WO2018199141A1 - ポリビニルアルコール系フィルム、偏光膜および偏光板、ならびにポリビニルアルコール系フィルムの製造方法 - Google Patents
ポリビニルアルコール系フィルム、偏光膜および偏光板、ならびにポリビニルアルコール系フィルムの製造方法 Download PDFInfo
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- WO2018199141A1 WO2018199141A1 PCT/JP2018/016754 JP2018016754W WO2018199141A1 WO 2018199141 A1 WO2018199141 A1 WO 2018199141A1 JP 2018016754 W JP2018016754 W JP 2018016754W WO 2018199141 A1 WO2018199141 A1 WO 2018199141A1
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- Prior art keywords
- film
- polyvinyl alcohol
- swelling
- stretching
- alcohol film
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Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- the present invention relates to a polyvinyl alcohol film that is a material for forming a polarizing film having excellent dyeability, a high degree of polarization, and little color unevenness, a polarizing film and a polarizing plate using the polyvinyl alcohol film, and the polyvinyl
- the present invention relates to a method for producing an 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 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 for improving the stretchability of the polyvinyl alcohol film for example, a method for specifying the ratio of the speed of the cast drum when the film is formed to the final winding speed of the polyvinyl alcohol film (for example, a patent) Document 2), a method of floating a film after film formation with a cast drum (for example, see Patent Document 3), and a method for controlling the tension in the drying process of the formed film (for example, see Patent Document 4).
- a film having a thickness of 40 ⁇ m or less and a degree of swelling before and after stretching in water at 30 ° C. in a specific range 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 have poor stretchability when manufacturing a polarizing film. Insufficient to improve.
- 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.
- the degree of swelling before and after stretching in water at 30 ° C. is a specific polyvinyl alcohol film, so that wrinkles during stretching are prevented and a highly stretchable polyvinyl alcohol film is obtained.
- it is not possible to control the wrinkle at the time of swelling it is insufficient for producing a polarizing film having excellent uniformity.
- the productivity of the polyvinyl alcohol film is insufficient.
- 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 present inventors have found that in a long polyvinyl alcohol film having a thickness of 40 ⁇ m or less and a swelling degree of 190 to 230% on a mass basis, the length direction (MD)
- the range of the ratio of the dimensional basis swelling to the dimensional basis swelling degree in the width direction (TD) is adjusted to a specific range, and the mass-based swelling degree after stretching in water is adjusted to a specific range
- the present inventors have found that it is possible to obtain a polarizing film that is excellent in the balance between swelling and stretchability during the production of a polarizing film, does not break even during the production of a thin polarizing film, exhibits high polarization performance, and has little color unevenness.
- the first gist of the present invention is a polyvinyl alcohol film which is a long polyvinyl alcohol film having a thickness of 40 ⁇ m or less and satisfies the following formulas (1) to (3). . 190% ⁇ S A ⁇ 230% (1) 220% ⁇ S B ⁇ 310% (2) 1.01 ⁇ S Y / S X ⁇ 1.20 (3)
- S A represents the degree of swelling based on mass when the polyvinyl alcohol film is immersed in 30 ° C. water for 5 minutes
- S B is the mass-based swelling degree when the polyvinyl alcohol film is uniaxially stretched in 30 ° C.
- S X represents the dimensional standard swelling degree in the width direction (TD) when the polyvinyl alcohol film is immersed in water at 30 ° C. for 5 minutes
- S Y is the polyvinyl alcohol. It represents the dimensional standard swelling degree in the length direction (MD) when the system film is immersed in water at 30 ° C. for 5 minutes.
- 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.
- the film-forming process which forms the aqueous solution of polyvinyl alcohol-type resin by the continuous casting method, and performs continuous drying and continuous extending
- a method for producing a polyvinyl alcohol film comprising a drying / stretching process, wherein the produced polyvinyl alcohol film satisfies the following formulas (1) to (3):
- the manufacturing method of a film is the fourth gist. 190% ⁇ S A ⁇ 230% (1) 220% ⁇ S B ⁇ 310% (2) 1.01 ⁇ S Y / S X ⁇ 1.20 (3) [In the above formula (1), S A represents the degree of swelling based on mass when the polyvinyl alcohol film is immersed in 30 ° C.
- S B is the mass-based swelling degree when the polyvinyl alcohol film is uniaxially stretched in 30 ° C. water at a stretching speed of 0.12 m / min so that the stretching ratio is 3 times.
- S X represents the dimensional standard swelling degree in the width direction (TD) when the polyvinyl alcohol film is immersed in water at 30 ° C. for 5 minutes
- S Y is the polyvinyl alcohol. It represents the dimensional standard swelling degree in the length direction (MD) when the system film is immersed in water at 30 ° C. for 5 minutes.
- the polyvinyl alcohol-based film of the present invention is a long polyvinyl alcohol-based film having a thickness of 40 ⁇ m or less and a mass-based swelling degree (S A ) of 190 to 230%, and a dimension-based swelling in the length direction (MD).
- the ratio (S Y / S X ) of the degree (S Y ) to the dimension-based swelling degree (S X ) in the width direction (TD) is in a specific range, and the mass-based ratio after stretching in water Since the degree of swelling (S B ) is in a specific range, it is excellent in swelling and stretchability at the time of manufacturing a polarizing film, making itself thin (thickness of 40 ⁇ m or less), and manufacturing a thin polarizing film Even if it is used, it is possible to prevent breakage. Furthermore, when the polyvinyl alcohol film is used, a polarizing film having high polarization performance and little color unevenness 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 a film forming process by the continuous casting method, and the film is continuously dried and continuously stretched while being transported in the flow direction. And the drying / stretching step to be applied, the production conditions in each step are combined, and the polyvinyl alcohol film of the present invention satisfying the formulas (1) to (3) can be obtained.
- the film formed is stretched in the width direction (TD) temporarily exceeding 1.3 times, and the final stretch ratio in the width direction (TD) is 1.
- 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 40 ⁇ m or less, and satisfies the following formulas (1) to (3). 190% ⁇ S A ⁇ 230% (1) 220% ⁇ S B ⁇ 310% (2) 1.01 ⁇ S Y / S X ⁇ 1.20 (3) [In the above formula (1), S A represents the degree of swelling based on mass when the polyvinyl alcohol film is immersed in 30 ° C.
- S B when uniaxially stretched to the draw ratio at a drawing speed of the polyvinyl alcohol film of 0.12 m / min in water at 30 °C (240% / min) triples Represents the degree of swelling based on the mass of
- S X represents the dimensional standard swelling degree in the width direction (TD) when the polyvinyl alcohol film is immersed in water at 30 ° C. for 5 minutes
- S Y is the polyvinyl alcohol. This represents the degree of swelling in the length direction (MD) when the system film is immersed in water at 30 ° C. for 5 minutes.
- the thickness of the polyvinyl alcohol film of the present invention needs to be very thin as 40 ⁇ m or less, preferably 5 to 40 ⁇ m from the viewpoint of thinning the polarizing film, and particularly preferably avoiding breakage. It is 10 to 40 ⁇ m, more preferably 10 to 30 ⁇ m. If the polyvinyl alcohol film is too thick, the tension becomes high during stretching in the polarizing film production process described later, which is not preferable. In addition, even if it is too thin, it tends to be easily broken during the production of the polarizing film.
- the polyvinyl alcohol film of the present invention is controlled such that the specific swelling degree when immersed in water at 30 ° C. falls within a specific range. Due to this controlled degree of swelling, the polyvinyl alcohol film is made very thin with a thickness of 40 ⁇ m or less and has excellent performance.
- the polyvinyl alcohol film of the present invention has a mass-based swelling degree (S A ) of 190% ⁇ S A ⁇ 230% when immersed in water at 30 ° C. for 5 minutes. It is controlled to become.
- the mass-based swelling degree (S A ) is preferably 195% ⁇ S A ⁇ 225%, particularly preferably 195% ⁇ S A ⁇ 220%.
- the value of the degree of swelling (S A ) is too small, the stretchability during the production of the polarizing film described later is lowered, so the object of the present invention cannot be achieved, and the value of the degree of swelling (S A ) is If it is too large, wrinkles are generated in the swelling process during the production of the polarizing film, and color unevenness is likely to occur in the polarizing film, so that the object of the present invention cannot be achieved.
- the degree of swelling (S A ) is an index indicating the water retention ability when a polyvinyl alcohol film is immersed in water, and the polyvinyl alcohol film is immersed in water at 30 ° C. for 5 minutes as it is (without stretching).
- the subsequent mass can be obtained as a percentage by dividing by the mass after dipping and drying at 105 ° C. for 16 hours, and can be measured, for example, by the method described later in Examples.
- the polyvinyl alcohol film of the present invention was uniaxially stretched in water at 30 ° C. so that the draw ratio was 3 times at a draw speed of 0.12 m / min (240% / min).
- the mass-based swelling degree (S B ) is controlled so that 220% ⁇ S B ⁇ 310%.
- the degree of swelling (S B ) on a mass basis is preferably 225% ⁇ S B ⁇ 300%, particularly preferably 230% ⁇ S B ⁇ 280%, particularly preferably 230% ⁇ S B ⁇ 260%.
- the value of the degree of swelling (S B ) is too small, the stretchability during the production of the polarizing film described later is deteriorated, so the object of the present invention cannot be achieved, and the value of the degree of swelling (S B ) is If it is too large, wrinkles are generated in the swelling / dying process during the production of the polarizing film, and color unevenness is likely to occur in the polarizing film, so that the object of the present invention cannot be achieved.
- the degree of swelling (S B ) is an index showing the water retention ability of the polyvinyl alcohol film after stretching the polyvinyl alcohol film in water at 30 ° C. at a draw ratio of 3 times. Obtained as a percentage by dividing the mass after stretching at a stretching rate of 3 times at a stretching rate of 0.12 m / min (240% / min) in water by the mass after stretching and drying at 105 ° C. for 16 hours. For example, it can be measured by the method described later in the examples. In general, when a polarizing film is produced from a polyvinyl alcohol film, the film is introduced into a high-temperature drawing tank after swelling and dyeing at 30 ° C.
- the degree of swelling (S B ) when stretched in water at a stretch ratio of 3 times is the stretchability of the film in a high-temperature stretching tank. It is an indicator.
- the polyvinyl alcohol-based film of the present invention has a dimension-based swelling degree (S X ) in the width direction (TD) when immersed in 30 ° C. water for 5 minutes, and a 30 ° C.
- the degree of swelling (S Y ) in the length direction (MD) when immersed in water for 5 minutes is controlled so as to satisfy the relationship of 1.01 ⁇ S Y / S X ⁇ 1.20. Yes.
- This ratio (S Y / S X ) is preferably 1.03 ⁇ S Y / S X ⁇ 1.18, particularly preferably 1.05 ⁇ S Y / S X ⁇ 1.15.
- the degree of swelling is an index showing the spread when the polyvinyl alcohol film is immersed in water, and the polyvinyl alcohol film is left in water at 30 ° C. for 5 minutes without being stretched.
- the length direction (MD) and width direction (TD) dimensions after immersion can be obtained as percentages by dividing by the dimensions before immersion in water, for example, measured by the method described later in Examples. can do.
- 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 (1) to (3) are controlled by combining at least one of these conditions and the stretching condition in the width direction (TD).
- the measurement position of the degree of swelling (S A , S B , S X , S Y ) in the above formulas (1) to (3) is in the region of 500 mm ⁇ 500 mm of the polyvinyl alcohol film.
- 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, so 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 film forming method in the case where 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 is too small, the drying length is insufficient and the speed tends to be difficult to output, and if it is 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 rotational speed 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). More preferably, the conditions of the drying process 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 further 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 film formed 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 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 very thin as 40 ⁇ m or less, preferably 5 to 40 ⁇ m from the viewpoint of thinning the polarizing film, Particularly preferably, the thickness is 10 to 40 ⁇ m, more preferably 10 to 38 ⁇ m from the viewpoint of avoiding breakage.
- 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.
- a polyvinyl alcohol film is dried 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, the liquid crystal display tends to be unable to achieve high brightness.
- 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 degree of swelling of the polyvinyl alcohol film measuring method (S B) A rectangular second sample of 5 cm in the width direction (TD) and 15 cm in the flow direction (MD) is cut out from the central portion in the width direction of the polyvinyl alcohol film, and the flow of the second sample so that the distance between chucks is 5 cm. After sandwiching both ends in the direction (MD) with a chuck, it is immersed in water at 30 ° C., and the draw ratio is 3 times (after stretching) at a stretching speed of 0.12 m / min (240% / min) immediately in the water. Uniaxial stretching was performed so that the distance between the chucks of the second sample was 15 cm.
- a third sample of a square having a width direction (TD) of 10 cm and a flow direction (MD) of 10 cm is cut out from the central portion of the polyvinyl alcohol film in the width direction, and the third sample is placed on a flat glass plate.
- the dimensions in the width direction (TD) and the flow direction (MD) were each measured with calipers.
- 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.
- the 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 through 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.
- 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. 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 were as shown in Table 1 below.
- Example 3 In Example 1, the same procedure was followed except that the polyvinyl alcohol resin aqueous solution was discharged onto a cast drum having a surface temperature of 88 ° C. (discharge speed: 1.9 m / min) and cast to form a film with a water content of 10% by weight. A film (width 2 m, thickness 45 ⁇ m) was formed. Next, the film was stretched 1.2 times in the width direction (TD) at 80 ° C. using a stretching machine in the same manner as in Example 1, and the film thus formed was placed in a dryer at a fixed width of 2.4 m and 135 ° C. A polyvinyl alcohol film (width 2.4 m, thickness 35 ⁇ m, length 2 km) was obtained.
- TD width direction
- 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 were as shown in Table 1 below.
- Example 4 In Example 1, the same procedure was followed except that the polyvinyl alcohol resin aqueous solution was discharged onto a cast drum having a surface temperature of 88 ° C. (discharge speed: 1.9 m / min) and cast to form a film with a water content of 10% by weight. A film (width 2 m, thickness 45 ⁇ m) was formed. Next, in the same manner as in Example 1, the film was stretched 1.4 times in the width direction (TD) at 80 ° C. using a stretching machine and then stressed to a fixed width of 2.4 m (equivalent to 1.2 times stretching) at 135 ° C.
- TD width direction
- Shrinkage was performed by relaxation to obtain a polyvinyl alcohol film (width 2.4 m, thickness 34 ⁇ m, length 2 km).
- 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 polyvinyl alcohol film did not break or wrinkle, nor did it break.
- the properties of the obtained polarizing film were as shown in Table 1 below.
- Example 1 a polyvinyl alcohol resin aqueous solution was discharged (discharge speed: 1.3 m / min) and cast onto a cast drum having a surface temperature of 80 ° C. to form a film.
- Polyvinyl alcohol was obtained in the same manner as in Example 1 except that the film was heat-treated at 130 ° C. using a floating dryer without being stretched in the width direction (TD) using a stretching machine.
- a system film (width 2 m, thickness 30 ⁇ m, length 2 km) was obtained.
- the properties of the obtained polyvinyl alcohol film were as shown in Table 1 below.
- Example 2 a polyvinyl alcohol resin aqueous solution was discharged (discharge speed: 1.3 m / min) and cast onto a cast drum having a surface temperature of 80 ° C. to form a film.
- Polyvinyl alcohol was obtained in the same manner as in Example 1 except that the film was subjected to heat treatment at 120 ° C. using a floating dryer without being stretched in the width direction (TD) using a stretching machine.
- a system film (width 2 m, thickness 30 ⁇ m, length 2 km) was obtained.
- the properties of the obtained polyvinyl alcohol film were as shown in Table 1 below.
- 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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Abstract
Description
そして、上記膨潤工程において重要なことは、ポリビニルアルコール系フィルムを厚み方向に速やかに膨潤させること、および上記染色工程においてフィルム内部に染料がスムーズに浸入できるようにポリビニルアルコール系フィルムを均一に膨潤させることである。
また、上記延伸工程は、染色後のフィルムを流れ方向(MD)に延伸して、ポリビニルアルコール系フィルム中の二色性染料を高度に配向させる工程であり、偏光膜の偏光性能を向上させるためには、この延伸工程において、原反となるポリビニルアルコール系フィルムが流れ方向(MD)に良好な延伸性を示すことが重要である。
また、ポリビニルアルコール系フィルムの延伸性を改良する方法として、例えば、フィルムを製膜する時のキャストドラムの速度と最終的なポリビニルアルコール系フィルム巻き取り速度との比を特定する方法(例えば、特許文献2参照)、キャストドラムで製膜後にフィルムを浮遊させて乾燥する方法(例えば、特許文献3参照)、製膜されたフィルムの乾燥工程における引っ張り具合を制御する方法(例えば、特許文献4参照)、厚み40μm以下で30℃における水中延伸前後の膨潤度が特定の範囲にあるフィルム(例えば、特許文献5参照)が提案されている。
また、上記特許文献4に開示の技術では、ポリビニルアルコール系フィルムの膜厚を均一にできるものの、高分子の配向までは制御できず、偏光膜製造時の膨潤性や延伸性を改良するには不充分である。
190%≦SA≦230%・・・(1)
220%≦SB≦310%・・・(2)
1.01≦SY/SX≦1.20・・・(3)
〔上記式(1)中、SAは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの質量基準の膨潤度を表し、
上記式(2)中、SBは、上記ポリビニルアルコール系フィルムを30℃の水中で0.12m/分の延伸速度で延伸倍率が3倍になるように一軸延伸したときの質量基準の膨潤度を表し、
上記式(3)中、SXは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの幅方向(TD)の寸法基準の膨潤度を表し、SYは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの長さ方向(MD)の寸法基準の膨潤度を表す。〕
190%≦SA≦230%・・・(1)
220%≦SB≦310%・・・(2)
1.01≦SY/SX≦1.20・・・(3)
〔上記式(1)中、SAは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの質量基準の膨潤度を表し、
上記式(2)中、SBは、上記ポリビニルアルコール系フィルムを30℃の水中で0.12m/分の延伸速度で延伸倍率が3倍になるように一軸延伸したときの質量基準の膨潤度を表し、
上記式(3)中、SXは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの幅方向(TD)の寸法基準の膨潤度を表し、SYは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの長さ方向(MD)の寸法基準の膨潤度を表す。〕
本発明のポリビニルアルコール系フィルムは、厚みが40μm以下の長尺のポリビニルアルコール系フィルムであって、下記式(1)~(3)を満足することを特徴とするポリビニルアルコール系フィルムである。
190%≦SA≦230%・・・(1)
220%≦SB≦310%・・・(2)
1.01≦SY/SX≦1.20・・・(3)
〔上記式(1)中、SAは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの質量基準の膨潤度を表し、
上記式(2)中、SBは、上記ポリビニルアルコール系フィルムを30℃の水中で0.12m/分(240%/分)の延伸速度で延伸倍率が3倍になるように一軸延伸したときの質量基準の膨潤度を表し、
上記式(3)中、SXは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの幅方向(TD)の寸法基準の膨潤度を表し、SYは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬したときの長さ方向(MD)の寸法基準の膨潤度を表す。〕
上記ポリビニルアルコール系フィルムの厚みが厚すぎると、後述する偏光膜製造過程における延伸時に張力が高くなり好ましくない。なお、薄すぎても偏光膜製造時に破断しやすくなる傾向がある。
上記膨潤度(SA)の値が小さすぎると、後述する偏光膜製造時の延伸性が低下するため、本発明の目的を達成することができず、上記膨潤度(SA)の値が大きすぎると、偏光膜製造時の膨潤工程において皺が発生し、偏光膜に色ムラが発生しやすくなるため、本発明の目的を達成することができない。
上記膨潤度(SB)の値が小さすぎると、後述する偏光膜製造時の延伸性が悪化するため、本発明の目的を達成することができず、上記膨潤度(SB)の値が大きすぎると、偏光膜製造時の膨潤・染色工程において皺が発生し、偏光膜に色ムラが発生しやすくなるため、本発明の目的を達成することができない。
この膨潤・染色工程でポリビニルアルコール系フィルムは3倍弱に延伸されることから、水中で延伸倍率3倍に延伸したときの上記膨潤度(SB)は高温の延伸槽におけるフィルムの延伸性の指標となるものである。
上記比(SY/SX)の値が小さすぎると、後述する偏光膜製造時の延伸性が悪化するため、本発明の目的を達成することができず、上記比(SY/SX)の値が大きすぎると、偏光膜製造時の膨潤工程において皺が発生し、偏光膜に色ムラが発生しやすくなるため、本発明の目的を達成することができない。
まず、本発明で使用されるポリビニルアルコール系樹脂、およびそのポリビニルアルコール系樹脂水溶液に関して説明する。
本発明において、ポリビニルアルコール系フィルムを構成す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、すなわち、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。必要に応じて、酢酸ビニルと、少量(通常、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あげられる。これらは単独でもしくは2種以上併せて用いることができる。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。
ここで、本発明における平均ケン化度は、JIS K 6726に準じて測定されるものである。
本発明のポリビニルアルコール系フィルムは、キャスト法や溶融押出し法で製造されるが、本発明においては、透明性、厚み精度、表面平滑性等の点から、キャスト法が好ましく、特に好ましくは、生産性の点から、連続キャスト法である。
ここで、キャスト型がキャストドラムである場合の製膜方法を説明する。
上記ポリビニルアルコール系樹脂水溶液の温度が低すぎると、流動不良となる傾向があり、高すぎると、発泡する傾向がある。
上記ポリビニルアルコール系樹脂水溶液の粘度が低すぎると、流動不良となる傾向があり、高すぎると、流延が困難となる傾向がある。
上記吐出速度が遅すぎると、生産性が低下する傾向があり、速すぎると、流延が困難となる傾向がある。
上記直径が小さすぎると、乾燥長が不足し速度が出にくい傾向があり、大きすぎると、輸送性が低下する傾向がある。
上記キャストドラムの幅が小さすぎると、生産性が低下する傾向がある。
上記回転速度が遅すぎると、生産性が低下する傾向があり、速すぎると、乾燥が不充分となる傾向がある。
上記表面温度が低すぎると、乾燥不良となる傾向があり、高すぎると、発泡してしまう傾向がある。
上記製膜されたフィルムの含水率は、0.5~15重量%であることが好ましく、特に好ましくは1~13重量%、さらに好ましくは2~12重量%である。上記含水率が低すぎても高すぎても、目的とする膨潤性や延伸性の発現が困難となる傾向にある。
上記含水率の調整は、幅方向(TD)の延伸前のフィルムの含水率が高すぎる場合は、幅方向(TD)への延伸前にフィルムを乾燥することが好ましく、逆に、幅方向(TD)の延伸前のフィルムの含水率が低すぎる場合は、幅方向(TD)への延伸前に調湿することが好ましい。より好ましくは、含水率が上記範囲となるように乾燥工程の条件を調整することである。
上記クリップのピッチが広すぎると、延伸後のフィルムにたわみが生じたり、得られるポリビニルアルコール系フィルムの面内の均一性が低下したりする傾向がある。また、クリップの挟持位置(クリップの先端部)は、製膜されたフィルムの幅方向両端縁から100mm以下が好ましい。クリップの挟持位置(先端部)がフィルム幅方向中心部に位置しすぎると、破棄するフィルム端部が増大し、製品幅が狭くなる傾向にある。
幅固定の搬送工程を挿入する場合、固定幅を、1段階目の連続的な延伸後の幅よりも狭めることも可能である。延伸直後のフィルムは応力緩和のために収縮しやすく、脱水に伴う収縮も起きるため、固定幅をこれらの収縮幅まで狭めることが可能である。ただし、収縮幅以上に狭めると、フィルムにたわみが生じるため、好ましくない。
上記連続的な延伸は、先に述べたように、フィルムの乾燥工程後に行われることが好ましいが、フィルムの乾燥工程前、乾燥工程中、および乾燥工程後の少なくとも一つにて行われる。
この場合、一時的に1.3倍を超えて延伸した後、延伸倍率1.05~1.3の固定幅で、フィルムを単純に搬送すればよい。この方法により、フィルムの応力緩和がなされ、特に薄型フィルムの場合に、破断を回避することが可能になる。
上記熱処理温度が低すぎると、寸法安定性が低下しやすい傾向があり、逆に、高すぎると、偏光膜製造時の延伸性が低下する傾向がある。
また、熱処理時間は1~60秒間であることが好ましく、特に好ましくは5~30秒間である。熱処理時間が短すぎると、寸法安定性が低下する傾向があり、逆に、長すぎると、偏光膜製造時の延伸性が低下する傾向がある。
このようにして、本発明のポリビニルアルコール系フィルムが得られる。このポリビニルアルコール系フィルムは、流れ方向(MD)に長く、芯管にロール状に巻き取られることにより、フィルム巻装体に作製される。
本発明のポリビニルアルコール系フィルムの厚みは、先に述べたように、40μm以下と非常に薄くなっていることが必要であり、好ましくは、偏光膜の薄型化の点で5~40μmが好ましく、特に好ましくは、破断回避の点で10~40μm、さらに好ましくは10~38μmである。
本発明の偏光膜は、上記ポリビニルアルコール系フィルムを、前記フィルム巻装体から繰り出して水平方向に搬送し、膨潤、染色、ホウ酸架橋、延伸、洗浄、乾燥等の工程を経て製造される。
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(H1)より、下記式にしたがって算出される。
偏光度(%)=〔(H11-H1)/(H11+H1)〕1/2
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。
本発明の偏光膜は、色ムラが少なく、偏光性能に優れた偏光板を製造するのに好適である。
本発明の偏光板は、本発明の偏光膜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することにより、作製される。保護フィルムとしては、たとえば、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等のフィルムまたはシートがあげられる。
ポリビニルアルコール系フィルムの幅方向中央部から、幅方向(TD)に10cm、流れ方向(MD)に20cmの長方形のフィルム状サンプルを切り出し、このフィルム状サンプルをさらに幅が3mm、長さが20cmの短冊状にカットした。その後、これらの短冊状の第1サンプル全てを30℃の1,000gの水中にそのまま浸漬した。30分間浸漬後に短冊状の第1サンプルを取り出し、遠心分離機を用いて3,000rpmで5分間遠心脱水し、脱水後の質量「N」(短冊状のサンプル全ての合計)を測定した。続いて、短冊状の上記第1サンプルを105℃の乾燥機で16時間乾燥した後、質量「M」(短冊状の第1サンプル全ての合計)を測定し、下記式により膨潤度(SA)を算出した。なお同様の測定を3回行い、その平均値を採用した。
膨潤度(SA)(%) =100×N/M
ポリビニルアルコール系フィルムの幅方向中央部から幅方向(TD)に5cm、流れ方向(MD)に15cmの長方形の第2サンプルを切り出し、チャック間距離が5cmとなるように、上記第2サンプルの流れ方向(MD)の両端部をチャックで挟んだ後、30℃の水中に浸漬し、その水中で直ちに0.12m/分(240%/分)の延伸速度で延伸倍率が3倍(延伸後の第2サンプルの上記チャック間距離が15cm)になるように一軸延伸した。延伸後、上記第2サンプルを水中から取り出し、温度20℃、相対湿度65%RHの環境中で1分以内に、ろ紙を用いて延伸後の第2サンプル表面の水分をふき取り、その第2サンプルの質量「L」を測定した。続いてその第2サンプルを105℃の乾燥機で16時間乾燥した後、質量「K」を測定し、下記式により、30℃の水中で延伸倍率3倍に延伸した後の膨潤度(SB)を算出した。なお同様の測定を5回行い、その平均値を採用した。
膨潤度(SB)(%)=100×L/K
ポリビニルアルコール系フィルムの幅方向中央部から幅方向(TD)10cm、流れ方向(MD)10cmの正方形の第3サンプルを切り出し、この第3サンプルを平坦なガラス板上に載せ、その第3サンプルの幅方向(TD)および流れ方向(MD)の寸法を各々ノギスにて計測した。つぎに、上記第3サンプルを、30℃に調整されたイオン交換水槽に5分間浸漬した後、取り出し、直ちに、平坦なガラス板上に載せ、その第3サンプルの幅方向(TD)および流れ方向(MD)の寸法を各々ノギスにて計測し、下記式により、膨潤度(SXおよびSY)を算出した。なお、上記操作は23℃、50%RHの環境下で行なった。
膨潤度(SX)(%)=(浸漬後のTDの寸法/浸漬前のTDの寸法)×100
膨潤度(SY)(%)=(浸漬後のMDの寸法/浸漬前のMDの寸法)×100
得られた偏光膜の幅方向の中央部から、長さ4cm×幅4cmの試験片を切り出し、自動偏光フィルム測定装置(日本分光社製:VAP7070)を用いて、偏光度(%)と単体透過率(%)を測定した。
得られた偏光膜の幅方向の中央部から、長さ30cm×幅30cmの試験片を切り出し、クロスニコル状態の2枚の偏光板(単体透過率43.5%、偏光度99.9%)の間に45°の角度で挟んだのちに、表面照度14,000lxのライトボックスを用いて、透過モードで光学的な色ムラを観察し、以下の基準で評価した。
(評価基準)
○・・・色ムラがなかった。
△・・・かすかに色ムラがあった。
×・・・はっきりとした色ムラがあった。
(ポリビニルアルコール系フィルムの作製)
5,000Lの溶解缶に、重量平均分子量142,000、ケン化度99.8モル%のポリビニルアルコール系樹脂1,000kg、水2,500kg、可塑剤としてグリセリン105kg、および界面活性剤としてポリオキシエチレンラウリルアミン0.25kgを入れ、撹拌しながら150℃まで昇温して加圧溶解を行い、濃度調整により樹脂濃度25重量%のポリビニルアルコール系樹脂の水溶液を得た。ついで、そのポリビニルアルコール系樹脂水溶液を、2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より、表面温度が80℃のキャストドラムに吐出(吐出速度1.3m/分)および流延して製膜した。その製膜したフィルムをキャストドラムから剥離し、流れ方向(MD)に搬送しながら、そのフィルムの表面と裏面とを合計10本の熱ロールに交互に接触させながら乾燥を行った。それにより、含水率7重量%のフィルム(幅2m、厚み30μm)を得た。つぎに、上記フィルムの左右両端部をクリップピッチ45mmのクリップで挟持し、そのフィルムを流れ方向(MD)に速度8m/分で搬送しながら、延伸機を用いて80℃で幅方向(TD)に1.2倍延伸した後、そのフィルムを固定幅2.4mで130℃の乾燥機中を搬送させ、ポリビニルアルコール系フィルム(幅2.4m、厚み25μm、長さ2km)を得た。得られたポリビニルアルコール系フィルムの特性は後記の表1に示される通りであった。最後に、そのポリビニルアルコール系フィルムを芯管にロール状に巻き取り、フィルム巻装体を得た。
得られたポリビニルアルコール系フィルムを上記フィルム巻装体から繰り出し、水平方向に搬送しながら、水温30℃の水槽に浸漬して膨潤させながら流れ方向(MD)に1.7倍に延伸した。その膨潤工程で、フィルムに折れや皺は発生しなかった。ついで、ヨウ素0.5g/L、ヨウ化カリウム30g/Lよりなる30℃の水溶液中に浸漬して染色しながら流れ方向(MD)に1.6倍に延伸し、つぎに、ホウ酸40g/L、ヨウ化カリウム30g/Lの組成の水溶液(50℃)に浸漬してホウ酸架橋しながら流れ方向(MD)に2.1倍に一軸延伸した。最後に、ヨウ化カリウム水溶液で洗浄を行い、50℃で2分間乾燥して総延伸倍率5.8倍の偏光膜を得た。この偏光膜製造中に破断は起きなかった、また、得られた偏光膜の特性は後記の表1に示される通りであった。
上記で得られた偏光膜の両面に、ポリビニルアルコール水溶液を接着剤として用いて、膜厚40μmのトリアセチルセルロースフィルムを貼合し、70℃で乾燥して偏光板を得た。
実施例1において、延伸機を用いて80℃で幅方向(TD)に1.4倍延伸した後、130℃で固定幅2.4m(1.2倍延伸相当)まで応力緩和により収縮し搬送する以外は、実施例1と同様にしてポリビニルアルコール系フィルム(幅2.4m、厚み25μm、長さ2km)を得た。得られたポリビニルアルコール系フィルムの特性は後記の表1に示される通りであった。
さらに、上記ポリビニルアルコール系フィルムを用いて、実施例1と同様にして、偏光膜および偏光板を得た。偏光膜製造時の膨潤工程において、上記ポリビニルアルコール系フィルムに折れや皺の発生はなく、また破断も起きなかった。得られた偏光膜の特性は後記の表1に示される通りであった。
実施例1において、ポリビニルアルコール系樹脂水溶液を表面温度が88℃のキャストドラムに吐出(吐出速度1.9m/分)および流延して製膜した以外は同様に行い、含水率10重量%のフィルム(幅2m、厚み45μm)を製膜した。ついで、実施例1と同様にして延伸機を用いて80℃で幅方向(TD)に1.2倍延伸した後、上記製膜したフィルムを固定幅2.4mで135℃の乾燥機中を搬送させ、ポリビニルアルコール系フィルム(幅2.4m、厚み35μm、長さ2km)を得た。得られたポリビニルアルコール系フィルムの特性は後記の表1に示される通りであった。
さらに、上記ポリビニルアルコール系フィルムを用いて、実施例1と同様にして、偏光膜および偏光板を得た。偏光膜製造時の膨潤工程において、上記ポリビニルアルコール系フィルムに折れや皺の発生はなく、また破断も起きなかった。得られた偏光膜の特性は後記の表1に示される通りであった。
実施例1において、ポリビニルアルコール系樹脂水溶液を表面温度が88℃のキャストドラムに吐出(吐出速度1.9m/分)および流延して製膜した以外は同様に行い、含水率10重量%のフィルム(幅2m、厚み45μm)を製膜した。ついで、実施例1と同様にして、延伸機を用いて80℃で幅方向(TD)に1.4倍延伸した後、135℃で固定幅2.4m(1.2倍延伸相当)まで応力緩和により収縮させ、ポリビニルアルコール系フィルム(幅2.4m、厚み34μm、長さ2km)を得た。得られたポリビニルアルコール系フィルムの特性は後記の表1に示される通りであった。
さらに、上記ポリビニルアルコール系フィルムを用いて、実施例1と同様にして、偏光膜および偏光板を得た。偏光膜製造時の膨潤工程において、上記ポリビニルアルコール系フィルムに折れや皺の発生はなく、また破断も起きなかった。得られた偏光膜の特性は後記の表1に示される通りであった。
実施例1において、表面温度が80℃のキャストドラムにポリビニルアルコール系樹脂水溶液を吐出(吐出速度1.3m/分)および流延して製膜した。その製膜したフィルムに対し、延伸機を用いた幅方向(TD)への延伸を行わずに、フローティングドライヤーを用いて130℃で熱処理を行った以外は実施例1と同様にして、ポリビニルアルコール系フィルム(幅2m、厚み30μm、長さ2km)を得た。得られたポリビニルアルコール系フィルムの特性は後記の表1に示される通りであった。
さらに、上記ポリビニルアルコール系フィルムを用いて、実施例1と同様にして、偏光膜および偏光板を製造したところ、膨潤工程において、上記ポリビニルアルコール系フィルムに折れや皺が発生した。得られた偏光膜の特性は後記の表1に示される通りであった。
実施例1において、表面温度が80℃のキャストドラムにポリビニルアルコール系樹脂水溶液を吐出(吐出速度1.3m/分)および流延して製膜した。その製膜したフィルムに対し、延伸機を用いた幅方向(TD)への延伸を行わずに、フローティングドライヤーを用いて120℃で熱処理を行った以外は実施例1と同様にして、ポリビニルアルコール系フィルム(幅2m、厚み30μm、長さ2km)を得た。得られたポリビニルアルコール系フィルムの特性は下記の表1に示される通りであった。
さらに、上記ポリビニルアルコール系フィルムを用いて、実施例1と同様にして、偏光膜および偏光板を製造したところ、膨潤工程において、上記ポリビニルアルコール系フィルムに折れや皺が発生した。得られた偏光膜の特性は下記の表1に示される通りであった。
一方、式(3)を満足しない比較例1および比較例2のポリビニルアルコール系フィルムは、偏光特性に劣り、色ムラも観察されるものであることがわかる。
Claims (6)
- 厚みが40μm以下の長尺のポリビニルアルコール系フィルムであって、下記式(1)~(3)を満足することを特徴とするポリビニルアルコール系フィルム。
190%≦SA≦230%・・・(1)
220%≦SB≦310%・・・(2)
1.01≦SY/SX≦1.20・・・(3)
上記式(1)中、SAは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの質量基準の膨潤度を表し、
上記式(2)中、SBは、上記ポリビニルアルコール系フィルムを30℃の水中で0.12m/分の延伸速度で延伸倍率が3倍になるように一軸延伸したときの質量基準の膨潤度を表し、
上記式(3)中、SXは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの幅方向の寸法基準の膨潤度を表し、SYは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬したときの長さ方向の寸法基準の膨潤度を表す。 - 請求項1記載のポリビニルアルコール系フィルムが用いられていることを特徴とする偏光膜。
- 請求項2記載の偏光膜と、その偏光膜の少なくとも片面に設けられた保護フィルムとを備えていることを特徴とする偏光板。
- ポリビニルアルコール系樹脂の水溶液を連続キャスト法により製膜する製膜工程と、その製膜したフィルムを、流れ方向に搬送しながら、そのフィルムに対し連続的な乾燥および連続的な延伸を施す乾燥・延伸工程とを備えたポリビニルアルコール系フィルムの製造方法であって、製造されるポリビニルアルコール系フィルムが、下記式(1)~(3)を満足するようにすることを特徴とするポリビニルアルコール系フィルムの製造方法。
190%≦SA≦230%・・・(1)
220%≦SB≦310%・・・(2)
1.01≦SY/SX≦1.20・・・(3)
上記式(1)中、SAは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの質量基準の膨潤度を表し、
上記式(2)中、SBは、上記ポリビニルアルコール系フィルムを30℃の水中で0.12m/分の延伸速度で延伸倍率が3倍になるように一軸延伸したときの質量基準の膨潤度を表し、
上記式(3)中、SXは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬させたときの幅方向の寸法基準の膨潤度を表し、SYは、上記ポリビニルアルコール系フィルムを30℃の水中に5分間浸漬したときの長さ方向の寸法基準の膨潤度を表す。 - 上記乾燥・延伸工程において、上記製膜したフィルムを幅方向に1.05~1.3倍延伸することを特徴とする請求項4記載のポリビニルアルコール系フィルムの製造方法。
- 上記乾燥・延伸工程において、上記製膜したフィルムを幅方向に、一時的に1.3倍を超えて延伸した後、最終的な幅方向の延伸倍率が1.3倍以下になるよう寸法収縮させることを特徴とする請求項4または5記載のポリビニルアルコール系フィルムの製造方法。
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