WO2016093277A1 - 偏光フィルムの製造方法及び偏光フィルム - Google Patents
偏光フィルムの製造方法及び偏光フィルム Download PDFInfo
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- WO2016093277A1 WO2016093277A1 PCT/JP2015/084533 JP2015084533W WO2016093277A1 WO 2016093277 A1 WO2016093277 A1 WO 2016093277A1 JP 2015084533 W JP2015084533 W JP 2015084533W WO 2016093277 A1 WO2016093277 A1 WO 2016093277A1
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- film
- stretching
- polarizing film
- polarizing
- polyvinyl alcohol
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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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- 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
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
Definitions
- the present invention relates to a method for producing a polarizing film that can be used as a constituent member of a polarizing plate.
- the present invention also relates to a polarizing film and a polarizing plate including the polarizing film.
- a polarizing film obtained by adsorbing and orienting a dichroic dye such as iodine or a dichroic dye on a uniaxially stretched polyvinyl alcohol resin film.
- a polarizing film is produced by sequentially performing a dyeing treatment for dyeing a polyvinyl alcohol-based resin film with a dichroic dye, a crosslinking treatment with a crosslinking agent, and a uniaxial stretching treatment during the production process [for example, JP-A-07-325218 (Patent Document 1)].
- the polarizing film is used in an image display device typified by a liquid crystal display device.
- a polarizing film is usually a polarizing plate obtained by laminating a protective film on one side or both sides thereof, and is incorporated into an image display device.
- a liquid crystal display device includes a liquid crystal panel in which polarizing plates are bonded to both surfaces of a liquid crystal cell as an image display element.
- the optical properties for example, the degree of polarization
- MD contraction force the contraction force in the absorption axis direction of the polarizing film
- the polarizing plate is likely to be warped (curved) in a high temperature environment and a high humidity environment. This warpage problem becomes more prominent as the polarizing plate is thinner.
- liquid crystal panel When a liquid crystal panel is constructed by laminating a polarizing plate that generates warpage to a liquid crystal cell, the liquid crystal panel is also warped in some cases. The warpage of the liquid crystal panel may adversely affect the visibility of the liquid crystal display device.
- the present invention provides a polarizing film, a polarizing film, and a method for producing a polarizing plate shown below.
- a dyeing step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye A crosslinking step of treating the film after the dyeing step with a crosslinking agent; A first stretching step of uniaxially stretching the polyvinyl alcohol-based resin film during and / or before the crosslinking step; A second stretching step in which the film after the crosslinking step is further uniaxially stretched in a high temperature and high humidity atmosphere at a temperature of 40 to 100 ° C. and an absolute humidity of 40 g / m 3 or more;
- the manufacturing method of a polarizing film containing A dyeing step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye.
- a crosslinking step of treating the film after the dyeing step with a crosslinking agent A first stretching step of uniaxially stretching the polyvinyl alcohol-based resin
- the method further includes a washing step of washing the polyvinyl alcohol-based resin film with a washing solution containing water after the crosslinking step,
- a washing step of washing the polyvinyl alcohol-based resin film with a washing solution containing water after the crosslinking step The production method according to any one of [1] to [4], wherein the second stretching step is performed after the washing step.
- TD / MD ratio (intensity at TD) / (peak intensity at MD) [In the formula, the peak intensity at MD is an average value of peak intensity at ⁇ angles 0 ° and 180 ° of the azimuth distribution curve, and the intensity at TD is an average value of intensity at ⁇ angles 90 ° and 270 °. is there.
- required according to is 0.142 or less when the thickness of the said polarizing film is 10 micrometers or more, and 0.160 or less when the thickness of the said polarizing film is less than 10 micrometers.
- a polarizing plate comprising the polarizing film according to [7] and a protective film laminated on at least one surface thereof.
- a polarizing film that exhibits excellent optical properties while suppressing an increase in MD contraction force and a method for producing the same.
- a polarizing plate and a liquid crystal panel using the polarizing film according to the present invention show good visibility.
- the manufacturing method of the polarizing film which concerns on this invention is the following processes: Dyeing step S20 for dyeing a polyvinyl alcohol resin film with a dichroic dye, A crosslinking step S30 for treating the film after the dyeing step with a crosslinking agent; A first stretching step S40 in which a polyvinyl alcohol-based resin film is uniaxially stretched during and / or before the crosslinking step, and the film after the crosslinking step is heated at a high temperature of 40 to 100 ° C. and an absolute humidity of 40 g / m 3 or more. Second stretching step S60 for further uniaxial stretching in a humid atmosphere including.
- the manufacturing method of the polarizing film which concerns on this invention can further include other processes other than the above,
- the specific example is the swelling process S10 performed before dyeing process S20, and bridge
- the various processing steps included in the production method according to the present invention can be carried out continuously by continuously conveying a polyvinyl alcohol-based resin film, which is a raw film, along the film conveyance path of the polarizing film production apparatus.
- the film transport path includes equipment (processing bath, furnace, etc.) for performing the various processing steps in the order of execution.
- the treatment bath refers to a bath containing a treatment liquid for treating a polyvinyl alcohol resin film, such as a swelling bath, a dyeing bath, a crosslinking bath, and a washing bath.
- the film transport path can be constructed by arranging guide rolls, nip rolls and the like at appropriate positions in addition to the above equipment.
- the guide roll can be arranged before and after each treatment bath or in the treatment bath, whereby the film can be introduced and immersed in the treatment bath and pulled out from the treatment bath.
- two or more guide rolls are provided in each treatment bath, and the film can be immersed in each treatment bath by transporting the film along these guide rolls.
- a saponified polyvinyl acetate-based resin As the polyvinyl alcohol-based resin constituting the polyvinyl alcohol-based resin film that is a raw fabric film, a saponified polyvinyl acetate-based resin can be used.
- the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
- examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
- the degree of saponification of the polyvinyl alcohol-based resin is usually about 85 mol% or more, preferably about 90 mol% or more, more preferably about 99 mol% or more.
- (meth) acryl means at least one selected from acryl and methacryl. The same applies to “(meth) acryloyl”.
- the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like may be used.
- the average degree of polymerization of the polyvinyl alcohol-based resin is preferably 100 to 10,000, more preferably 1500 to 8000, and further preferably 2000 to 5000.
- the average degree of polymerization of the polyvinyl alcohol resin can be determined according to JIS K 6726 (1994). If the average degree of polymerization is less than 100, it is difficult to obtain preferable polarization performance, and if it exceeds 10,000, film processability may be inferior.
- the thickness of the polyvinyl alcohol-based resin film is, for example, about 10 to 150 ⁇ m, and is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, further preferably 50 ⁇ m or less, and still more preferably 40 ⁇ m or less from the viewpoint of thinning the polarizing film. is there.
- the polyvinyl alcohol-based resin film which is a raw film, can be prepared, for example, as a roll (rolled product) of a long unstretched polyvinyl alcohol-based resin film.
- the polarizing film is also obtained as a long object.
- the swelling treatment in this step is a treatment that is carried out as necessary for the purpose of removing foreign matter from the polyvinyl alcohol-based resin film that is the raw fabric film, removing the plasticizer, imparting easy dyeability, plasticizing the film, Specifically, it can be a treatment of immersing a polyvinyl alcohol-based resin film in a swelling bath containing water.
- the film may be immersed in one swelling bath or sequentially in two or more swelling baths. You may perform a uniaxial stretching process with respect to a film before a swelling process, a swelling process, or before a swelling process and a swelling process.
- the swelling bath may be water (for example, pure water) or an aqueous solution to which a water-soluble organic solvent such as alcohol is added.
- the temperature of the swelling bath when dipping the film is usually about 10 to 70 ° C., preferably about 15 to 50 ° C., and the dipping time of the film is usually about 10 to 600 seconds, preferably about 20 to 300 seconds. is there.
- the dyeing process in this step is a process performed for the purpose of adsorbing and orienting the dichroic dye to the polyvinyl alcohol resin film, and specifically, the polyvinyl alcohol resin film in a dye bath containing the dichroic dye. It can be a process of immersing. The film may be immersed in one dyeing bath or sequentially in two or more dyeing baths. In order to improve the dyeability of the dichroic dye, the film subjected to the dyeing process may be subjected to at least some uniaxial stretching treatment. Instead of the uniaxial stretching process before the dyeing process, or in addition to the uniaxial stretching process before the dyeing process, the uniaxial stretching process may be performed during the dyeing process.
- the dichroic dye can be iodine or a dichroic organic dye.
- the dichroic organic dye include: Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Spura Blue G, Spura Blue GL, Spura Orange GL, Direct Includes Sky Blue, Direct First Orange S and First Black.
- a dichroic dye may be used individually by 1 type, and may use 2 or more types together.
- an aqueous solution containing iodine and potassium iodide can be used for the dyeing bath.
- potassium iodide other iodides such as zinc iodide may be used, or potassium iodide and other iodides may be used in combination.
- compounds other than iodide for example, boric acid, zinc chloride, cobalt chloride and the like may coexist.
- boric acid it is distinguished from the crosslinking treatment described later in that it contains iodine.
- the iodine content in the aqueous solution is usually about 0.01 to 1 part by weight per 100 parts by weight of water.
- the content of iodide such as potassium iodide is usually about 0.5 to 20 parts by weight per 100 parts by weight of water.
- the temperature of the dyeing bath when dipping the film is usually about 10 to 45 ° C., preferably about 10 to 40 ° C., more preferably about 20 to 35 ° C., and the dipping time for the film is usually 30 to 600 ° C. About 2 seconds, preferably about 60 to 300 seconds.
- an aqueous solution containing the dichroic organic dye can be used for the dyeing bath.
- the content of the dichroic organic dye in the aqueous solution is usually about 1 ⁇ 10 ⁇ 4 to 10 parts by weight, preferably about 1 ⁇ 10 ⁇ 3 to 1 part by weight per 100 parts by weight of water.
- a dyeing assistant or the like may coexist, and for example, an inorganic salt such as sodium sulfate or a surfactant may be contained.
- a dichroic organic dye may be used individually by 1 type, and may use 2 or more types together.
- the temperature of the dyeing bath when dipping the film is, for example, about 20 to 80 ° C., preferably about 30 to 70 ° C., and the dipping time of the film is usually about 30 to 600 seconds, preferably about 60 to 300 seconds. is there.
- the cross-linking treatment for treating the polyvinyl alcohol-based resin film after the dyeing step with a cross-linking agent is a treatment performed for the purpose of water resistance and hue adjustment by cross-linking, specifically, a dyeing step in a cross-linking bath containing a cross-linking agent. It can be a process of immersing the later film. The film may be immersed in one crosslinking bath or sequentially in two or more crosslinking baths. You may perform a uniaxial stretching process at the time of a crosslinking process.
- crosslinking agent examples include boric acid, glyoxal, and glutaraldehyde, and boric acid is preferably used. Two or more crosslinking agents can be used in combination.
- the content of boric acid in the crosslinking bath is usually about 0.1 to 15 parts by weight, preferably about 1 to 10 parts by weight per 100 parts by weight of water.
- the crosslinking bath preferably contains iodide in addition to boric acid.
- the iodide content in the crosslinking bath is usually about 0.1 to 15 parts by weight, preferably about 5 to 12 parts by weight per 100 parts by weight of water.
- examples of iodide include potassium iodide and zinc iodide.
- compounds other than iodide such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulfate, and the like, may coexist in the crosslinking bath.
- the temperature of the crosslinking bath when dipping the film is usually about 50 to 85 ° C., preferably about 50 to 70 ° C., and the dipping time for the film is usually about 10 to 600 seconds, preferably about 20 to 300 seconds. is there.
- the polyvinyl alcohol-based resin film is used in the crosslinking step S30 and / or before that, that is, any one or two or more from the swelling step S10 to the crosslinking step S30.
- Uniaxial stretching is performed in stages.
- the film subjected to the dyeing process is preferably a film subjected to at least some uniaxial stretching treatment, or instead of the uniaxial stretching treatment before the dyeing treatment, or In addition to the uniaxial stretching process before the dyeing process, it is preferable to perform the uniaxial stretching process during the dyeing process.
- the uniaxial stretching treatment in the first stretching step S40 may be either dry stretching in which stretching is performed in the air or wet stretching in which stretching is performed in a bath, or both of them may be performed.
- the uniaxial stretching treatment may be inter-roll stretching, hot roll stretching, tenter stretching, or the like, in which longitudinal uniaxial stretching is performed with a difference in peripheral speed between two nip rolls, and preferably includes inter-roll stretching.
- the draw ratio based on the raw film (the cumulative draw ratio in the case where the drawing process is performed in two or more stages) is about 3 to 8 times. In order to impart good polarization characteristics, the draw ratio is preferably 4 times or more, more preferably 4.5 times or more.
- the stretching ratio in the first stretching step S40 is 7 times or less, further 6 times or less, and further 5 times or less. Also good.
- the cleaning process in this step is a process performed as necessary for the purpose of removing chemicals such as excess cross-linking agent and dichroic dye attached to the polyvinyl alcohol-based resin film, and uses a cleaning solution containing water.
- This is a treatment for washing the polyvinyl alcohol-based resin film after the crosslinking step.
- it can be a treatment of immersing the polyvinyl alcohol-based resin film after the crosslinking step in a cleaning bath (cleaning liquid).
- the film may be immersed in one cleaning bath or sequentially in two or more cleaning baths.
- the cleaning process may be a process of spraying the cleaning liquid as a shower on the polyvinyl alcohol-based resin film after the crosslinking step, or a combination of the above immersion and spraying.
- the cleaning liquid may be water (for example, pure water) or an aqueous solution to which a water-soluble organic solvent such as alcohol is added.
- the temperature of the cleaning liquid can be about 5 to 40 ° C., for example.
- the cleaning step S50 is an optional step and may be omitted. As described later, the cleaning process may be performed during the second stretching process S60 (the high temperature and high humidity process in the second stretching process S60 is a cleaning process). May also serve as). Preferably, 2nd extending process S60 is performed with respect to the film after performing washing
- Second stretching step S60 The second stretching treatment in this step is a treatment for further uniaxially stretching the film after the crosslinking step S30 in a high temperature and high humidity atmosphere having a temperature of 40 to 100 ° C. and an absolute humidity of 40 g / m 3 or more.
- a uniaxial stretching process is performed simultaneously with the wet process.
- cleaning process S50 it is preferable to perform a 2nd extending
- the drying process high temperature process at an absolute humidity of less than 40 g / m 3
- the stretching ratio in the first stretching step S40 is kept low by performing the second stretching treatment, a sufficient stretching ratio can be ensured as the total stretching ratio, so that it is an excellent optical film for a polarizing film. Properties can be imparted.
- the stretching process is performed in a high-temperature and high-humidity atmosphere, an increase in MD contraction force can be effectively suppressed.
- the improvement of optical properties and the suppression of the increase in MD contraction force can be achieved by the stretching treatment in a high-temperature and high-humidity atmosphere while the orientation of the dichroic dye can be improved.
- the present invention is particularly effective for improving optical properties when the original film to be used is thin, for example, when using an original film having a thickness of 40 ⁇ m or less.
- the MD contraction force increases when simply increasing the stretching ratio in the first stretching step S40, and the polarizing plate, and thus This causes the problem of warping of the liquid crystal panel.
- Providing the second stretching step S60 and carrying out the stretching treatment in a high-temperature and high-humidity atmosphere effectively prevents the film from being broken, and effectively extends the total stretching ratio (cumulative stretching ratio combined with the stretching in the first stretching step S40). It is also advantageous in that it can be increased, and it is also advantageous in terms of an increase in the area of the polarizing film to be taken by increasing the total draw ratio and a reduction in the basic unit.
- the uniaxial stretching treatment in the second stretching step S60 is usually dry stretching because it is necessary to perform stretching in a high temperature and high humidity atmosphere.
- the uniaxial stretching treatment may be inter-roll stretching, hot roll stretching, tenter stretching, or the like in which longitudinal uniaxial stretching is performed with a difference in peripheral speed between two nip rolls, and is preferably inter-roll stretching.
- the draw ratio in this step is usually 1.01 to 1.4 times, and preferably 1.1 to 1.4 times from the viewpoint of improving optical properties. Setting the draw ratio to 1.4 times or less is advantageous for suppressing an increase in MD shrinkage force and film breakage.
- the stretching process in a high-temperature and high-humidity atmosphere is performed, for example, while performing the high-temperature and high-humidity process by introducing the film after the crosslinking step S30 into a furnace (heating furnace), booth or room where the temperature and humidity can be adjusted Can be a process to do.
- heating means such as a far-infrared heater and a heat roll may be used in combination with the treatment introduced into the furnace (heating furnace), booth or room.
- the second stretching step S60 is preferably performed after the cleaning step S50, but the stretching process and the cleaning process in a high-temperature and high-humidity atmosphere, such as spraying a cleaning liquid while stretching in a predetermined high-temperature and high-humidity atmosphere, are performed.
- the second stretching step S60 may also serve as a cleaning process, for example, when the film is substantially cleaned by being placed in a high-temperature and high-humidity atmosphere.
- the atmospheric temperature in the second stretching treatment is 40 ° C. or higher as described above, and preferably 55 ° C. or higher from the viewpoint of more effectively suppressing the increase in MD shrinkage force and maintaining the transportability of the film. More preferably, it is 60 ° C. or higher. Moreover, the said atmospheric temperature is 100 degrees C or less as mentioned above, Preferably it is 90 degrees C or less from a viewpoint of obtaining the outstanding optical characteristic.
- the absolute humidity of the atmosphere in which the second stretching treatment is performed is 40 g / m 3 or more as described above, and preferably 75 g / m 3 or more, more preferably 85 g, from the viewpoint of more effectively suppressing the increase in the MD shrinkage force. / M 3 or more, more preferably 100 g / m 3 or more.
- the absolute humidity is preferably 550 g / m 3 or less, more preferably 400 g / m 2.
- m 3 or less more preferably 300 g / m 3 or less, and particularly preferably 160 g / m 3 or less.
- the time for the second stretching treatment is preferably 5 seconds or more, more preferably from the viewpoint of more effectively suppressing the increase in the MD shrinkage force and obtaining excellent optical properties. Is 10 seconds or more. Further, although the time depends on the temperature, if it is too long, there is a concern about deterioration of optical characteristics. Therefore, it is preferably 60 minutes or less, more preferably 30 minutes or less, and even more preferably 10 minutes or less. Especially preferably, it is 5 minutes or less.
- the second stretching process may be a process of transporting a long polyvinyl alcohol-based resin film along the film transport path and continuously introducing and passing it through the furnace or the like, and stretching the film.
- the tension of the film in the stretching treatment under a high humidity atmosphere is preferably 50 to 5000 N / m from the viewpoint of more effectively suppressing the increase in the MD shrinkage force. From the viewpoint of suppressing wrinkling of the film, the film tension is more preferably 300 to 1500 N / m.
- the second stretching treatment may also serve as a treatment for drying the polyvinyl alcohol-based resin film, that is, a treatment for reducing the moisture content, and usually the drying treatment is performed at the same time unless extreme high temperature and high humidity conditions are adopted. The Thereby, it is not always necessary to separately perform a drying process before or after the second stretching process.
- the moisture content of the film subjected to the second stretching treatment is usually about 13 to 50% by weight, although it depends on the thickness of the film.
- the degree of decrease in the moisture content due to the second stretching treatment that is, the difference between the moisture content before the second stretching treatment and the moisture content after the second stretching treatment (moisture content difference ⁇ S) also depends on the thickness of the film. It is 5 to 45% by weight, preferably 8 to 35% by weight. For example, when the thickness of the raw film is about 40 ⁇ m or less, the moisture content difference ⁇ S can be less than 15% by weight.
- the moisture content of the film after the second stretching process is also 5 to 30% by weight, although it depends on the thickness of the film. From the viewpoint of properties, it is preferably 6 to 15% by weight. If the moisture content is too low, the film tends to tear during conveyance, and if the moisture content is too high, curling tends to occur at the film edge due to moisture release.
- the thinner the film the more easily the moisture is dissipated. Therefore, the thinner the original film, the lower the moisture content before and during the second stretching process. If the moisture content is too low, the film transportability tends to be lowered. Therefore, when the thickness of the raw film is about 40 ⁇ m or less, it is preferable to set the temperature of the second stretching process to be low and to be 40 to 70 ° C.
- the second stretching step S60 may be performed immediately after the crosslinking step S30 or the cleaning step S50, or may be performed after performing other steps following the crosslinking step S30 or the cleaning step S50.
- a drying treatment high temperature treatment at an absolute humidity of less than 40 g / m 3
- a polarizing film in which a dichroic dye is adsorbed and oriented on a uniaxially stretched polyvinyl alcohol-based resin film can be obtained.
- the thickness of the polarizing film is usually 5 to 40 ⁇ m, preferably 30 ⁇ m or less. According to the polarizing film obtained by the present invention, even when the thickness is as thin as 30 ⁇ m or less, and even as thin as 25 ⁇ m or less, it can have excellent optical characteristics and can suppress an increase in MD contraction force. .
- a drying process (a high temperature process at an absolute humidity of less than 40 g / m 3 ) may be performed after the second stretching step S60.
- this drying process is performed as necessary.
- the obtained polarizing film can also be conveyed, for example, to the next polarizing plate production step (step of bonding a protective film on one or both sides of the polarizing film) as it is.
- the polarizing film according to the present invention is a film in which a dichroic dye is adsorbed and oriented on a uniaxially stretched polyvinyl alcohol-based resin film, and wide angle X-ray diffraction (WAXD: Wide Angle X-ray Diffraction). ), which is characterized by a TD / MD ratio representing the orientation of the polyvinyl alcohol resin constituting the polarizing film in the MD, measured by the through method.
- WAXD Wide Angle X-ray Diffraction
- the TD / MD ratio is preferably 0.142 or less, more preferably 0.14 or less. , 0.13 or less, more preferably 0.11 or less.
- the TD / MD ratio of the polarizing film is usually 0.02 or more, preferably 0.08 or more.
- the thickness of the polarizing film having a thickness of 10 ⁇ m or more is usually 30 ⁇ m or less, preferably 15 ⁇ m or less, more preferably 14 ⁇ m or less, and preferably 11 ⁇ m or more, more preferably 12 ⁇ m or more.
- the TD / MD ratio is preferably 0.160 or less, more preferably 0.155 or less, and 0.148 or less. More preferably.
- the TD / MD ratio of the polarizing film is usually 0.02 or more, preferably 0.13 or more.
- the thickness of the polarizing film having a thickness of less than 10 ⁇ m is usually 3 ⁇ m or more, preferably 7 ⁇ m or more, and preferably 9 ⁇ m or less.
- a polarizing film exhibiting the TD / MD ratio as described above can be suitably manufactured by the polarizing film manufacturing method according to the present invention described above.
- TD / MD ratio here is measured in accordance with the method as described in the Example section mentioned later.
- the polarizing film according to the present invention is a film in which a dichroic dye is adsorbed and oriented on a uniaxially stretched polyvinyl alcohol-based resin film, and the wave number representing a crosslinked state of the polarizing film by a crosslinking agent. It can be characterized by the ratio of the Raman scattered light intensity in the absorption axis direction and the Raman scattered light intensity in the transmission axis direction at 775 cm ⁇ 1 (hereinafter also referred to as “Raman scattered light intensity ratio”).
- Raman scattered light intensity ratio the Raman scattered light intensity ratio in the absorption axis direction and the Raman scattered light intensity in the transmission axis direction at 775 cm ⁇ 1
- the Raman scattered light intensity ratio is preferably 0.81 or more, and more preferably 0.87 or more.
- the Raman scattered light intensity ratio is usually 1.00 or less, preferably 0.95 or less.
- the polarizing film showing the Raman scattered light intensity ratio as described above can be preferably manufactured by the above-described manufacturing method of the polarizing film according to the present invention.
- the Raman scattered light intensity ratio here is measured according to the method described in the section of Examples described later.
- the polarizing film according to the present invention is a film in which a dichroic dye is adsorbed and oriented on a uniaxially stretched polyvinyl alcohol-based resin film, exhibits a TD / MD ratio within the above range, and The Raman scattered light intensity ratio within the above range is shown.
- the TD / MD ratio within the above range and the Raman scattered light intensity ratio within the above range are advantageous for obtaining excellent optical characteristics while suppressing an increase in MD contraction force.
- a protective film is bonded (laminated) via an adhesive to at least one surface of a polarizing film produced as described above or exhibiting at least one of the TD / MD ratio and the Raman scattered light intensity ratio.
- a polarizing plate can be obtained.
- thermoplastic resins for example, polyolefin resins such as chain polyolefin resins (polypropylene resins, etc.), cyclic polyolefin resins (norbornene resins, etc.); celluloses such as triacetyl cellulose and diacetyl cellulose Ester resins; Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; Polycarbonate resins; (Meth) acrylic resins such as polymethyl methacrylate resins; or a mixture or copolymer thereof It can be a transparent resin film.
- polyolefin resins such as chain polyolefin resins (polypropylene resins, etc.), cyclic polyolefin resins (norbornene resins, etc.); celluloses such as triacetyl cellulose and diacetyl cellulose Ester resins; Polyester resins such as polyethylene terephthalate, polyethylene na
- the protective film may be a protective film having both optical functions such as a retardation film and a brightness enhancement film.
- a retardation film provided with an arbitrary retardation value by stretching a transparent resin film made of the above material (uniaxial stretching or biaxial stretching) or forming a liquid crystal layer or the like on the film. It can be.
- a surface treatment layer such as a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, or an antifouling layer can be formed on the surface of the protective film opposite to the polarizing film.
- the thickness of the protective film is preferably thin from the viewpoint of reducing the thickness of the polarizing plate, but if it is too thin, the strength is lowered and the workability is poor, so that it is preferably 5 to 150 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably. 10 to 50 ⁇ m.
- an active energy ray curable adhesive such as an ultraviolet curable adhesive, an aqueous solution of a polyvinyl alcohol resin, or an aqueous solution in which a crosslinking agent is blended.
- water-based adhesives such as urethane emulsion adhesives.
- the ultraviolet curable adhesive can be a mixture of a radical polymerizable (meth) acrylic compound and a photo radical polymerization initiator, a mixture of a cationic polymerizable epoxy compound and a photo cationic polymerization initiator, or the like. Further, a cationic polymerizable epoxy compound and a radical polymerizable (meth) acrylic compound may be used in combination, and a photo cationic polymerization initiator and a photo radical polymerization initiator may be used in combination as an initiator.
- the adhesive When using an active energy ray-curable adhesive, the adhesive is cured by irradiating active energy rays after bonding.
- the light source of the active energy ray is not particularly limited, but an active energy ray (ultraviolet ray) having a light emission distribution at a wavelength of 400 nm or less is preferable.
- a black light lamp, a microwave excitation mercury lamp, a metal halide lamp or the like is preferably used.
- the bonding surface of the polarizing film and / or the protective film is subjected to corona treatment, flame treatment, plasma treatment, ultraviolet light.
- Surface treatments such as irradiation treatment, primer coating treatment, and saponification treatment may be applied.
- the polarizing plate of the present invention can also be produced by laminating a protective film on a polarizing film that is a single layer film, but is not limited to this method, and is described in, for example, JP-A-2009-98653. It can also be produced by a method using a base film. The latter method is advantageous for obtaining a polarizing plate having a thin polarizing film (polarizer layer), and can include, for example, the following steps.
- a resin layer forming step of forming a polyvinyl alcohol-based resin layer by drying to obtain a laminated film A stretching step of stretching a laminated film to obtain a stretched film;
- the 1st bonding process of bonding a protective film using the adhesive agent on the polarizer layer of a light-polarizing laminated film, and obtaining a bonding film The peeling process which peels and removes a base film from a bonding film, and obtains the polarizing plate with a single-sided protective film.
- protective films are laminated on both sides of the polarizer layer (polarizing film)
- it further includes a second bonding step in which the protective film is bonded to the polarizer surface of the polarizing plate with a single-side protective film using an adhesive.
- stretching process may be included in the dyeing process (for example, after the bridge
- a polarizing film contained in the polarizing laminate film, a polarizing plate with a single-sided protective film, and a polarizing plate with a double-sided protective film obtained through the second laminating step, or a polarizing film isolated therefrom are also included in the present invention.
- the polarizing film belongs, and preferably exhibits at least one of a TD / MD ratio within the above range and a Raman scattered light intensity ratio within the above range.
- Example 1 A long polyvinyl alcohol (PVA) raw film having a thickness of 30 ⁇ m (trade name “Kuraray Poval Film VF-PE # 3000” manufactured by Kuraray Co., Ltd., average polymerization degree 2400, saponification degree 99.9 mol% or more) It was continuously conveyed while being unwound from the roll, and immersed in a swelling bath made of pure water at 20 ° C. for a residence time of 31 seconds (swelling step). Thereafter, the film drawn out from the swelling bath was immersed in a dye bath at 30 ° C.
- PVA polyvinyl alcohol
- the film pulled out from the crosslinking bath was immersed in a cleaning bath made of pure water at 5 ° C. for a residence time of 3 seconds (cleaning step). Subsequently, it is introduced into a heating furnace capable of adjusting humidity to perform a high temperature and high humidity treatment with a residence time of 189 seconds, and a longitudinal uniaxial stretching treatment is performed by stretching between rolls in the air (second stretching step), and a thickness of 12 A polarizing film having a thickness of .6 ⁇ m and a width of 208 mm was obtained.
- the temperature and absolute humidity in the heating furnace were 60 ° C. and 78 g / m 3 , respectively, and the film tension during the second stretching step was 755 N / m.
- the moisture content of the film immediately before and after the introduction of the heating furnace was 19.0 wt% and 9.2 wt%, respectively, and the moisture content difference ⁇ S was 9.8 wt%.
- the draw ratio D2 based on the film immediately before the introduction of the heating furnace was 1.01.
- Table 1 shows the total stretching ratio D1 in the first stretching step, the temperature and absolute humidity in the heating furnace, the stretching ratio D2 in the second stretching process, the residence time in the heating furnace, and the film tension in the second stretching process.
- a polarizing film was produced in the same manner as in Example 1 except that it was as described above.
- the temperature in the heating furnace and the absolute humidity were 60 ° C. and 12 g / m 3 , respectively.
- the heating furnace only the heating (drying) treatment was performed instead of the high-temperature and high-humidity treatment. Further, no stretching treatment was performed in this heat treatment.
- the total draw ratio D1 in the first drawing step was set to 4.81 times lower than the 5.36 times in Example 1 by lowering the draw ratio in the crosslinking step.
- the absolute humidity in the heating furnace was calculated from the measured values of the furnace temperature and relative humidity.
- the thickness of the obtained polarizing film was measured using a digital micrometer “MH-15M” manufactured by Nikon Corporation. Moreover, the moisture content of the film (polarizing film) was calculated
- the moisture content shown in Table 1 is obtained by obtaining a measured value using the moisture meter and substituting it into the calibration curve (conversion formula) to convert the moisture content (% by weight) by the dry weight method. .
- the moisture content difference ⁇ S was calculated by subtracting the moisture content immediately after introduction from the moisture content immediately before introducing the heating furnace.
- A400 LOG [100 / ⁇ TD transmittance (%) at a wavelength of 400 nm ⁇ ]
- A700 LOG [100 / ⁇ TD transmittance (%) at a wavelength of 700 nm ⁇ ]
- MD transmittance is the transmittance when the direction of polarized light emitted from the Glan-Thompson prism is parallel to the transmission axis of the polarizing film sample, and is represented by “MD” in the above formula.
- the “TD transmittance” is the transmittance when the direction of polarized light emitted from the Glan-Thompson prism is orthogonal to the transmission axis of the polarizing film sample, and is represented by “TD” in the above formula.
- the obtained single transmittance and degree of polarization are corrected for visibility by JIS Z 8701: 1999 “color display method—XYZ color system and X 10 Y 10 Z 10 color system” with a two-degree field of view (C light source).
- the visibility corrected single transmittance (Ty) and the visibility corrected polarization degree (Py) were obtained.
- the “TD / MD ratio” representing the orientation of the polyvinyl alcohol-based resin constituting the polarizing film in the MD is determined by a through method of wide angle X-ray diffraction (WAXD: Wide Angle X-ray Diffraction). Asked. First, a plurality of rectangular films having a long side in the absorption axis direction (MD, stretching direction) were cut out from the obtained polarizing film. A plurality of cut out films were fixed so that their MDs (long sides) were parallel, and this was used as a measurement sample. The thickness of the measurement sample was about 0.1 mm.
- X-ray diffractometer “NANO-Viewer” manufactured by Rigaku Corporation, X-ray output conditions: Cu target, 40 kV, 20 mA.
- the uncorrected azimuth distribution curve refers to an azimuth distribution curve before performing background correction.
- measurement was performed under the same conditions except that the measurement sample was removed from the X-ray optical axis, and the background of the azimuth distribution curve was calculated.
- azimuth distribution curve After performing the transmittance correction, the background was removed from the above-mentioned uncorrected azimuth distribution curve to obtain an azimuth distribution curve after the background correction (hereinafter also simply referred to as “azimuth distribution curve”). .
- the peak in this azimuth distribution curve is an orientation peak.
- the MD of the measurement sample was installed in the vertical direction, and the ⁇ angle at the maximum intensity of the orientation peak appearing in the horizontal direction was 0 °.
- the ⁇ angle (0 ° and 180 °) at the maximum intensity of the orientation peak is derived from the component oriented in the MD of the polarizing film.
- TD / MD ratio (intensity at TD) / (peak intensity at MD)
- the peak intensity in MD means an average value of peak intensities at ⁇ angles of 0 ° and 180 °.
- the strength at TD means the strength at the ⁇ angle 0 ° and the ⁇ angle shifted by 90 ° from 180 °, that is, the average value of the strength at the ⁇ angle 90 ° and the strength at the ⁇ angle 270 °.
- TD / MD ratio These average values when the TD / MD ratio is determined according to the above formula for all orientation peaks present in the azimuth distribution curve.
- the Raman scattered light intensity in the stretching direction of the analytical film at a wave number of 775 cm ⁇ 1 is such that the laser beam is perpendicular to the surface of the analytical film so that the polarization plane of the laser light is parallel to the stretching direction of the analytical film. Incidence was measured by making the plane of polarization of the analyzer parallel to the plane of polarization of the laser light.
- the intensity of Raman scattered light in the direction orthogonal to the stretching direction of the analytical film at a wave number of 775 cm ⁇ 1 is the surface of the analytical film so that the polarization plane of the laser light is perpendicular to the stretching direction of the analytical film. Measurement was performed such that the plane of incidence was more perpendicular and the plane of polarization of the analyzer was parallel to the plane of polarization of the laser light.
- Example 11 A long polyvinyl alcohol (PVA) raw film (trade name “Kuraray Poval Film VF-PE # 2000” manufactured by Kuraray Co., Ltd., average polymerization degree 2400, saponification degree 99.9 mol% or more) having a thickness of 20 ⁇ m While being continuously unwound from the roll, it was uniaxially stretched 4.1 times in a dry manner, and further immersed in a swelling bath made of pure water at 30 ° C. with a residence time of 50 seconds while maintaining the tension state ( Swelling step). Thereafter, the film drawn out from the swelling bath was immersed in a dye bath at 30 ° C.
- PVA polyvinyl alcohol
- the film drawn from the crosslinking bath was immersed in a cleaning bath made of pure water at 4 ° C. for a residence time of 7 seconds (cleaning step), and subsequently introduced into a heating furnace capable of adjusting the humidity, thereby maintaining the residence time.
- cleaning step While performing high-temperature and high-humidity treatment in 95 seconds, longitudinal uniaxial stretching was performed by stretching between rolls in the air (second stretching step) to obtain a polarizing film having a thickness of 8.0 ⁇ m and a width of 218 mm.
- the temperature and absolute humidity in the heating furnace were 70 ° C. and 133 g / m 3 , respectively, and the film tension during the second stretching step was 280 N / m.
- the moisture content of the film immediately before and after the introduction of the heating furnace was 15.1 wt% and 11.4 wt%, respectively, and the moisture content difference ⁇ S was 3.7 wt%.
- the draw ratio D2 based on the film immediately before the introduction of the heating furnace was 1.05.
- Example 12 Comparative Examples 3 to 4> Example 11 except that the temperature and absolute humidity in the heating furnace, the draw ratio D2 in the second stretching step, the residence time in the heating furnace, and the film tension in the second stretching step were as shown in Table 2. Similarly, a polarizing film was produced.
- first PVA layer a 9.5 ⁇ m-thick polyvinyl alcohol-based resin layer
- a primer layer having a thickness of 0.2 ⁇ m is formed on the surface of the base film opposite to the surface on which the first PVA layer is formed in the same manner as described above, and a polyvinyl alcohol resin layer is formed on the primer layer.
- a forming coating solution is applied and dried at 90 ° C. for 4 minutes to form a 9.4 ⁇ m-thick polyvinyl alcohol-based resin layer (hereinafter referred to as “second PVA layer”) on the primer layer.
- second PVA layer a 9.4 ⁇ m-thick polyvinyl alcohol-based resin layer
- the stretched film produced in (5) above contains 30 iodine containing potassium iodide / water of 7.5 / 100 (weight ratio). It was immersed in a dyeing bath at 0 ° C. for a residence time of 230 seconds (dyeing step). Next, the film drawn from the dyeing bath was immersed in a 78 ° C. crosslinking bath having potassium iodide / boric acid / water of 10 / 9.5 / 100 (weight ratio) for a residence time of 240 seconds. It was immersed in a crosslinking bath at 70 ° C. in which potassium fluoride / boric acid / water was 4.5 / 5.0 / 100 (weight ratio) for a residence time of 77 seconds (crosslinking step).
- the film drawn out from the crosslinking bath was immersed in a cleaning bath made of pure water at 4 ° C. for a residence time of 22 seconds (cleaning step), and subsequently introduced into a heating furnace capable of adjusting the humidity, thereby maintaining the residence time.
- a polarizing laminate film containing a layer was obtained.
- the temperature and absolute humidity in the heating furnace were 80 ° C. and 117 g / m 3 , respectively, and the film tension during the second stretching step was 1338 N / m.
- the moisture content of the film immediately before and after the introduction of the heating furnace was 18.2 wt% and 10.6 wt%, respectively, and the moisture content difference ⁇ S was 7.6 wt%.
- the draw ratio D2 based on the film immediately before the introduction of the heating furnace was 1.05.
- Table 3 summarizes the manufacturing conditions of the polarizing laminate film in Example 13 and Comparative Example 5, the moisture content of the polarizing film immediately before and after the introduction of the heating furnace (second stretching step), and the moisture content difference ⁇ S, which is the difference between them. It was. Moreover, about the said item (Excluding TD / MD ratio), the characteristic of the polarizing film in Example 13 and Comparative Example 5 was measured. The results are shown in Table 3. In addition, for the measurement of optical characteristics using a spectrophotometer with an integrating sphere [“V7100” manufactured by JASCO Corporation], a polarizing film formed from the first PVA layer is obtained from the obtained polarizing laminated film.
- a laminated film from which the film was peeled and removed was used as a measurement sample. At this time, measurement was performed by entering light from the side of the polarizing film (polarizing film formed from the second PVA layer). Moreover, MD contraction force took out only the polarizing film formed from the 2nd PVA layer from the obtained polarizing laminated film, and made this into the measurement sample.
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Abstract
Description
[1] ポリビニルアルコール系樹脂フィルムを二色性色素で染色する染色工程と、
染色工程後のフィルムを架橋剤で処理する架橋工程と、
前記架橋工程中及び/又はそれより前に、ポリビニルアルコール系樹脂フィルムを一軸延伸する第1延伸工程と、
架橋工程後のフィルムを、温度40~100℃、絶対湿度40g/m3以上の高温高湿雰囲気下でさらに一軸延伸する第2延伸工程と、
を含む、偏光フィルムの製造方法。
前記洗浄工程の後に、前記第2延伸工程を実施する、[1]~[4]のいずれかに記載の製造方法。
広角X線回折測定により得られる方位角分布曲線に基づき、下記式:
TD/MD比=(TDにおける強度)/(MDにおけるピーク強度)
〔式中、MDにおけるピーク強度は、前記方位角分布曲線のβ角度0°と180°におけるピーク強度の平均値であり、TDにおける強度は、β角度90°と270°における強度の平均値である。〕
に従って求められるTD/MD比が、前記偏光フィルムの厚みが10μm以上であるとき0.142以下であり、前記偏光フィルムの厚みが10μm未満であるとき0.160以下である、偏光フィルム。
図1を参照して、本発明に係る偏光フィルムの製造方法は、以下の工程:
ポリビニルアルコール系樹脂フィルムを二色性色素で染色する染色工程S20、
染色工程後のフィルムを架橋剤で処理する架橋工程S30、
架橋工程中及び/又はそれより前に、ポリビニルアルコール系樹脂フィルムを一軸延伸する第1延伸工程S40、及び
架橋工程後のフィルムを、温度40~100℃、絶対湿度40g/m3以上の高温高湿雰囲気下でさらに一軸延伸する第2延伸工程S60
を含む。
本工程における膨潤処理は、原反フィルムであるポリビニルアルコール系樹脂フィルムの異物除去、可塑剤除去、易染色性の付与、フィルムの可塑化等の目的で必要に応じて実施される処理であり、具体的には、水を含有する膨潤浴にポリビニルアルコール系樹脂フィルムを浸漬させる処理であることができる。当該フィルムは、1つの膨潤浴に浸漬されてもよいし、2以上の膨潤浴に順次浸漬されてもよい。膨潤処理前、膨潤処理時、又は膨潤処理前及び膨潤処理時に、フィルムに対して一軸延伸処理を行ってもよい。
本工程における染色処理は、ポリビニルアルコール系樹脂フィルムに二色性色素を吸着、配向させる目的で行われる処理であり、具体的には、二色性色素を含有する染色浴にポリビニルアルコール系樹脂フィルムを浸漬させる処理であることができる。当該フィルムは、1つの染色浴に浸漬されてもよいし、2以上の染色浴に順次浸漬されてもよい。二色性色素の染色性を高めるために、染色工程に供されるフィルムは、少なくともある程度の一軸延伸処理が施されていてもよい。染色処理前の一軸延伸処理の代わりに、あるいは染色処理前の一軸延伸処理に加えて、染色処理時に一軸延伸処理を行ってもよい。
染色工程後のポリビニルアルコール系樹脂フィルムを架橋剤で処理する架橋処理は、架橋による耐水化や色相調整等の目的で行う処理であり、具体的には、架橋剤を含有する架橋浴に染色工程後のフィルムを浸漬させる処理であることができる。当該フィルムは、1つの架橋浴に浸漬されてもよいし、2以上の架橋浴に順次浸漬されてもよい。架橋処理時に一軸延伸処理を行ってもよい。
上述のように、偏光フィルムの製造にあたり、ポリビニルアルコール系樹脂フィルムは、架橋工程S30中及び/又はそれより前に、すなわち、膨潤工程S10の前から架橋工程S30までのいずれか1又は2以上の段階で一軸延伸処理される。二色性色素の染色性を高める観点から、染色工程に供されるフィルムは、少なくともある程度の一軸延伸処理を施したフィルムであることが好ましく、又は染色処理前の一軸延伸処理の代わりに、あるいは染色処理前の一軸延伸処理に加えて、染色処理時に一軸延伸処理を行うことが好ましい。
本工程における洗浄処理は、ポリビニルアルコール系樹脂フィルムに付着した余分な架橋剤や二色性色素等の薬剤を除去する目的で必要に応じて実施される処理であり、水を含有する洗浄液を用いて架橋工程後のポリビニルアルコール系樹脂フィルムを洗浄する処理である。具体的には、洗浄浴(洗浄液)に架橋工程後のポリビニルアルコール系樹脂フィルムを浸漬させる処理であることができる。当該フィルムは、1つの洗浄浴に浸漬されてもよいし、2以上の洗浄浴に順次浸漬されてもよい。あるいは、洗浄処理は、架橋工程後のポリビニルアルコール系樹脂フィルムに対して洗浄液をシャワーとして噴霧する処理であってもよく、上記の浸漬と噴霧とを組み合わせてもよい。
本工程における第2延伸処理は、架橋工程S30後のフィルムを温度40~100℃、絶対湿度40g/m3以上の高温高湿雰囲気下でさらに一軸延伸する処理であり、換言すれば、高温高湿処理と同時に一軸延伸処理を行うものである。洗浄工程S50を実施する場合には、洗浄工程後のフィルムに対して第2延伸処理を行うことが好ましい。洗浄工程S50の後、乾燥処理(絶対湿度40g/m3未満での高温処理)を実施する場合には、乾燥処理後のフィルムに対して第2延伸処理を行うことが好ましい。
以上のようにして製造される、又は、上記TD/MD比及び上記ラマン散乱光強度比の少なくとも一方を示す偏光フィルムの少なくとも片面に、接着剤を介して保護フィルムを貼合(積層)することにより偏光板を得ることができる。保護フィルムとしては、熱可塑性樹脂、例えば、鎖状ポリオレフィン系樹脂(ポリプロピレン系樹脂等)、環状ポリオレフィン系樹脂(ノルボルネン系樹脂等)のようなポリオレフィン系樹脂;トリアセチルセルロースやジアセチルセルロースのようなセルロースエステル系樹脂;ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレートのようなポリエステル系樹脂;ポリカーボネート系樹脂;ポリメタクリル酸メチル系樹脂のような(メタ)アクリル系樹脂;又はこれらの混合物、共重合物等からなる透明樹脂フィルムであることができる。
積層フィルムを延伸して延伸フィルムを得る延伸工程、
延伸フィルムのポリビニルアルコール系樹脂層を二色性色素で染色して偏光子層(偏光フィルムに相当)を形成することにより偏光性積層フィルムを得る染色工程、
偏光性積層フィルムの偏光子層上に接着剤を用いて保護フィルムを貼合して貼合フィルムを得る第1貼合工程、
貼合フィルムから基材フィルムを剥離除去して片面保護フィルム付の偏光板を得る剥離工程。
厚み30μmの長尺のポリビニルアルコール(PVA)原反フィルム〔(株)クラレ製の商品名「クラレポバールフィルムVF-PE#3000」、平均重合度2400、ケン化度99.9モル%以上〕をロールから巻き出しながら連続的に搬送し、20℃の純水からなる膨潤浴に滞留時間31秒で浸漬させた(膨潤工程)。その後、膨潤浴から引き出したフィルムを、ヨウ化カリウム/水が2/100(重量比)であるヨウ素を含む30℃の染色浴に滞留時間122秒で浸漬させた(染色工程)。次いで、染色浴から引き出したフィルムを、ヨウ化カリウム/ホウ酸/水が12/4.1/100(重量比)である56℃の架橋浴に滞留時間70秒で浸漬させ、続いて、ヨウ化カリウム/ホウ酸/水が9/2.9/100(重量比)である40℃の架橋浴に滞留時間13秒で浸漬させた(架橋工程)。染色工程及び架橋工程において、浴中でのロール間延伸により縦一軸延伸を行った(第1延伸工程)。原反フィルムを基準とする総延伸倍率D1は5.36倍とした。
第1延伸工程における総延伸倍率D1、加熱炉内の温度及び絶対湿度、第2延伸工程における延伸倍率D2、加熱炉内での滞留時間、第2延伸工程時のフィルム張力を表1に示されるとおりとしたこと以外は実施例1と同様にして、偏光フィルムを作製した。
乾燥重量法による水分率(重量%)=0.0495×(水分計測定値)-38.8379
のとおり求めた。この際、乾燥重量法による水分率は、105℃で2時間乾燥させたときの偏光フィルムの重量をW1、乾燥前の偏光フィルムの重量をW0とするとき、次式:
乾燥重量法による水分率(重量%)={(W0-W1)÷W0}×100
に従って求めた。表1に記載の水分率は、上記水分計を用いて測定値を得、これを上記検量線(換算式)に代入して、乾燥重量法による水分率(重量%)に換算したものである。加熱炉導入直前の水分率から導入直後の水分率を差し引くことにより、水分率差ΔSを算出した。
下記の項目について、各実施例及び比較例で得られた偏光フィルムの特性を測定した。結果を表1に示す。
得られた偏光フィルムについて、積分球付き分光光度計〔日本分光(株)製の「V7100」〕を用いて波長380~780nmの範囲におけるMD透過率とTD透過率を測定し、下記式:
単体透過率(%)=(MD+TD)/2
偏光度(%)={(MD-TD)/(MD+TD)}×100
に基づいて各波長における単体透過率及び偏光度を算出した。また、下記式:
A400 =LOG[100/{波長400nmにおけるTD透過率(%)}]
A700 =LOG[100/{波長700nmにおけるTD透過率(%)}]
に基づいて、波長400nmにおける吸光度(A400)及び波長700nmにおける吸光度(A700)を算出した。
得られた偏光フィルムから、吸収軸方向(MD、延伸方向)を長辺とする幅2mm、長さ10mmの測定用試料を切り出した。この試料をエスアイアイ・ナノテクノロジー(株)製の熱機械分析装置(TMA)「EXSTAR-6000」にセットし、寸法を一定に保持したまま、80℃で4時間保持したときに発生する長辺方向(吸収軸方向、MD)の収縮力(MD収縮力)を測定した。
偏光フィルムを構成するポリビニルアルコール系樹脂のMDへの配向性を表す「TD/MD比」を、広角X線回折(WAXD:Wide Angle X-ray Diffraction)のスルー法により求めた。まず、得られた偏光フィルムから、吸収軸方向(MD、延伸方向)を長辺とする長方形のフィルムの複数枚切り出した。切り出したフィルムを、それらのMD(長辺)が平行となるように複数枚重ねて固定し、これを測定用試料とした。測定用試料の厚みは0.1mm程度とした。下記のX線回折装置を用い、測定用試料の表面に対して垂直な方向から、下記のX線出力条件でX線を測定用試料の一方の表面に照射し、透過法での回折像を撮像した。
X線出力条件:Cuターゲット、40kV、20mA。
TD/MD比=(TDにおける強度)/(MDにおけるピーク強度)
に従って、TD/MD比を求めた。MDにおけるピーク強度とは、β角度0°と180°におけるピーク強度の平均値を意味する。TDにおける強度とは、β角度0°と180°から90°ずれたβ角度における強度を意味しており、すなわち、β角度90°における強度とβ角度270°における強度との平均値を意味する。方位角分布曲線に存在するすべて配向性ピークについて上記式に従ってTD/MD比を求めたときのこれらの平均値を本明細書における「TD/MD比」とする。
得られた偏光フィルムのラマン散乱光強度比を求めるために、染色浴がヨウ素を含まないこと以外は各実施例及び各比較例と同様にして分析用フィルムを作製した。得られた偏光フィルムのラマン散乱光強度比は、この分析用フィルムのラマン散乱光強度比と同じであると認められる。
ラマン散乱光強度比=(波数775cm-1における分析用フィルムの延伸方向のラマン散乱光強度)/(波数775cm-1における分析用フィルムの延伸方向と直交する方向のラマン散乱光強度)
に従って求め、これを、得られた偏光フィルムのラマン散乱光強度比とした。
・励起波長:532nm、
・グレーチング:600 l/mm、
・スリット幅:100×1000μm、
・アパーチャ:φ40μm、
・対物レンズ:100倍。
厚み20μmの長尺のポリビニルアルコール(PVA)原反フィルム〔(株)クラレ製の商品名「クラレポバールフィルムVF-PE#2000」、平均重合度2400、ケン化度99.9モル%以上〕をロールから巻き出しながら連続的に搬送しながら、乾式で4.1倍に一軸延伸し、さらに緊張状態を保ったまま、30℃の純水からなる膨潤浴に滞留時間50秒で浸漬させた(膨潤工程)。その後、膨潤浴から引き出したフィルムを、ヨウ化カリウム/水が5/100(重量比)であるヨウ素を含む30℃の染色浴に滞留時間88秒で浸漬させた(染色工程)。次いで、染色浴から引き出したフィルムを、ヨウ化カリウム/ホウ酸/水が18/5.6/100(重量比)である65℃の架橋浴に滞留時間115秒で浸漬させた(架橋工程)。染色工程及び架橋工程において、浴中でのロール間延伸によりさらに縦一軸延伸を行った。原反フィルムを基準とする総延伸倍率D1は4.26倍とした。
加熱炉内の温度及び絶対湿度、第2延伸工程における延伸倍率D2、加熱炉内での滞留時間、第2延伸工程時のフィルム張力を表2に示されるとおりとしたこと以外は実施例11と同様にして、偏光フィルムを作製した。
(1)基材フィルムの作製
エチレンユニットを約5重量%含むプロピレン/エチレンのランダム共重合体(住友化学(株)製の商品名「住友ノーブレン W151」、融点Tm=138℃)からなる樹脂層の両側にプロピレンの単独重合体であるホモポリプロピレン(住友化学(株)製の商品名「住友ノーブレンFLX80E4」、融点Tm=163℃)からなる樹脂層を配置した3層構造の基材フィルムを、多層押出成形機を用いた共押出成形により作製した。得られた基材フィルムの合計の厚みは100μmであり、各層の厚み比(FLX80E4/W151/FLX80E4)は3/4/3であった。
ポリビニルアルコール粉末(日本合成化学工業(株)製の商品名「Z-200」、平均重合度1100、ケン化度99.5モル%)を95℃の熱水に溶解し、濃度3重量%のポリビニルアルコール水溶液を調製した。得られた水溶液に架橋剤(田岡化学工業(株)製の商品名「スミレーズレジン650」)をポリビニルアルコール粉末2重量部に対して1重量部の割合で混合して、プライマー層形成用塗工液を得た。
ポリビニルアルコール粉末((株)クラレ製の商品名「PVA124」、平均重合度2400、平均ケン化度98.0~99.0モル%)を95℃の熱水に溶解し、濃度8重量%のポリビニルアルコール水溶液を調製し、これをポリビニルアルコール系樹脂層形成用塗工液とした。
上記(1)で作製した基材フィルムを連続的に搬送しながら、その一方の面にコロナ処理を施し、次いでコロナ処理された面に小径グラビアコーターを用いて上記(2)で調製したプライマー層形成用塗工液を連続的に塗工し、60℃で3分間乾燥させることにより、厚み0.2μmのプライマー層を形成した。引き続き、フィルムを搬送しながら、プライマー層上にカンマコーターを用いて上記(3)で調製したポリビニルアルコール系樹脂層形成用塗工液を連続的に塗工し、90℃で4分間乾燥させることにより、プライマー層上に厚み9.5μmのポリビニルアルコール系樹脂層(以下、「第1のPVA層」という。)を形成した。
上記(4)で作製した積層フィルムを連続的に搬送しながら、ニップロール間での延伸方法により延伸温度160℃で縦方向(フィルム搬送方向)に5.3倍の倍率で一軸延伸して延伸フィルムを得た(第1延伸工程)。延伸フィルムにおいて、第1のPVA層の厚みは5.0μm、第2のPVA層の厚みは4.9μmとなった。
上記(5)で作製した延伸フィルムを、ヨウ化カリウム/水が7.5/100(重量比)であるヨウ素を含む30℃の染色浴に滞留時間230秒で浸漬させた(染色工程)。次いで、染色浴から引き出したフィルムを、ヨウ化カリウム/ホウ酸/水が10/9.5/100(重量比)である78℃の架橋浴に滞留時間240秒で浸漬させ、続いて、ヨウ化カリウム/ホウ酸/水が4.5/5.0/100(重量比)である70℃の架橋浴に滞留時間77秒で浸漬させた(架橋工程)。
加熱炉内の温度及び絶対湿度、第2延伸工程における延伸倍率D2、第2延伸工程時のフィルム張力を表3に示されるとおりとしたこと以外は実施例13と同様にして、偏光フィルムを作製した。比較例5において、加熱炉内の温度、絶対湿度はそれぞれ65℃、8g/m3であり、加熱炉では高温高湿処理ではなく、加熱(乾燥)処理を行ったのみであり、また、延伸は行わなかった(D2=1.00倍)。
Claims (8)
- ポリビニルアルコール系樹脂フィルムを二色性色素で染色する染色工程と、
染色工程後のフィルムを架橋剤で処理する架橋工程と、
前記架橋工程中及び/又はそれより前に、ポリビニルアルコール系樹脂フィルムを一軸延伸する第1延伸工程と、
架橋工程後のフィルムを、温度40~100℃、絶対湿度40g/m3以上の高温高湿雰囲気下でさらに一軸延伸する第2延伸工程と、
を含む、偏光フィルムの製造方法。 - 前記第2延伸工程で行う一軸延伸の倍率が1.01~1.4倍である、請求項1に記載の製造方法。
- 前記第2延伸工程によってフィルムの水分率を低下させる、請求項1又は2に記載の製造方法。
- 前記第2延伸工程前後のフィルムの水分率の差は、15重量%未満である、請求項3に記載の製造方法。
- 前記架橋工程の後に、水を含有する洗浄液を用いてポリビニルアルコール系樹脂フィルムを洗浄する洗浄工程をさらに含み、
前記洗浄工程の後に、前記第2延伸工程を実施する、請求項1~4のいずれか1項に記載の製造方法。 - 前記第2延伸工程における前記一軸延伸は、乾式延伸である、請求項1~5のいずれか1項に記載の製造方法。
- ポリビニルアルコール系樹脂フィルムに二色性色素が吸着配向されている偏光フィルムであって、
広角X線回折測定により得られる方位角分布曲線に基づき、下記式:
TD/MD比=(TDにおける強度)/(MDにおけるピーク強度)
〔式中、MDにおけるピーク強度は、前記方位角分布曲線のβ角度0°と180°におけるピーク強度の平均値であり、TDにおける強度は、β角度90°と270°における強度の平均値である。〕
に従って求められるTD/MD比が、前記偏光フィルムの厚みが10μm以上であるとき0.142以下であり、前記偏光フィルムの厚みが10μm未満であるとき0.160以下である、偏光フィルム。 - 請求項7に記載の偏光フィルムと、その少なくとも一方の面に積層される保護フィルムとを含む、偏光板。
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KR102645969B1 (ko) | 2024-03-08 |
TW201626004A (zh) | 2016-07-16 |
TWI685685B (zh) | 2020-02-21 |
JPWO2016093277A1 (ja) | 2017-09-21 |
CN107003464A (zh) | 2017-08-01 |
KR20170095923A (ko) | 2017-08-23 |
CN107003464B (zh) | 2020-05-19 |
JP6422507B2 (ja) | 2018-11-14 |
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