WO2018199140A1 - 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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- WO2018199140A1 WO2018199140A1 PCT/JP2018/016753 JP2018016753W WO2018199140A1 WO 2018199140 A1 WO2018199140 A1 WO 2018199140A1 JP 2018016753 W JP2018016753 W JP 2018016753W WO 2018199140 A1 WO2018199140 A1 WO 2018199140A1
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- Prior art keywords
- film
- polyvinyl alcohol
- width direction
- alcohol film
- sample
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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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- 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 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).
- 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 thick polyvinyl alcohol film used in the examples with a thickness of about 45 ⁇ m has a certain improvement effect on the swellability during the production of the polarizing film, but the polarizing film is further improved. It is difficult to cope with thinning, and in a polyvinyl alcohol film having a thin film thickness of 40 ⁇ m or less, it is insufficient for improving the swellability and stretchability during the production of the polarizing film.
- 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.
- a long polyvinyl alcohol film having a thickness of 40 ⁇ m or less is immersed in water at 30 ° C. for 30 seconds in the length direction (MD).
- MD length direction
- the amount of elongation in the width direction (TD) when immersed in water at 30 ° C. for 300 seconds the amount of elongation in the width direction (TD) when immersed in water at 30 ° C.
- the present invention is a long polyvinyl alcohol film having a thickness of 40 ⁇ m or less, and a rectangle of width direction (TD) 40 mm ⁇ length direction (MD) 270 mm cut out from the central portion in the width direction of the polyvinyl alcohol film.
- the elongation amount of the said length direction (MD) in the part of 250 mm except the length direction (MD) both ends before immersion WMD30 is 30 mm or more and 50 mm or less, and about this 2nd sample of the rectangle of width direction (TD) 270mm x length direction (MD) 40mm cut out from the width direction center part of the said polyvinyl alcohol-type film, this 2nd sample Is immersed in water at 30 ° C. for 300 seconds, at a 250 mm portion excluding both ends in the width direction (TD) before immersion.
- Elongation amount W TD300 in the width direction (TD) to the polyvinyl alcohol film is 15mm or more 60mm or less with a first aspect that.
- 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 a first sample of a rectangle having a width direction of 40 mm and a flow direction of 270 mm cut out from a width direction central portion of the produced polyvinyl alcohol film.
- the elongation WMD30 in the length direction in the 250 mm portion excluding both ends in the length direction before immersion is adjusted to 30 mm or more and 50 mm or less, and manufactured.
- a second sample of the rectangle, the second sample when immersed for 300 seconds in 30 ° C. water, in the width direction of the elongation amount W TD300 in the portion of 250mm excluding the widthwise ends before immersion is 15mm or more 60mm or less
- the polyvinyl alcohol film of the present invention is a long polyvinyl alcohol film having a thickness of 40 ⁇ m or less, and when it is immersed in water at 30 ° C. for a specific time, the elongation amount W MD30 in the length direction (MD) and Since the above-mentioned amount of elongation WTD300 in the width direction (TD) is in a specific range, it is excellent in swelling property and stretchability at the time of manufacturing a polarizing film, and is thin (40 ⁇ m or less in thickness) itself. Even if it is used for manufacturing a polarizing film, 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 productivity of a polarizing film using the polyvinyl alcohol film is improved.
- 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 process to be applied, the manufacturing conditions in each of these processes are combined, and the elongation WMD30 in the length direction (MD) when immersed in water at 30 ° C. for a specific time and The polyvinyl alcohol film of the present invention can be obtained in which the elongation amount W TD300 in the width direction (TD) is in a specific range.
- the elongation amount WMD30 and the elongation amount WTD300 are suitable, A polyvinyl alcohol film excellent in swelling property and stretchability during film production 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 when immersed in water at 30 ° C., the polyvinyl alcohol film is specific in the length direction (MD) and the width direction (TD). Indicates the amount of elongation. That is, about the 1st rectangular sample of the width direction (TD) 40mm x length direction (MD) 270mm cut out from the width direction center part of the said polyvinyl alcohol-type film, this 1st sample was immersed in 30 degreeC water for 30 second.
- the length extension WMD30 in the 250 mm portion excluding both ends in the length direction before immersion is 30 mm or more and 50 mm or less.
- this 2nd sample was immersed in 30 degreeC water for 300 second.
- W TD300 in the 250 mm portion excluding both ends in the width direction before immersion is 15 mm or more and 60 mm or less.
- 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 38 ⁇ 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 was controlled such that the elongation amount in the length direction (MD) and the width direction (TD) when in water at 30 ° C. was in a specific range. Is. With this controlled elongation, the polyvinyl alcohol film is made very thin with a thickness of 40 ⁇ m or less and has excellent performance.
- the elongation amount in the length direction (MD) is in a 250 mm portion excluding both end portions in the length direction before immersion when the first sample is immersed in water at 30 ° C. for 30 seconds.
- the elongation WMD30 in the length direction (MD) is controlled to be 30 mm or more and 50 mm or less.
- the elongation ( WMD30 ) in the length direction (MD) is preferably 31 mm ⁇ W MD30 ⁇ 48 mm, particularly preferably 32 mm ⁇ W MD30 ⁇ 45 mm, and more preferably 33 mm ⁇ W MD30 ⁇ 43 mm.
- WMD30 If the value of WMD30 is too small, the stretchability at the time of producing a polarizing film described later deteriorates, so that the object of the present invention cannot be achieved. If the value of WMD30 is too large, the polarizing film is produced. Since sagging occurs and wrinkles and creases occur, the object of the present invention cannot be achieved.
- the amount of elongation in the width direction is the width direction in the 250 mm portion excluding both ends in the width direction before immersion when the second sample is immersed in water at 30 ° C. for 300 seconds.
- Elongation WTD300 is controlled to be 15 mm or more and 60 mm or less.
- the amount of extension W TD300 in the width direction (TD) is preferably 16 mm ⁇ W TD300 ⁇ 55 mm, particularly preferably 17 mm ⁇ W TD300 ⁇ 50 mm, and more preferably 18 mm ⁇ W TD300 ⁇ 45 mm. If the value of W TD300 is too small, uneven dyeing occurs during the production of the polarizing film, so that the object of the present invention cannot be achieved. If the value of W TD300 is too large, the film becomes wide during the production of the polarizing film. The object of the present invention cannot be achieved because of excessive spreading in the direction and wrinkles and folds.
- a method of stretching in the width direction (TD) is preferred.
- 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 WMD30 and WTD300 are controlled by combining at least one of these conditions and the stretching condition in the width direction (TD).
- the value of the W MD30 and W TD300 in the present invention is measured, for example, by the following method.
- the measurement position of these WMD30 and WTD300 exists in the area
- the first sample with the clip is put into the water, Immediately immerse the first sample with the long side vertical (vertical). Immediately after the immersion, the rod-shaped jig is hooked on the upper part of the water tank, and the long side of the first sample is fixed vertically. Thereafter, a metal ruler is immersed in water, and the distance between marked lines is measured 30 seconds after the immersion of the first sample.
- the elongation (W MD30 ) (unit: mm) is calculated by subtracting the original distance between marked lines (250 mm) from the measured value read in 0.5 mm increments.
- the second sample with the clip is put into the water, Immediately immerse the second sample with the long side vertical (vertical). Immediately after the immersion, the rod-shaped jig is hooked on the upper part of the water tank, and the long side of the second sample is fixed vertically. Thereafter, a metal ruler is immersed in water, and the distance between marked lines is measured 300 seconds after the immersion of the second sample.
- the elongation (W TD300 ) (unit: mm) is calculated by subtracting the original distance between marked lines (250 mm) from the measured value read in 0.5 mm increments.
- 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, there is a tendency that sufficient optical performance is difficult to obtain when the polyvinyl alcohol resin is used as an optical film, and if it is too large, it is difficult to stretch the polyvinyl alcohol film at the time of producing a 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 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 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).
- 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, productivity tends to decrease, and if it is too fast, drying tends to be insufficient.
- 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 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 7 m, more preferably 3 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 particularly preferably used as a raw material for a polarizing film because of its excellent stretchability.
- 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, 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.
- Example 1 (Preparation of polyvinyl alcohol film)
- 1,000 kg of polyvinyl alcohol resin having a weight average molecular weight of 142,000 and a saponification degree of 99.8 mol%, 2,500 kg of water, 105 kg of glycerin as a plasticizer, and polyoxy as a surfactant 0.25 kg of ethylene laurylamine was added, and the mixture was heated to 150 ° C. with stirring and dissolved under pressure.
- concentration an aqueous solution of a polyvinyl alcohol resin having a resin concentration of 25% by weight was obtained.
- 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, after stretching 1.1 times in the width direction (TD) at 80 ° C. using a stretching machine in the same manner as in Example 1, the film formed above was placed in a dryer at a fixed width of 2.2 m and 135 ° C. A polyvinyl alcohol film (width 2.2 m, thickness 38 ⁇ m, length 2 km) was obtained.
- TD width direction
- the properties of the obtained polyvinyl alcohol film were as shown in Table 1. 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 1 a polyvinyl alcohol film (width 2 m, thickness 30 ⁇ m, thickness of 2 ⁇ m, 30 ⁇ m in width, in the same manner as in Example 1 except that the film formed was not stretched in the width direction (TD) using a stretching machine. 2 km) 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 properties of the obtained polarizing film were as shown in Table 1 below.
- the polarizing film obtained from the polyvinyl alcohol film of Examples 1 to 3 satisfying the above specific range together with the elongation amount of (TD) has high polarization characteristics and is uniform without color unevenness. I know that there is.
- the polarizing film obtained from the polyvinyl alcohol-based film of Comparative Example 1 in which the amount of elongation in the width direction (TD) is larger than the specified range is inferior in polarization characteristics and color unevenness is observed. I understand that.
- 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)、30℃の水に30秒間浸漬したときの長さ方向(MD)の伸び量を特定の範囲に調整すると共に、30℃の水に300秒間浸漬したときの幅方向(TD)の伸び量を特定の範囲に調整する方法(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。
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、30℃の水に浸漬したときに、長さ方向(MD)および幅方向(TD)において特定の伸び量を示す。すなわち、上記ポリビニルアルコール系フィルムの幅方向中央部から切り出す幅方向(TD)40mm×長さ方向(MD)270mmの長方形の第1サンプルについて、この第1サンプルを30℃の水に30秒間浸漬したときの、浸漬前の長さ方向両端部を除く250mmの部分における長さ方向の伸び量WMD30が30mm以上50mm以下となっている。さらに、上記ポリビニルアルコール系フィルムの幅方向中央部から切り出す幅方向(TD)270mm×長さ方向(MD)40mmの長方形の第2サンプルについて、この第2サンプルを30℃の水に300秒間浸漬したときの、浸漬前の幅方向両端部を除く250mmの部分における幅方向の伸び量WTD300が15mm以上60mm以下となっている。
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WMD30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、またWMD30の値が大きすぎると、偏光膜製造時にたるみが発生し、皺や折れが発生するため、本発明の目的を達成することができない。
上記WTD300の値が小さすぎると、偏光膜製造時に染色ムラが発生するため、本発明の目的を達成することができず、またWTD300の値が大きすぎると、偏光膜製造時にフィルムが幅方向に広がりすぎ、皺や折れが発生するため、本発明の目的を達成することができない。
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)40mm×長さ方向(MD)270mmの長方形の第1サンプルを切り出す。ついで、この第1サンプルの長さ方向(MD)の両端縁から10mmずつ内側に油性インク(線の太さが0.3mm)で標線を入れる。両端部の標線から外側の部分を市販のクリップ(チャック幅40mm、質量7.3g)で挟み、一方の上記クリップは棒状冶具で固定する。標線間距離が250mmであることを確認後、円筒状の透明な水槽に蓄えた30℃に調温した純水に、上記クリップが付いた第1サンプルをその全体が水中に入るように、速やかに上記第1サンプルの長辺を垂直(鉛直)にして浸漬する。浸漬直後に水槽上部に上記棒状冶具を引っ掛けて上記第1サンプルの長辺を垂直(鉛直)にして固定する。その後、金属製の物差しを水中に浸漬して、上記第1サンプルの浸漬から30秒後に標線間距離を測定する。0.5mm刻みで読み取った測定値から元の標線間距離(250mm)を引いて伸び量(WMD30)(単位はmm)を算出する。
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)270mm×長さ方向(MD)40mmの長方形の第2サンプルを切り出す。ついで、この第2サンプルの幅方向(TD)の両端縁から10mmずつ内側に油性インク(線の太さが0.3mm)で標線を入れる。両端部の標線から外側の部分を市販のクリップ(チャック幅40mm、質量7.3g)で挟み、一方の上記クリップは棒状冶具で固定する。標線間距離が250mmであることを確認後、円筒状の透明な水槽に蓄えた30℃に調温した純水に、上記クリップが付いた第2サンプルをその全体が水中に入るように、速やかに上記第2サンプルの長辺を垂直(鉛直)にして浸漬する。浸漬直後に水槽上部に上記棒状冶具を引っ掛けて上記第2サンプルの長辺を垂直(鉛直)にして固定する。その後、金属製の物差しを水中に浸漬して、上記第2サンプルの浸漬から300秒後に標線間距離を測定する。0.5mm刻みで読み取った測定値から元の標線間距離(250mm)を引いて伸び量(WTD300)(単位はmm)を算出する。
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工程を説明する。
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。特に好ましくは、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)40mm×長さ方向(MD)270mmの長方形の第1サンプルを切り出した。ついで、この第1サンプルの270mm長の両端から10mmずつ内側に油性インク(線の太さが0.3mm)で標線を入れた。両端部の標線から外側の部分を市販のクリップ(チャック幅40mm、質量7.3g)で挟み、一方のクリップは棒状冶具で固定した。標線間距離が250mmであることを確認後、円筒状の透明な水槽に蓄えた30℃に調温した純水に、クリップが付いた第1サンプルをその全体が水中に入るように、速やかに上記第1サンプル長辺を垂直(鉛直)に浸漬した。浸漬直後に水槽上部に棒状冶具を引っ掛けて上記第1サンプル長辺を垂直(鉛直)になるように固定した。その後、金属製の物差しを水中に浸漬して、上記第1サンプルの浸漬から30秒後に標線間距離を測定した。0.5mm刻みで読み取った当該測定値から元の標線間距離(250mm)を引いて伸び量(WMD30)(単位はmm)を算出した。
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)270mm×長さ方向(MD)40mmの長方形の第2サンプルを切り出した。ついで、ごき第2サンプルの270mm長の両端から10mmずつ内側に油性インク(線の太さが0.3mm)で標線を入れた。両端部の標線から外側の部分を市販のクリップ(チャック幅40mm、質量7.3g)で挟み、一方のクリップは棒状冶具で固定する。標線間距離が250mmであることを確認後、円筒状の透明な水槽に蓄えた30℃に調温した純水に、クリップが付いた第2サンプルをその全体が水中に入るように、速やかに第2サンプル長辺を垂直(鉛直)に浸漬した。浸漬直後に水槽上部に棒状冶具を引っ掛けて上記第2サンプル長辺を垂直(鉛直)になるように固定した。その後、金属製の物差しを水中に浸漬して、上記第2サンプルの浸漬から300秒後に標線間距離を測定した。0.5mm刻みで読み取った当該測定値から元の標線間距離(250mm)を引いて伸び量(WTD300)(単位はmm)を算出した。
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1.1倍延伸した後、上記製膜したフィルムを固定幅2.2m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2.2m、厚み38μm、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、製膜したフィルムを、延伸機を用いた幅方向(TD)への延伸をしなかったこと以外は、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、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。
これに対して、幅方向(TD)の伸び量が上記特定する範囲よりも大きい比較例1のポリビニルアルコール系フィルムから得られる偏光膜は、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 (7)
- 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、
そのポリビニルアルコール系フィルムの幅方向中央部から切り出す幅方向40mm×長さ方向270mmの長方形の第1サンプルについて、
この第1サンプルを30℃の水に30秒間浸漬したときの、浸漬前の長さ方向両端部を除く250mmの部分における上記長さ方向の伸び量WMD30が30mm以上50mm以下であり、
かつ、上記ポリビニルアルコール系フィルムの幅方向中央部から切り出す幅方向270mm×長さ方向40mmの長方形の第2サンプルについて、
この第2サンプルを30℃の水に300秒間浸漬したときの、浸漬前の幅方向両端部を除く250mmの部分における幅方向の伸び量WTD300が15mm以上60mm以下である
ことを特徴とするポリビニルアルコール系フィルム。 - 上記ポリビニルアルコール系フィルムの幅が2m以上であることを特徴とする請求項1記載のポリビニルアルコール系フィルム。
- 請求項1または2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3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の幅方向中央部から切り出す幅方向40mm×流れ方向270mmの長方形の第1サンプルについて、
この第1サンプルを30℃の水に30秒間浸漬したときの、浸漬前の長さ方向両端部を除く250mmの部分における長さ方向の伸び量WMD30が30mm以上50mm以下になるようにし、
かつ、製造さ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切り出す幅方向270mm×流れ方向40mmの長方形の第2サンプルについて、
この第2サンプルを30℃の水に300秒間浸漬したときの、浸漬前の幅方向両端部を除く250mmの部分における幅方向の伸び量WTD300が15mm以上60mm以下になるようにする
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。 - 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5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5または6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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JPWO2018199140A1 (ja) | 2020-03-12 |
TWI798217B (zh) | 2023-04-11 |
KR20190139852A (ko) | 2019-12-18 |
CN110431458A (zh) | 2019-11-08 |
CN110431458B (zh) | 2021-09-14 |
TW201841718A (zh) | 2018-12-01 |
KR102463852B1 (ko) | 2022-11-04 |
JP2023083360A (ja) | 2023-06-15 |
JP7335696B2 (ja) | 2023-08-30 |
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