resin aqueous solution may include plastics commonly used such as glycerin, diglycerin, triglycerin, ethylene glycol, triethylene glycol, polyethylene glycol, and trimethylolpropane as necessary. It is preferable from the point of film forming property to contain an agent and at least one surfactant of nonionic property, anionic property, and cationic property. These may be used alone or in combination of two or more.
• the resin concentration of the aqueous polyvinyl alcohol resin solution thus obtained is preferably 15 to 60% by weight, particularly preferably 17 to 55% by weight, and further preferably 20 to 50% by weight. If the resin concentration of the aqueous solution is too low, the drying load increases and the production capacity tends to decrease. If it is too high, the viscosity becomes too high and uniform dissolution tends to be difficult.
• the obtained polyvinyl alcohol-based resin aqueous solution is defoamed.
• the defoaming method include static defoaming and defoaming with a multi-screw extruder.
• the multi-screw extruder may be a multi-screw extruder having a vent, and a biaxial extruder having a vent is usually used.
• the polyvinyl alcohol film of the present invention is produced by a casting method or a melt extrusion method.
• the casting method is preferable from the viewpoint of transparency, thickness accuracy, surface smoothness, etc., and production is particularly preferable. From the point of view, it is a continuous casting method.
• the continuous casting method refers to, for example, forming a film by continuously discharging and casting the aqueous solution of the polyvinyl alcohol resin from a T-type slit die to a casting mold such as a rotating cast drum, an endless belt, or a resin film. It is a method to do.
• a casting mold such as a rotating cast drum, an endless belt, or a resin film. It is a method to do.
• the film forming process when the cast mold is a cast drum will be described.
• the temperature of the polyvinyl alcohol resin aqueous solution at the exit of the T-type slit die is preferably 80 to 100 ° C., and particularly preferably 85 to 98 ° C. When the temperature of the aqueous polyvinyl alcohol resin solution is too low, there is a tendency to cause poor flow, and when it is too high, there is a tendency to foam.
• the viscosity of the polyvinyl alcohol-based resin aqueous solution is preferably 50 to 200 Pa ⁇ s at discharge (at the preferable temperature of 80 to 100 ° C.), particularly preferably 70 to 150 Pa (at the particularly preferable temperature of 85 to 98 ° C.). -S.
• the viscosity of the polyvinyl alcohol-based resin aqueous solution is too low, there is a tendency to cause poor flow, and when it is too high, casting tends to be difficult.
• the discharge speed of the aqueous polyvinyl alcohol resin solution discharged from the T-type slit die onto the cast drum is preferably 0.2 to 5 m / min, particularly preferably 0.4 to 4 m / min, and more preferably 0.8. 6-3 m / min. If the discharge speed is too slow, productivity tends to decrease, and if it is too fast, casting tends to be difficult.
• the cast drum has a diameter of preferably 2 to 5 m, particularly preferably 2.4 to 4.5 m, and more preferably 2.8 to 4 m. If the diameter of the cast drum is too small, the drying length tends to be insufficient and the speed tends to be difficult to output, and if too large, the transportability tends to decrease.
• the width of the cast drum is preferably 4 m or more, particularly preferably 4.5 m or more, more preferably 5 m or more, and particularly preferably 5 to 7 m. When the width of the cast drum is too small, the productivity tends to decrease.
• the rotation speed of the cast drum is preferably 5 to 50 m / min, particularly preferably 6 to 40 m / min, and more preferably 7 to 35 m / min. If the rotation speed of the cast drum is too slow, the productivity tends to decrease, and if it is too fast, the drying tends to be insufficient.
• the surface temperature of the cast drum is preferably 40 to 99 ° C., particularly preferably 60 to 95 ° C. If the surface temperature is too low, drying tends to be poor, and if it is too high, foaming tends to occur.
• the moisture content of the formed film is preferably 0.5 to 15% by weight, particularly preferably 1 to 13% by weight, and more preferably 2 to 12% by weight. If the water content is too low or too high, the desired swelling and stretchability tend to be difficult to develop.
• the film is preferably dried before stretching in the width direction (TD).
• the moisture content of the film before stretching in (TD) is too low, it is preferable to condition the humidity before stretching in the width direction (TD).
• the conditions of the drying step are adjusted so that the moisture content falls within the above range.
• the drying is performed continuously.
• This continuous drying can be performed by a known method using a heating roll, an infrared heater or the like, but in the present invention, it is preferably performed with a plurality of heating rolls, and particularly preferably, the temperature of the heating roll is 40 It is ⁇ 150 ° C., more preferably 50 to 140 ° C. Moreover, you may provide a humidity control area before extending
• the stretching in the width direction (TD) causes neck-in depending on the Poisson's ratio in the flow direction (MD), and dehydration shrinkage also occurs in the flow direction (MD) during drying. Due to these contractions, even if the rotation speed of the transport roll and the heating roll is constant, an appropriate tension is obtained in the flow direction (MD), and complicated control of the rotation speed as in Patent Document 2 is unnecessary.
• the dimension of the film in the flow direction (MD) is preferably constant, and particularly preferably, the dimensional change rate in the flow direction (MD) is 0.8 before and after stretching in the width direction (TD). It is -1.2, Especially preferably, it is 0.9-1.1.
• the transport speed of the formed film in the flow direction (MD) is preferably 5 to 30 m / min, particularly preferably 7 to 25 m / min, and more preferably 8 to 20 m / min. If this transport speed is too slow, the productivity tends to decrease, and if it is too fast, the in-plane uniformity tends to decrease.
• the method of simultaneously transporting the formed film in the flow direction (MD) and stretching in the width direction (TD) is not particularly limited.
• both ends of the film in the width direction are sandwiched by a plurality of clips.
• the arrangement of the clips at each end is preferably 200 mm or less, particularly preferably 100 mm or less, and more preferably 50 mm or less. If the pitch of the clip is too wide, the stretched film tends to bend, or the in-plane uniformity of the resulting polyvinyl alcohol film tends to decrease.
• the clip clamping position (the tip of the clip) is preferably 100 mm or less from both edges in the width direction of the film formed. If the clip clamping position (tip portion) is positioned too far in the center in the film width direction, the film end to be discarded increases and the product width tends to narrow.
• the draw ratio in the width direction (TD) is preferably 1.05 to 1.3 times, particularly preferably 1.05 to 1.25 times, more preferably 1.1 to 1.2 times. It is. Even if the draw ratio in the width direction (TD) is too high or too low, the in-plane uniformity tends to decrease.
• the stretching in the width direction (TD) is continuously performed.
• This continuous stretching may be performed in one step (one time), or may be performed in a plurality of steps (a plurality of times) so that the total stretching ratio falls within the range of the stretching ratio (also referred to as sequential stretching).
• simple transport with the width direction (TD) fixed may be performed, and then the second and subsequent stages of continuous stretching may be performed.
• the stress is relaxed by inserting a simple width fixing conveyance process after continuous stretching in the first stage, and breakage can be avoided. .
• the fixed width can be narrower than the width after continuous stretching in the first stage.
• the continuous stretching is preferably performed after the film drying process, but is performed at least one before, during, and after the film drying process.
• the film is temporarily stretched in the width direction (TD) exceeding 1.3 times, and then the final draw ratio in the width direction (TD) is 1.05. It is possible to use a method of dimensional shrinkage so as to be ⁇ 1.3 times. In this case, after the film is temporarily stretched over 1.3 times, the film may be simply conveyed with a fixed width of a stretch ratio of 1.05 to 1.3. By this method, the stress of the film is relaxed, and breakage can be avoided particularly in the case of a thin film.
• stretching in the width direction (TD) of the formed film is preferably performed at an atmospheric temperature of 50 to 150 ° C.
• the atmospheric temperature at the time of stretching is particularly preferably 60 to 140 ° C, more preferably 70 to 130 ° C. Even if the atmospheric temperature at the time of stretching is too low or too high, the in-plane uniformity tends to decrease.
• the ambient temperature during the stretching may be changed at each stretching stage.
• the stretching time during stretching in the width direction (TD) of the film formed is preferably 2 to 60 seconds, particularly preferably 5 to 45 seconds, and more preferably 10 to 30 seconds. If this stretching time is too short, the film tends to break, and conversely, if it is too long, the equipment load tends to increase. When performing sequential stretching, the stretching time may be changed at each stretching step.
• the temperature of this heat treatment is preferably 60 to 200 ° C., particularly preferably 70 to 150 ° C.
• the heat treatment by the floating dryer is a process of blowing hot air, and the heat treatment temperature means the temperature of the hot air to be blown. If the heat treatment temperature is too low, the dimensional stability tends to decrease, and conversely, if it is too high, the stretchability during the production of the polarizing film tends to decrease.
• the heat treatment time is preferably 1 to 60 seconds, and particularly preferably 5 to 30 seconds. If the heat treatment time is too short, the dimensional stability tends to decrease. Conversely, if the heat treatment time is too long, the stretchability during the production of the polarizing film tends to decrease.
• the polyvinyl alcohol film of the present invention is obtained.
• This polyvinyl alcohol-based film is long in the flow direction (MD), and is made into a film winding body by being wound in a roll shape around a core tube.
• the thickness of the polyvinyl alcohol film of the present invention needs to be 5 to 60 ⁇ m, preferably 5 to 50 ⁇ m from the viewpoint of thinning the polarizing film, and particularly preferably, From the viewpoint of avoiding breakage, the thickness is 5 to 45 ⁇ m, more preferably 10 to 40 ⁇ m.
• the width of the polyvinyl alcohol film of the present invention is preferably 2 m or more, particularly preferably 2 to 6 m from the viewpoint of avoiding breakage.
• the length of the polyvinyl alcohol film of the present invention is preferably 2 km or more, particularly preferably 3 km or more in terms of increasing the area, and more preferably 3 to 50 km in terms of transport weight.
• the polyvinyl alcohol film of the present invention is excellent in stretchability, it is particularly preferably used as a raw material for a polarizing film.
• the polarizing film of the present invention is produced through steps such as swelling, dyeing, boric acid crosslinking, stretching, washing, and drying by feeding the polyvinyl alcohol film out of the film winding body and transporting it in the horizontal direction.
• the swelling process is performed before the dyeing process.
• water is usually used as the treatment liquid.
• the treatment liquid may contain a small amount of an iodide compound, an additive such as a surfactant, alcohol and the like.
• the temperature of the swelling bath is usually about 10 to 45 ° C., and the immersion time in the swelling bath is usually about 0.1 to 10 minutes.
• the dyeing step is performed by bringing a liquid containing iodine or a dichroic dye into contact with the polyvinyl alcohol film.
• a liquid containing iodine or a dichroic dye into contact with the polyvinyl alcohol film.
• 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.
• 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 preferable that potassium iodide coexists in the solution from the viewpoint of stabilizing the polarization performance.
• the temperature during the treatment is preferably about 30 to 70 ° C., and the treatment time is preferably about 0.1 to 20 minutes. If necessary, the stretching operation may be performed during the treatment.
• the stretching step it is preferable to stretch the polyvinyl alcohol film in a uniaxial direction [flow direction (MD)] 3 to 10 times, preferably 3.5 to 6 times.
• a slight stretching stretching to prevent shrinkage in the width direction (TD) or more
• the temperature during stretching is preferably 40 to 70 ° C.
• the stretching ratio may be finally set within the above range, and the stretching operation may be performed not only in one step (one time) but also in the polarizing film manufacturing process a plurality of times.
• the washing step is performed, for example, by immersing the polyvinyl alcohol film in an aqueous iodide solution such as water or potassium iodide, and the precipitate generated on the surface of the polyvinyl alcohol film can be removed.
• an aqueous potassium iodide solution the potassium iodide concentration is 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 is performed, for example, by drying a polyvinyl alcohol film in the atmosphere at 40 to 80 ° C. for 1 to 10 minutes.
• the polarization degree of the polarizing film is preferably 99.5% or more, more preferably 99.8% 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 determined by the light transmittance (H 11 ) measured at the wavelength ⁇ and the two polarized films in a state where two polarizing films are overlapped so that the orientation directions thereof are the same. 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 alignment directions are orthogonal to each other.
• Polarization degree (%) [(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 polarizing film of the present invention is suitable for producing a polarizing plate with little color unevenness and excellent polarization performance.
• the polarizing plate of the present invention is produced by bonding an optically isotropic resin film as a protective film to one or both sides of the polarizing film of the present invention via an adhesive.
• 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 the liquid adhesive composition is uniformly applied to the polarizing film or the protective film, or both, the both are bonded and pressure-bonded. It is performed by irradiating active energy rays.
• a curable resin such as a urethane resin, an acrylic resin, or a urea resin is applied to one or both surfaces of the polarizing film and cured to form a cured layer, whereby a polarizing plate can be obtained. If it does in this way, the said hardened layer becomes a substitute of the said protective film, and can attain thinning.
• the polarizing film and polarizing plate using the polyvinyl alcohol film of the present invention are excellent in polarizing performance, and are portable information terminals, personal computers, televisions, projectors, signage, electronic desk calculators, electronic watches, word processors, electronic papers, game machines. , Video, camera, photo album, thermometer, audio, liquid crystal display devices such as automobiles and machinery instruments, sunglasses, anti-glare glasses, stereoscopic glasses, wearable display, display elements (CRT, LCD, organic EL, electronic paper) Etc.) It is preferably used for reflection-reducing layers, optical communication equipment, medical equipment, building materials, toys and the like.
• the properties ( ⁇ n MDA , ⁇ n MDB , ⁇ n MDC , ⁇ n TDA , ⁇ n TDB ) of the polyvinyl alcohol film and the properties of the polarizing film (degree of polarization, single transmittance, color unevenness) and polarization in the examples and comparative examples described later The plate characteristics (light leakage resistance) were measured and evaluated as follows.
• the observation was performed using an objective lens 40 times, and the average value of retardation was adopted with a line width of 3 pixels.
• the obtained retardation distribution data in the thickness direction of the slice piece is divided by the thickness of the slice piece of 10 ⁇ m to obtain the birefringence distribution in the thickness direction of the slice piece, and the maximum birefringence in the vicinity of both sides of the slice piece
• the values were birefringence ⁇ n MDA and ⁇ n MDB on both sides of the slice piece, respectively. At this time, the larger value was set as ⁇ n MDA and the smaller value as ⁇ n MDB . Further, the birefringence ⁇ n MDC at the central portion in the thickness direction of the slice piece was used.
• the observation was performed using an objective lens 40 times, and the average value of retardation was adopted with a line width of 3 pixels.
• the obtained retardation distribution data in the thickness direction of the slice piece is divided by the thickness of the slice piece of 10 ⁇ m to obtain the birefringence distribution in the thickness direction of the slice piece, and the maximum birefringence in the vicinity of both sides of the slice piece
• the values are set to birefringence ⁇ n TDA and ⁇ n TDB on both sides of the slice piece, respectively. At this time, the larger value was set as ⁇ n TDA and the smaller value as ⁇ n TDB .
• Example 1> (Preparation of polyvinyl alcohol film)
• An aqueous polyvinyl alcohol resin solution having a resin concentration of 25% by weight was obtained by adjusting the concentration.
• this polyvinyl alcohol-based resin aqueous solution is supplied to a twin-screw extruder and defoamed, and then the aqueous solution temperature is set to 95 ° C. and discharged from a T-type slit die discharge port onto a cast drum having a surface temperature of 80 ° C. (Speed 1.3 m / min) and cast to form a film.
• the film formed was peeled off from the cast drum, and dried while being conveyed in the flow direction (MD) while bringing the front and back surfaces of the film into contact with a total of 10 hot rolls. Thereby, a film (width 2 m, thickness 30 ⁇ m) having a moisture content of 7% by weight was obtained.
• the both right and left ends of the film are sandwiched between clips with a clip pitch of 45 mm, and the film is conveyed in the flow direction (MD) at a speed of 8 m / min, using a stretching machine at 80 ° C. in the width direction (TD). Then, the film was conveyed in a dryer at a fixed width of 2.4 m and 130 ° C. to obtain a polyvinyl alcohol film (width 2.4 m, thickness 25 ⁇ m, length 2 km). The properties of the obtained polyvinyl alcohol film were as shown in Table 1 below. Finally, the polyvinyl alcohol film was wound around a core tube in a roll shape to obtain a film winding body.
• the obtained polyvinyl alcohol film was drawn out from the film wound body and stretched 1.7 times in the flow direction (MD) while being immersed and swollen in a water bath at a water temperature of 30 ° C. while being transported in the horizontal direction. During the swelling process, the film did not break or wrinkle.
• the film was stretched 1.6 times in the flow direction (MD) while being immersed in an aqueous solution of 30 g / L of iodine 0.5 g / L and 30 g / L of potassium iodide while being dyed, and then boric acid 40 g / L.
• a 40 ⁇ m thick triacetylcellulose film was bonded and dried at 70 ° C. to obtain a polarizing plate.
• the properties of the obtained polarizing plate were as shown in Table 1 below.
• Example 2 In Example 1, the film was stretched 1.4 times in the width direction (TD) at 80 ° C. using a stretching machine, and then contracted by stress relaxation to a fixed width of 2.4 m (equivalent to 1.2 times stretching) at 130 ° C.
• a polyvinyl alcohol film (width 2.4 m, thickness 25 ⁇ m, length 2 km) was obtained in the same manner as Example 1 except that.
• the properties of the obtained polyvinyl alcohol film were as shown in Table 1 below.
• a polarizing film and a polarizing plate were obtained in the same manner as in Example 1. In the swelling step during the production of the polarizing film, the polyvinyl alcohol film did not break or wrinkle, nor did it break.
• the properties of the obtained polarizing film and polarizing plate were as shown in Table 1 below.
• Example 3 a discharge rate during film formation was 0.8 m / min, a film having a water content of 5% by weight (width 2 m, thickness 20 ⁇ m) was formed, and a width direction (TD) at 80 ° C. using a stretching machine. ) And then a polyvinyl alcohol film (width) in the same manner as in Example 1 except that the film is shrunk by stress relaxation to a fixed width of 2.4 m (equivalent to 1.2 times stretching) at 130 ° C. 2.4 m, thickness 17 ⁇ m, length 2 km). The properties of the obtained polyvinyl alcohol film were as shown in Table 1.
• a polarizing film and a polarizing plate were obtained in the same manner as in Example 1.
• the polyvinyl alcohol film did not break or wrinkle, nor did it break.
• the properties of the obtained polarizing film and polarizing plate were as shown in Table 1.
• Example 4 In Example 1, a polyvinyl alcohol resin aqueous solution was discharged (discharge speed: 2.5 m / min) and cast onto a cast drum having a surface temperature of 90 ° C. to form a film. The film formed was peeled from the cast drum and dried while being conveyed in the flow direction (MD) while the front and back surfaces of the formed film were alternately brought into contact with a total of 10 hot rolls. Thereby, a film (width 2 m, thickness 60 ⁇ m) having a water content of 10% by weight was obtained.
• MD flow direction
• the left and right ends of the film are sandwiched between clips with a clip pitch of 45 mm, and the film is conveyed in the flow direction (MD) at a speed of 8 m / min, using a stretching machine at 80 ° C. in the width direction (TD).
• a polyvinyl alcohol film (width 2.2 m, thickness 55 ⁇ m, length 2 km) was obtained in the same manner as in Example 1 except that the film was stretched 1.1 times.
• the properties of the obtained polyvinyl alcohol film were as shown in Table 1 below.
• a polarizing film and a polarizing plate were obtained in the same manner as in Example 1. In the swelling step during the production of the polarizing film, the polyvinyl alcohol film did not break or wrinkle, nor did it break.
• the properties of the obtained polarizing film and polarizing plate were as shown in Table 1 below.
• Example 5 a polyvinyl alcohol resin aqueous solution was discharged (discharge speed 1.9 m / min) and cast onto a cast drum having a surface temperature of 88 ° C. to form a film.
• the film formed was peeled from the cast drum and dried while being conveyed in the flow direction (MD) while the front and back surfaces of the formed film were alternately brought into contact with a total of 10 hot rolls. Thereby, a film (width 2 m, thickness 45 ⁇ m) having a water content of 10% by weight was obtained.
• the left and right ends of the film are sandwiched between clips with a clip pitch of 45 mm, and the film is conveyed in the flow direction (MD) at a speed of 8 m / min, using a stretching machine at 80 ° C. in the width direction (TD).
• the film was stretched 1.4 times in the same manner as in Example 1 except that the film was contracted by stress relaxation to 135 m at a fixed width of 2.4 m (equivalent to 1.2 times stretching). 4 m, thickness 34 ⁇ m, length 2 km).
• the properties of the obtained polyvinyl alcohol film were as shown in Table 1 below. Further, using the polyvinyl alcohol film, a polarizing film and a polarizing plate were obtained in the same manner as in Example 1. In the swelling step during the production of the polarizing film, the polyvinyl alcohol film did not break or wrinkle, nor did it break. The properties of the obtained polarizing film and polarizing plate were as shown in Table 1 below.
• Example 1 a polyvinyl alcohol resin aqueous solution was discharged (discharge speed: 3.1 m / min) and cast onto a cast drum having a surface temperature of 93 ° C. to form a film.
• the film was formed in the same manner as in Example 1 except that the film was subjected to heat treatment with a heat treatment roll having a surface temperature of 105 ° C. without being stretched in the width direction (TD) using a stretching machine.
• a polyvinyl alcohol film (width 2 m, thickness 75 ⁇ m, length 2 km) having a rate of 2.6% by weight was obtained.
• the properties of the obtained polyvinyl alcohol film were as shown in Table 1 below.
• a polarizing film and a polarizing plate were obtained in the same manner as in Example 1.
• the properties of the obtained polarizing film and polarizing plate are as shown in Table 1 below. When an 80 ° C. heat resistance test was performed, light leakage was confirmed.
• Example 2 the film was formed in the same manner as in Example 1 except that the film was subjected to heat treatment with a heat treatment roll having a surface temperature of 105 ° C. without being stretched in the width direction (TD) using a stretching machine.
• a polyvinyl alcohol film (width 2 m, thickness 30 ⁇ m, length 2 km) having a water content of 1% by weight was obtained.
• the properties of the obtained polyvinyl alcohol film were as shown in Table 1 below.
• the polarizing film and the polarizing plate were produced using the polyvinyl alcohol film in the same manner as in Example 1, the film was broken or wrinkled in the swelling process.
• the characteristics of the obtained polarizing film and polarizing plate were as shown in Table 1 below.
• the birefringence ⁇ n MDA in the flow direction (MD) of the first surface of the polyvinyl alcohol film the birefringence ⁇ n MDB in the flow direction (MD) of the second surface, and the thickness.
• the polarizing films obtained from the polyvinyl alcohol films of Examples 1 to 5 in which the birefringence ⁇ n MDC in the central portion in the direction satisfies all of the formulas (A) to (C) have high polarization characteristics and color unevenness It can be seen that this is a small, uniform and excellent polarizing film.
• the polarizing plate obtained from the thick polyvinyl alcohol film of Comparative Example 1 having a film thickness of 75 ⁇ m generated strong light leakage during the heat resistance test.
• the polyvinyl alcohol-type film of the comparative example 2 which does not satisfy Formula (C) was inferior in a polarization characteristic, and the color nonuniformity was also observed.
• a thin polyvinyl alcohol film having a thickness of 60 ⁇ m or less can obtain a uniform polarizing film having high polarization characteristics and no color unevenness by satisfying the formulas (A) to (C). It can be seen that a polarizing plate with good light leakage resistance can be obtained.
• the polarizing film comprising the polyvinyl alcohol film of the present invention is excellent in polarization performance, such as a portable information terminal, personal computer, TV, projector, signage, electronic desk calculator, electronic watch, word processor, electronic paper, game machine, video, For cameras, photo albums, thermometers, audio, liquid crystal display devices such as automobile and machinery instruments, sunglasses, anti-glare glasses, stereoscopic glasses, wearable displays, display elements (CRT, LCD, organic EL, electronic paper, etc.) It is preferably used for a reflection reducing layer, an optical communication device, a medical device, a building material, a toy and the like.

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