WO2023074639A1 - ポリビニルアルコールフィルム - Google Patents

ポリビニルアルコールフィルム Download PDF

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Publication number
WO2023074639A1
WO2023074639A1 PCT/JP2022/039578 JP2022039578W WO2023074639A1 WO 2023074639 A1 WO2023074639 A1 WO 2023074639A1 JP 2022039578 W JP2022039578 W JP 2022039578W WO 2023074639 A1 WO2023074639 A1 WO 2023074639A1
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Prior art keywords
film
pva
pva film
elastic modulus
composite elastic
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PCT/JP2022/039578
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English (en)
French (fr)
Japanese (ja)
Inventor
絵美 川崎
裕史 田邊
稔 岡本
修 風藤
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to CN202280071608.6A priority Critical patent/CN118176446A/zh
Priority to JP2023556439A priority patent/JPWO2023074639A1/ja
Priority to KR1020247007636A priority patent/KR20240087665A/ko
Publication of WO2023074639A1 publication Critical patent/WO2023074639A1/ja
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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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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 polyvinyl alcohol films.
  • a polarizer which has the function of transmitting and shielding light, is a basic component of a liquid crystal display (LCD) along with a liquid crystal that changes the polarization state of light.
  • LCD liquid crystal display
  • Many polarizing plates have a structure in which a protective film such as a cellulose triacetate (TAC) film is attached to the surface of a polarizing film.
  • TAC cellulose triacetate
  • a polyvinyl alcohol film hereinafter, "polyvinyl alcohol” may be abbreviated as "PVA”
  • PVA polyvinyl alcohol film
  • I 3 - or I 5 - , etc. an iodine-based dye
  • dichroic organic dyes dichroic organic dyes to which dichroic dyes are adsorbed are mainstream.
  • Such a polarizing film can be produced by uniaxially stretching a PVA film containing a dichroic dye in advance, adsorbing a dichroic dye at the same time as the PVA film is uniaxially stretched, or dichroically stretching a PVA film after uniaxially stretching it. It is manufactured by, for example, adsorbing a dye.
  • LCDs have come to be used in a wide range of small devices such as calculators and wristwatches, notebook computers, liquid crystal televisions, vehicle navigation systems, mobile phones, tablet terminals, and measuring instruments used indoors and outdoors.
  • polarizing films that are more durable than other products, especially in terms of resistance to moisture and heat under high temperature and high humidity conditions.
  • Patent Document 1 As a polarizing film with excellent moisture and heat resistance, one containing PVA, a dichroic dye, and a specific organic acid is known (see Patent Document 1). Further, a method has been proposed in which the surface of a polarizing film is brought into contact with a treatment liquid containing a reducing agent in a specific proportion (see Patent Document 2).
  • Patent Document 1 since a specific organic acid is contained in the PVA film, when the PVA film is uniaxially stretched to produce a polarizing film, however, there is a problem that the orientation of the dichroic dye adsorbed on the PVA film is disturbed, and the polarizing performance of the obtained polarizing film is deteriorated.
  • the method described in Patent Document 2 requires an increase in the number of steps in manufacturing the polarizing film, and requires the use of a reducing agent, resulting in a problem of high cost.
  • the present invention has been made based on the circumstances as described above, and an object of the present invention is to produce a PVA film that can produce a polarizing film having excellent polarizing performance and resistance to moisture and heat without increasing the number of steps for producing the polarizing film. is to provide
  • the present inventors have made intensive studies to achieve the above object, and as a result, in a cross section that appears by cutting perpendicularly to the two surfaces of the PVA film, the composite elastic modulus near the surface and the central part in the thickness direction By adjusting the difference from the composite elastic modulus of to a specific range, it was found that a polarizing film with excellent polarizing performance and heat and humidity resistance could be produced, and based on these findings, the present invention was completed by further studies.
  • the present invention [1] A water-insoluble polyvinyl alcohol film, cut perpendicularly to the first surface and the second surface of the polyvinyl alcohol film.
  • Er1 (GPa) is the composite elastic modulus near the first surface
  • Er2 (GPa) is the composite elastic modulus near the second surface
  • Er2 (GPa) is the composite elastic modulus near the second surface.
  • Er1 is the composite elastic modulus of a region within 5 ⁇ m from the first surface toward the center in the thickness direction
  • Er2 is the center in the thickness direction from the second surface
  • Er3 is the composite elastic modulus of the region within 5 ⁇ m toward the center in the thickness direction.
  • the first surface and the second surface of the polyvinyl alcohol film, and the central part in the thickness direction of the cross section that appears by cutting perpendicularly to the first surface and the second surface are subjected to FT by the ATR method.
  • the crystallinity index of the first surface is Fg1
  • the crystallinity index of the second surface is Fg2
  • the crystallinity index of the central portion in the thickness direction is The polyvinyl alcohol film according to [1] above, wherein Fg1, Fg2 and Fg3 satisfy the following formulas (3) to (5) when Fg3. 0.70 ⁇ Fg1 ⁇ 0.90 (3) 0.70 ⁇ Fg2 ⁇ 0.90 (4) 0.30 ⁇ Fg3 ⁇ 0.50 (5)
  • Fg1 is the crystallinity index calculated when FT-IR measurement is performed on the first surface
  • Fg2 is the second surface.
  • Fg3 is a crystallinity index calculated when FT-IR measurement is performed, and Fg3 is a crystallinity index calculated when FT-IR measurement is performed on the central portion in the thickness direction of the cross section.
  • Fg1 and Fg2 satisfy the following formula (6).
  • FIG. 1 is a perspective view of a PVA film of the present invention
  • FIG. 2 is a cross-sectional view taken from a PVA film of the present invention cut perpendicular to the first and second surfaces, showing the locations of the PVA film where nanoindentation testing and FT-IR measurements were performed; It is a diagram.
  • FIG. 2 is a diagram schematically showing the ATR method in FT-IR measurement;
  • the composite elastic modulus of the PVA film of the present invention is , Er1 (GPa) is the composite elastic modulus in the vicinity of the first surface, Er2 (GPa) is the composite elastic modulus in the vicinity of the second surface, and Er3 (GPa) is the composite elastic modulus in the center in the thickness direction.
  • Er1, Er2 and Er3 satisfy the following equations (1) and (2). 0.40 ⁇ Er1 ⁇ Er3 ⁇ 1.20 (1) 0.40 ⁇ Er2 ⁇ Er3 ⁇ 1.20 (2)
  • Er1 is the composite elastic modulus in a region within 5 ⁇ m from the first surface toward the center in the thickness direction
  • Er2 is the composite elastic modulus in the region from the second surface to the center in the thickness direction
  • Er3 is the composite elastic modulus of the region within 5 ⁇ m toward the center in the thickness direction.
  • two surfaces perpendicular to the thickness direction 2 of the PVA film 1 are defined as the first surface 3 and the second surface 4, respectively. Accordingly, the first surface 3 and the second surface 4 of the PVA film 1 face each other.
  • the PVA film 1 was cut perpendicularly to the first surface 3 and the second surface 4 to prepare a sample in which a cross section 5 appeared. Then, as shown in FIG. 3, a nanoindentation test was performed on each position in the vicinity 6 of the first surface, the vicinity 7 of the second surface, and the central portion 8 in the thickness direction.
  • the vicinity 6 of the first surface is a region within 5 ⁇ m from the first surface 3 toward the central portion in the thickness direction.
  • the vicinity 7 of the second surface is a region within 5 ⁇ m from the second surface 4 toward the central portion in the thickness direction.
  • the central portion 8 in the thickness direction refers to a position on a straight line parallel to the first surface 3 and the second surface 4 that is equidistant from the first surface 3 and the second surface 4 in the thickness direction 2 .
  • the composite elastic modulus Er measured by the nanoindentation method can be calculated from the stiffness S and the contact projected area Ac using the following formula (7).
  • the stiffness S is calculated from the slope of the unloading curve in the load-displacement curve.
  • the slope of the unloading curve refers to the slope of the unloading curve at the time of high displacement, that is, the slope of the unloading curve immediately after the probe is press-fitted and the unloading is started.
  • the contact projected area Ac is the contact depth (difference in surface displacement at the surface surrounding the contact point determined from the slope of the unloading curve at a given indentation depth and maximum load) and probe geometry-specific constants and corrections It is obtained by a predetermined formula from the term.
  • the composite elastic modulus of the PVA film is affected by the PVA crystal elastic modulus, amorphous elastic modulus, crystallinity, and crystal size. Moreover, since the composite elastic modulus of the PVA film varies depending on the amount of moisture absorbed by the PVA film, the nanoindentation test was conducted in the environment of 23° C. and 40% RH in the present invention. Specifically, the test was performed by the method described later in Examples, and the composite elastic modulus was calculated.
  • the composite elastic modulus of PVA film is affected by the degree of crystallinity of PVA.
  • a PVA film has a crystalline region and an amorphous region, and the composite elastic modulus of the crystalline region is larger than that of the amorphous region.
  • the composite modulus of elasticity tends to increase.
  • the small crystal size, high degree of orientation, and high degree of polymerization of PVA are also factors that increase the composite elastic modulus of the PVA film.
  • PVA films have structural differences and physical property differences in the thickness direction.
  • the composite elastic moduli Er1 and Er2 in the vicinity of the first surface and the second surface in the PVA film of the present invention are larger than the composite elastic modulus Er3 in the central portion in the thickness direction, and it is necessary to adjust the difference between them within a specific range.
  • the difference between the composite elastic moduli Er1 and Er2 in the vicinity of the first surface and the second surface in the PVA film and the composite elastic modulus Er3 in the central portion in the thickness direction is larger than a specific range, that is, the first surface and the second surface
  • a specific range that is, the first surface and the second surface
  • the composite elastic moduli Er1 and Er2 in the vicinity of the surface of 2 are too large, or when the composite elastic modulus Er3 in the central portion in the thickness direction is too small, iodine dyes, etc.
  • the dichroic dye is not easily incorporated in the vicinity of the surface, and the central portion in the thickness direction is not dyed. As a result, the heat and humidity resistance of the obtained polarizing film or polarizing plate is lowered.
  • the difference between the composite elastic moduli Er1 and Er2 in the vicinity of the first and second surfaces of the PVA film and the composite elastic modulus Er3 in the central portion in the thickness direction is smaller than a specific range, that is, the first If the composite elastic moduli Er1 and Er2 in the vicinity of the surface and the second surface are too small, or if the composite elastic modulus Er3 in the central portion in the thickness direction is too large, stretching is required when the polarizing film is produced by uniaxially stretching the PVA film.
  • the stretching temperature is set so that the stress of the PVA film at the same time is the same, the orientation of the PVA in the vicinity of the surface is suppressed, and the iodine complex that exhibits the polarizing performance is less likely to be formed. Since the abundance ratio of the iodine complex tends to be higher in the vicinity of the surface than in the central portion in the thickness direction, there is a problem that the polarizing performance of the resulting polarizing film is remarkably lowered.
  • Er1-Er3 and Er2-Er3 must be 0.40 GPa or more and 1.20 GPa or less, as shown in the above formulas (1) and (2).
  • Er1-Er3 and Er2-Er3 By setting Er1-Er3 and Er2-Er3 to 0.40 GPa or more, when the PVA film is uniaxially stretched to produce a polarizing film, the first and second iodine complexes exhibiting polarizing performance have a high abundance ratio. Since the orientation of PVA near the surface is promoted, a polarizing film with excellent polarizing performance can be obtained.
  • Er1-Er3 and Er2-Er3 are preferably 0.42 GPa or more, more preferably 0.45 GPa or more, even more preferably 0.47 GPa or more, and particularly 0.50 GPa or more.
  • Er1-Er3 and Er2-Er3 are preferably 1.15 GPa or less, more preferably 1.10 GPa or less, even more preferably 1.05 GPa or less, particularly 0.98 GPa or less. preferable.
  • a method of adjusting Er1-Er3 and Er2-Er3 to 0.40 GPa or more and 1.20 GPa or less includes a method of appropriately adjusting the film forming conditions of the PVA film.
  • the temperature of the support that drools the film-forming stock solution, the temperature of the hot air that is blown onto the liquid coating on the support, the volatile content of the liquid coating when it is peeled off from the support, the support The volatile content/thickness of the liquid coating when peeled from the substrate, the surface temperature of the drying roll when drying the film after peeling from the support, the volatile content of the film when peeling off the drying roll (that is, the initial volatile content of the film when it is brought into contact with a heat treatment roll), a method of adjusting the surface temperature of the heat treatment roll for heat treatment, and the like.
  • the volatile content of the liquid coating when it is peeled off from the support depends on the volatile content of the film-forming stock solution, the temperature of the support, the temperature and speed of the hot air blown onto the liquid coating on the support, and the peripheral speed of the support, that is, the liquid Adjustment can be made by adjusting the time the coating is in contact with the support.
  • the volatile content of the film when the drying roll is peeled off depends on the selection of the film drying method, such as the method of passing the film through a drying oven or the method of contacting the drying roll, the temperature of the drying oven, the surface temperature of the drying roll, the drying time, etc.
  • the temperature of the support, the temperature of the hot air, the volatile content of the liquid coating when peeled from the support, the surface temperature of the drying roll, the volatile content of the film when peeled from the drying roll, or heat treatment is performed.
  • the value of Er1-Er3 or Er2-Er3 tends to increase as the surface temperature of the heat-treating roll increases.
  • Er1 is preferably 2.50 or more, more preferably 3.00 or more, and even more preferably 3.50 or more. Er1 is preferably 7.00 or less, more preferably 6.50 or less, and even more preferably 6.00 or less.
  • Er2 is preferably 2.50 or more, more preferably 3.00 or more, and even more preferably 3.50 or more. Er2 is preferably 7.00 or less, more preferably 6.50 or less, and even more preferably 6.00 or less.
  • Er3 is preferably 1.50 or more, more preferably 2.00 or more, and even more preferably 2.50 or more. Er3 is preferably 6.00 or less, more preferably 5.50 or less, even more preferably 5.00 or less.
  • the composite elastic modulus of the PVA film is affected by the degree of crystallinity.
  • Methods for evaluating crystallinity include X-ray diffraction, density, heat of fusion, FT-IR, and NMR.
  • FT-IR was chosen as a technique for evaluating locations equivalent to those evaluated.
  • the FT- Regarding the crystallinity index calculated during IR measurement the crystallinity index of the first surface is Fg1, the crystallinity index of the second surface is Fg2, and the crystallinity index of the central portion in the thickness direction is Fg3.
  • the Fg1, Fg2 and Fg3 satisfy the following formulas (3) to (5). 0.70 ⁇ Fg1 ⁇ 0.90 (3) 0.70 ⁇ Fg2 ⁇ 0.90 (4) 0.30 ⁇ Fg3 ⁇ 0.50 (5)
  • Fg1 is the crystallinity index calculated when FT-IR measurement is performed on the first surface
  • Fg2 is the FT for the second surface
  • Fg3 is the crystallinity index calculated when the -IR measurement is performed
  • Fg3 is the crystallinity index calculated when the FT-IR measurement is performed on the central portion in the thickness direction of the cross section.
  • the first surface 3 and the second surface 4 were each measured by FT-IR. Furthermore, as shown in FIG. 3, similarly to the nanoindentation test, the PVA film 1 was cut perpendicular to the first surface 3 and the second surface 4, and a sample with a cross section 5 was obtained. FT-IR measurement was performed on the central portion 8 in the thickness direction of the cross section 5.
  • the FT-IR measurement performed in the present invention is performed by the ATR method (total reflection absorption measurement method).
  • ATR method total reflection absorption measurement method
  • a sample here, PVA film 1
  • ATR prism 10 an objective lens
  • an infrared ray 11 is obliquely irradiated from within the ATR prism 10 to the sample.
  • It is a kind of reflective IR measurement method that measures the spectrum of the reflected light. It has the characteristic of obtaining a sharp spectrum with less noise than the usual reflection type IR measurement method.
  • the infrared rays 11 are not only reflected by the surface of the PVA film 1, but also the infrared rays that have slightly penetrated from the ATR prism 10 side to the film side are also reflected. Therefore, according to the FT-IR measurement by the ATR method, it is possible to obtain information on the surface layer of the film (the portion slightly recessed from the surface of the film in the depth direction).
  • the penetration depth 9 of the infrared rays that penetrate from the ATR prism 10 side to the PVA film 1 side is d
  • the value is given by the following equation (8).
  • n1 is the refractive index of the ATR prism
  • n2 is the refractive index of the film
  • ⁇ is the wavelength of the infrared rays
  • ⁇ is the incident angle of the infrared rays.
  • germanium having a refractive index of 4.0 was used as the base material of the ATR prism. Since the refractive index of the PVA film is 1.5, in the above formula (8), the penetration depth of infrared rays into the film surface layer when the incident angle of infrared rays is 45 ° and the wave number of infrared rays is 1140 cm -1 is calculated. Then, when germanium is used as the base material of the ATR prism, the penetration depth of infrared rays is about 0.5 ⁇ m, and it is possible to measure the very surface layer near the surface of the PVA film.
  • the crystallinity index calculated upon FT-IR measurement by the ATR method was calculated.
  • IR spectrum infrared absorption spectrum
  • This absorption peak is generally called the crystallization band of the PVA film, and is one of the peaks derived from the stretching vibration of the carbon bond (CC) of PVA. It is known that this crystallization band is emphasized and observed when the PVA polymer molecular chains in the PVA film are crystallized and the vibration phases of the PVA polymer molecular chains are aligned.
  • the higher the crystallinity of the PVA film the higher the peak intensity of the crystallization band.
  • an absorption peak is observed at 1425 cm ⁇ 1 due to bending vibration of methylene (—CH 2 —) which is the main chain of PVA. The intensity of this absorption peak is said to be independent of the crystallinity of the PVA film.
  • the crystallinity index (Fg1, Fg2) of the PVA film can be obtained.
  • the baselines of the infrared absorption spectra at 1140 cm ⁇ 1 and 1425 cm ⁇ 1 are drawn, and the heights from the baseline to the peak tops at 1140 cm ⁇ 1 and 1425 cm ⁇ 1 are taken as the absorption peak intensities of 1140 cm ⁇ 1
  • the value obtained by dividing the absorption peak intensity of 1425 cm ⁇ 1 by the peak intensity of 1425 cm ⁇ 1 was taken as the crystallinity index (Fg1, Fg2, Fg3).
  • the crystallinity indices Fg1 and Fg2 of the first surface and the second surface in the PVA film of the present invention are larger than the crystallinity index Fg3 of the central portion in the thickness direction, and are preferably adjusted within a specific range. If the crystallinity indices Fg1 and Fg2 of the first surface and the second surface of the PVA film are too large, the amount of amorphous regions in the PVA film is small. There is a problem that dichroic dyes such as colorants are difficult to incorporate, and the central portion in the thickness direction is not dyed. As a result, the heat and humidity resistance of the obtained polarizing film or polarizing plate is lowered.
  • the crystallinity indices Fg1 and Fg2 of the first surface and the second surface of the PVA film are too small, the orientation of the surface PVA is suppressed when the PVA film is uniaxially stretched to produce the polarizing film. Since the iodine complex that exhibits the polarizing performance becomes difficult to form, there is a problem that the polarizing performance of the obtained polarizing film is significantly deteriorated.
  • the crystallinity index Fg3 at the central portion in the thickness direction of the PVA film is too large, dichroic dyes such as iodine-based dyes are incorporated into the central portion in the thickness direction when the PVA film is uniaxially stretched to produce a polarizing film. There is a problem that it is difficult to stain and is not dyed. As a result, the heat and humidity resistance of the obtained polarizing film or polarizing plate is lowered.
  • Fg1 and Fg2 are preferably 0.70 or more.
  • Fg3 is preferably 0.30 or more.
  • Fg1 and Fg2 are preferably 0.90 or less.
  • Fg3 is preferably 0.50 or less.
  • Fg1, Fg2 and Fg3 are in the above range, when the PVA film is uniaxially stretched to produce a polarizing film, the central portion in the thickness direction is dyed to form an iodine complex, so the polarizing film has excellent heat and humidity resistance. can be obtained. Furthermore, a polarizing film having excellent polarizing performance can be obtained.
  • Fg1 and Fg2 are more preferably 0.72 or more, still more preferably 0.74 or more, and particularly preferably 0.76 or more.
  • Fg1 and Fg2 are more preferably 0.88 or less, still more preferably 0.86 or less, and particularly preferably 0.84 or less.
  • Fg3 is more preferably 0.31 or more, further preferably 0.32 or more, and particularly preferably 0.33 or more. Further, Fg3 is more preferably 0.49 or less, even more preferably 0.48 or less, and particularly preferably 0.47 or less.
  • the temperature of the support that drools the film-forming stock solution As a method for adjusting the film forming conditions of the PVA film, the temperature of the support that drools the film-forming stock solution, the temperature of the hot air that is blown onto the liquid coating on the support, the volatile content of the liquid coating when it is peeled off from the support, the support The volatile content/thickness of the liquid coating when peeled from the substrate, the surface temperature of the drying roll when drying the film after peeling from the support, the volatile content of the film when peeling off the drying roll (that is, the initial volatile content of the film when it is brought into contact with a heat treatment roll), a method of adjusting the surface temperature of the heat treatment roll for heat treatment, and the like.
  • the temperature of the support, the temperature of the hot air, the volatile content of the liquid coating when peeled from the support, the surface temperature of the drying roll, the volatile content of the film when peeled from the drying roll, or heat treatment is performed.
  • the values of Fg1 and Fg2 tend to increase as the surface temperature of the heat-treating roll increases.
  • the values of Fg1 and Fg2 tend to decrease as the surface temperature of the rolls decreases.
  • the absolute value of the difference between Fg1 and Fg2 is not necessarily limited, but Fg1 and Fg2 preferably satisfy the following formula (6).
  • PVA a polymer produced by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester monomer
  • vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and vinyl versatate.
  • vinyl acetate is preferable as the vinyl ester monomer.
  • the vinyl ester polymer is preferably a polymer obtained using only one or two or more vinyl ester monomers as a monomer, and is obtained using only one vinyl ester monomer as a monomer. more preferred.
  • the vinyl ester polymer may be a copolymer of one or more vinyl ester monomers and other monomers copolymerizable therewith.
  • Other monomers include, for example, ethylene; olefins having 3 to 30 carbon atoms such as propylene, 1-butene and isobutene; acrylic acid or salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid i -Acrylic esters such as propyl, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid or its salts; methacrylic acid Methyl, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacryl
  • N-vinylamides such as N-vinylformamide, N-vinylacetamide and N-vinylpyrrolidone
  • vinyl cyanides such as acrylonitrile and methacrylonitrile
  • vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride
  • vinylsilyl compounds such as vinyltrimethoxysilane; isopropenyl acetate and the like
  • the ratio of structural units derived from other monomers in the vinyl ester polymer is preferably 15 mol% or less, and 8 mol%, based on the number of moles of all structural units constituting the vinyl ester polymer. The following are more preferable.
  • crystallization of PVA tends to progress more slowly as the proportion of structural units derived from other monomers in the vinyl ester polymer increases. Therefore, by appropriately copolymerizing these other monomers in the above proportions, the composite elastic moduli (Er1, Er2 and Er3) and the crystallinity indices (Fg1, Fg2, Fg3) of the PVA film can be adjusted. .
  • the degree of polymerization of PVA is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 1,700 or more.
  • the flexibility of the PVA film can be improved by setting the degree of polymerization of PVA to the lower limit or higher.
  • the degree of polymerization of PVA is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 5,000 or less.
  • the degree of saponification of PVA is preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 99 mol% or more, because the obtained polarizing film has good moist heat resistance. It is preferably 99.3 mol % or more, and particularly preferably 99.3 mol % or more.
  • the degree of saponification of PVA refers to the ratio (mol% ). The degree of saponification can be measured according to the description of JIS K6726-1994.
  • the PVA film of the present invention may contain one type of PVA alone, or may contain two or more types of PVA having different degrees of polymerization, degree of saponification, degree of modification, and the like.
  • the modified PVA for example, ethylene-modified PVA can be used.
  • the degree of modification of PVA is preferably 0.01 mol % or more, more preferably 0.1 mol % or more, and even more preferably 1 mol % or more.
  • the degree of modification of PVA is preferably 15 mol % or less, more preferably 8 mol % or less, and even more preferably 5 mol % or less.
  • the content of PVA in the PVA film of the present invention is not necessarily limited, it is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more.
  • the PVA film of the present invention preferably contains a plasticizer.
  • a plasticizer By containing a plasticizer, it is possible to improve the handleability and stretchability of the PVA film.
  • plasticizers include polyhydric alcohols such as ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and sorbitol. These plasticizers may be used alone or in combination of two or more.
  • the plasticizer is preferably ethylene glycol or glycerin, and more preferably glycerin, because it is difficult to bleed out to the surface of the PVA film.
  • the content of the plasticizer in the PVA film of the present invention is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 4 parts by mass or more with respect to 100 parts by mass of PVA. preferable.
  • the content of the plasticizer is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less with respect to 100 parts by mass of PVA.
  • the PVA film of the present invention preferably contains a surfactant.
  • a surfactant can improve the handleability of the PVA film and the peelability of the PVA film from the film forming apparatus during production.
  • the surfactant is not particularly limited, and for example, anionic surfactants and nonionic surfactants are preferably used.
  • anionic surfactants include carboxylic acid surfactants such as potassium laurate; sulfate ester surfactants such as octyl sulfate; sulfonic acid surfactants such as dodecylbenzene sulfonate.
  • nonionic surfactants include alkyl ether surfactants such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; alkylphenyl ether surfactants such as polyoxyethylene octylphenyl ether; Alkyl ester type surfactants such as latex; Alkyl amine type surfactants such as polyoxyethylene lauryl amino ether; Alkyl amide type surfactants such as polyoxyethylene lauric acid amide; Polypropylene such as polyoxyethylene polyoxypropylene ether Glycol ether type surfactants; alkanolamide type surfactants such as lauric acid diethanolamide and oleic acid diethanolamide; and allyl phenyl ether type surfactants such as polyoxyalkylene allyl phenyl ether.
  • alkyl ether surfactants such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether
  • alkylphenyl ether surfactants such as polyoxyethylene
  • Such surfactants may be used singly or in combination of two or more.
  • nonionic surfactants are preferred, alkanolamide surfactants are more preferred, and aliphatic carboxylic acids (e.g., carbon Further preferred are dialkanolamides (eg, diethanolamide, etc.) of saturated or unsaturated aliphatic carboxylic acids of numbers 8 to 30, and the like.
  • the content of the surfactant in the PVA film of the present invention is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and 0.05 parts by mass with respect to 100 parts by mass of PVA. More preferably, it is at least 1 part.
  • the content of the surfactant is preferably 10 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less with respect to 100 parts by mass of PVA. , 0.3 parts by mass or less.
  • the PVA film of the present invention contains, in addition to PVA, a water-soluble polymer, moisture, an antioxidant, an ultraviolet absorber, a lubricant, a cross-linking agent, a coloring agent, a filler, an antiseptic, an antifungal agent, other polymer compounds, and the like. may be contained within a range that does not impair the effects of the present invention.
  • the ratio of the total mass of PVA, surfactants, plasticizers, and other components other than PVA to the total mass of the PVA film is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and 90 to 100% by mass is more preferable.
  • the upper limit of the average thickness of the PVA film of the present invention is not particularly limited, it is preferably 100 ⁇ m, more preferably 80 ⁇ m, even more preferably 60 ⁇ m, and particularly preferably 50 ⁇ m.
  • the lower limit of the average thickness is preferably 10 ⁇ m, more preferably 15 ⁇ m, and more preferably 20 ⁇ m from the viewpoint of obtaining a PVA film that satisfies the above formulas (1) and (2). is more preferred.
  • the value of Er1-Er3 or Er2-Er3 tends to increase as the average thickness of the PVA film increases. The smaller the average thickness of the PVA film, the smaller the value of Er1-Er3 or Er2-Er3.
  • the shape of the PVA film of the present invention is not particularly limited, it is preferably a long film because the polarizing film can be continuously produced with good productivity.
  • the length of the long film is not particularly limited, and can be appropriately set according to the application of the polarizing film to be produced, and can be, for example, within the range of 5 m or more and 20,000 m or less.
  • the width of the long film is not particularly limited, and can be, for example, 50 cm or more, but since wide polarizing films have been demanded in recent years, it is preferably 1 m or more, and more preferably 2 m or more. Preferably, it is more preferably 4 m or more.
  • the upper limit of the width of the long film is not particularly limited, but if the width is too wide, it tends to be difficult to stretch uniformly when producing a polarizing film with an apparatus that has been put into practical use. Therefore, the width of the PVA film is preferably 7 m or less.
  • the shape of the PVA film of the present invention is not particularly limited, and it may be a single layer film or a multilayer film (laminate). , preferably a single layer film.
  • the PVA film of the present invention is usually an unstretched film. Since the PVA film of the present invention is a non-stretched film, it can be suitably used as a film for producing an optical film such as a polarizing film. It should be noted that stretched forms of PVA films are also within the scope of the present invention.
  • the PVA film of the present invention is water insoluble. Since the PVA film is water-insoluble, the PVA film can be stretched without breaking when uniaxially stretched in an aqueous solution when producing an optical film such as a polarizing film.
  • the water-insoluble in the present invention means that when the PVA film is immersed in water (deionized water) at 30° C. according to the following procedures ⁇ 1> to ⁇ 4>, the PVA film does not completely dissolve and It means that even the part remains undissolved.
  • ⁇ 1> Place the PVA film in a thermo-hygrostat adjusted to 20° C. and 65% RH for 16 hours or longer to condition the humidity.
  • ⁇ 2> A rectangular sample with a length of 40 mm and a width of 35 mm was cut out from the humidity-conditioned PVA film. The sample is sandwiched and fixed between the two so that the length direction of the sample is parallel to the length direction of the window and the sample is positioned substantially in the center of the width direction of the window.
  • ⁇ 3> Put 300 mL of deionized water into a 500 mL beaker, and adjust the water temperature to 30° C. while stirring with a magnetic stirrer equipped with a 3 cm long bar at 280 rpm.
  • ⁇ 4> The sample fixed to the plastic plate in ⁇ 2> above is immersed in deionized water in a beaker for 1000 seconds while being careful not to contact the bar of the rotating magnetic stirrer.
  • the degree of swelling of the PVA film of the present invention is preferably 130% or more, more preferably 150% or more, more preferably 170% or more, from the viewpoint of the productivity and polarizing performance of the polarizing film.
  • the degree of swelling of the PVA film is preferably 300% or less, more preferably 280% or less, even more preferably 260% or less, from the viewpoint of the productivity and polarizing performance of the polarizing film.
  • the degree of swelling is 130% or more, the film swells sufficiently in the drawing bath and the dichroic dye is easily adsorbed, so that a polarizing film having high polarizing performance can be produced.
  • the degree of swelling of the PVA film can be adjusted by, for example, heat treatment conditions. Specifically, the degree of swelling can be adjusted to a small value by increasing the heat treatment conditions.
  • the degree of swelling of the PVA film can be obtained as a percentage by dividing the mass after immersing the PVA film sample in distilled water at 30°C for 15 minutes by the mass after drying at 105°C for 16 hours after immersion. This swelling degree can be specifically measured by the method described later in Examples.
  • the central portion in the width direction of the PVA film may be taken as a representative position.
  • the softening point of the PVA film of the present invention is preferably 60°C or higher, more preferably 65°C or higher, from the viewpoint of productivity and polarizing performance of the polarizing film.
  • the softening point of the PVA film of the present invention is preferably 80° C. or lower, more preferably 75° C. or lower, from the viewpoint of the productivity of the polarizing film and the polarizing performance.
  • the softening point of the PVA film can be obtained as the hot water deformation temperature when the PVA film sample is placed in distilled water at 25°C and the temperature is raised at a rate of 5°C/min. This softening point can be specifically measured by the method described later in Examples.
  • the central portion in the width direction of the PVA film may be taken as a representative position.
  • the haze of the PVA film of the present invention is preferably 2.0% or less, more preferably 1.5% or less, from the viewpoint of the optical properties and the polarizing performance of the obtained polarizing film.
  • the lower limit of haze is preferably 0.1%, more preferably 0.3%.
  • the haze can be obtained as a ratio (percentage) of the diffuse transmittance to the total light transmittance when the PVA film is irradiated with visible light.
  • the PVA film of the present invention has good water swelling properties by adjusting the degree of swelling to a suitable range by heat treatment or the like. Therefore, a polarizing film having high polarizing performance can be produced from the PVA film, and it can be suitably used as a raw film for producing an optical film such as a polarizing film.
  • the use of the PVA film of the present invention is not particularly limited, and it can also be used as a raw film such as a stretched film, an agricultural film, a packaging film, and the like.
  • the method for producing the PVA film of the present invention is not particularly limited, and any of the following methods can be adopted, for example. Examples of such methods include casting a film forming method, wet film forming method (method of discharging into a poor solvent), wet film forming method, A method of forming a film by a gel film-forming method (a method of cooling and gelling a film-forming undiluted solution and then removing the solvent by extraction), or a method of forming a film by a combination of these methods, or a film-forming undiluted solution obtained by using an extruder or the like is subjected to T Examples include a melt extrusion film-forming method and an inflation molding method in which a film is formed by extrusion from a die or the like.
  • the casting film-forming method and the melt extrusion film-forming method are preferable as the method for producing the PVA film. Using these methods, a homogeneous PVA film can be obtained with good productivity. A case of producing a PVA film using a casting film-forming method or a melt extrusion film-forming method will be described below.
  • the PVA film of the present invention is produced by a casting film forming method or a melt extrusion film forming method, first, a film forming stock solution containing PVA, a solvent, and optionally additives such as a plasticizer is prepared. prepare. Next, this film-forming stock solution is poured (supplied) in the form of a film onto a rotating support such as a metal roll or metal belt. As a result, a liquid coating of the membrane-forming stock solution is formed on the support. The liquid coating is solidified into a film by heating on the support to remove the solvent.
  • Examples of the method of heating the liquid coating include a method of increasing the temperature of the support itself with a heat medium or the like, and a method of blowing hot air onto the surface of the liquid coating opposite to the surface in contact with the support.
  • the solidified long film (PVA film) is peeled off from the support, dried with a drying roll, a drying oven, etc., if necessary, heat-treated, and wound into a roll.
  • the draw tensile elongation in the machine direction
  • the rate of crystallization and the degree of orientation at this time are Affected by moisture content and temperature.
  • Drying of a PVA film usually progresses as volatile matter evaporates from the released film surface that is not in contact with the support or drying roll. Therefore, in the drying process, the concentration distribution of volatiles such as moisture occurs in the thickness direction of the PVA film. A distribution occurs.
  • the distribution of the composite elastic modulus and the crystallinity index depends on the support temperature, hot air temperature, volatile content of the PVA film when peeled from the support, heat treatment method, volatile content of the PVA film during heat treatment, heat treatment temperature, etc. can be adjusted. Therefore, by appropriately adjusting each of the above factors, the crystallization and orientation of PVA can be moderately advanced, and the composite elastic modulus and crystallinity index of the PVA film can be adjusted.
  • the volatile fraction (concentration of volatile components such as solvents removed by volatilization or evaporation during film formation) of the film-forming stock solution is preferably 60% by mass or more, more preferably 65% by mass or more. preferable.
  • the volatile content of the film-forming stock solution is preferably 90% by mass or less, more preferably 80% by mass or less.
  • the viscosity of the film-forming stock solution can be adjusted to a suitable range, so that the film-forming properties of the liquid film cast on the support are improved and the film has a uniform thickness. It becomes easy to obtain a PVA film.
  • the membrane-forming stock solution may contain a dichroic dye if necessary.
  • the volatile content of the membrane-forming stock solution in the present specification refers to the value obtained by the following formula (9).
  • Volatile content (% by mass) of film-forming stock solution ⁇ (Wa-Wb)/Wa ⁇ x 100 (9)
  • Wa represents the mass (g) of the membrane-forming stock solution
  • Wb is the mass (g) after drying the membrane-forming stock solution of Wa (g) in an electric heat dryer at 105 ° C. ).
  • the method for preparing the membrane-forming stock solution is not particularly limited.
  • a method of melt-kneading the used PVA in a water-containing state together with additives such as a plasticizer and a surfactant can be used.
  • the film-forming stock solution generally passes through the die lip of a die such as a T-die and is poured onto a support such as a metal roll or metal belt in the form of a film.
  • the solvent evaporates from the surface of the drooled film-like undiluted solution that is not in contact with the support (hereinafter sometimes referred to as the free surface), while the solvent is volatilized from the surface that is in contact with the support. Since it does not substantially volatilize from the surface where the solvent is applied (hereinafter sometimes referred to as the touch surface), the distribution in the thickness direction of the film is such that the solvent concentration on the free surface side is low and the solvent concentration on the touch surface side is high. occur. Therefore, the solidification of PVA also proceeds from the free surface.
  • the crystallization of PVA progresses in parallel with the solidification of PVA. Crystallization of PVA is difficult to progress when the solvent concentration is too high or too low, and the volatile content of the drooled membrane-forming stock solution is 10% by mass or more and 50% by mass or less, although it depends on the primary structure of the PVA molecule. Easy to progress when In addition, the higher the temperature, the faster the crystallization rate of PVA, and the higher the temperature, the faster the volatilization rate of the solvent.
  • the difference between the composite elastic modulus in the vicinity of the surface and the composite elastic modulus in the central part in the thickness direction is within a specific range in a cross section that is cut perpendicular to the two surfaces of the PVA film. adjusting. Therefore, in order to obtain the PVA film of the present invention, it is only necessary to select conditions that increase the composite elastic modulus in the vicinity of the surface of the film while suppressing the improvement in the composite elastic modulus in the central portion in the thickness direction. For example, when the difference between the volatile content in the vicinity of the surface of the PVA film and the volatile content in the center in the thickness direction is large, that is, when the volatile content of the PVA film is high, the conditions for peeling from the support and drawing are applied. It is preferable to employ conditions for heat treatment. Moreover, it is also preferable to perform drying and heat treatment while a roll or the like is in direct contact with the surface of the PVA film.
  • the surface temperature of the support onto which the film-forming stock solution is poured is preferably 65° C. or higher, more preferably 70° C. or higher, and more preferably 75° C. or higher. More preferred.
  • the surface temperature of the support onto which the film forming stock solution is poured is preferably 120° C. or lower, more preferably 105° C. or lower, and preferably 99° C. or lower. More preferred.
  • drying of the liquid film drooled onto the support progresses at an appropriate speed.
  • hot air may be uniformly blown to the entire non-contact surface side of the liquid coating at a wind speed of 1 to 10 m/sec.
  • the temperature of the hot air blown to the non-contact surface side is preferably 50° C. or higher, more preferably 70° C. or higher.
  • the temperature of the hot air blown to the non-contact surface side is preferably 150° C. or lower, more preferably 120° C. or lower.
  • the value divided by the film thickness ( ⁇ m) is preferably 0.1% by mass/ ⁇ m or more, more preferably 0.2% by mass/ ⁇ m or more, and 0.3% by mass/ ⁇ m or more. It is even more preferable to have The value obtained by dividing the volatile content (% by mass) when peeled from the support by the thickness ( ⁇ m) of the PVA film after drying is preferably 1.0% by mass/ ⁇ m or less, and 0.8% by mass. / ⁇ m or less, more preferably 0.5% by mass/ ⁇ m or less.
  • the difference between the composite elastic modulus in the vicinity of the surface and the composite elastic modulus in the center in the thickness direction of the obtained PVA film becomes too small.
  • the difference between the composite elastic modulus near the surface of the obtained PVA film and the composite elastic modulus at the central portion in the thickness direction becomes too large, or It is not preferable because it makes peeling difficult.
  • the volatile content of the liquid coating or PVA film in this specification refers to the value obtained by the following formula (10).
  • Volatile content of liquid coating or PVA film (% by mass) ⁇ (Wc ⁇ Wd)/Wc ⁇ 100 (10)
  • Wc represents the mass (g) of the sample taken from the liquid coating or PVA film
  • Wd represents the sample Wc (g) in a vacuum dryer at a temperature of 50 ° C. and a pressure of 0.1 kPa or less. It represents the mass (g) when it is put in and dried for 4 hours.
  • the volatile content of the PVA film when peeled from the support can also be adjusted by changing the peripheral speed of the support such as a metal roll or metal belt.
  • the peripheral speed of the support is preferably 8 m/min or more, more preferably 11 m/min or more, and even more preferably 14 m/min or more.
  • the peripheral speed of the support is preferably 30 m/min or less, more preferably 27 m/min or less, and even more preferably 24 m/min or less.
  • the PVA film after being peeled off from the support is further dried as necessary.
  • the drying method is not particularly limited, and includes a method of passing through a drying oven and a method of contacting with a drying roll.
  • the PVA film is dried using a plurality of drying rolls, it is preferable that one surface and the other surface of the PVA film are alternately brought into contact with the drying rolls. This makes it possible to adjust the composite elastic modulus and crystallinity index of the PVA film on both sides (the first surface and the second surface) of the PVA film.
  • the number of drying rolls is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more.
  • the number of drying rolls is preferably 30 or less.
  • the temperature of the drying oven or the surface temperature of the drying roll is preferably 40°C or higher and 110°C or lower.
  • the upper limit of the temperature of the drying oven or the surface temperature of the drying roll is preferably 110°C, more preferably 100°C, even more preferably 90°C, and particularly preferably 85°C.
  • the lower limit of the temperature of the drying oven or the surface temperature of the drying roll is more preferably 45°C, more preferably 50°C.
  • the dried PVA film can be further heat-treated as necessary.
  • the composite elastic modulus and crystallinity index of the PVA film can be adjusted.
  • properties such as mechanical strength and swelling property of the PVA film can also be adjusted.
  • the heat treatment method is not particularly limited, and includes a method of blowing hot air with a floating dryer, a method of irradiating near infrared rays with an infrared lamp, and a method of contacting with a heat treatment roll.
  • a method of blowing hot air with a floating dryer includes a method of blowing hot air with a floating dryer, a method of irradiating near infrared rays with an infrared lamp, and a method of contacting with a heat treatment roll.
  • the PVA film A method of directly contacting the surface with a heat treatment roll is preferred.
  • the number of heat treatment rolls is preferably two or more, more preferably four or more.
  • the volatile content of the PVA film when brought into contact with the first heat treatment roll is preferably 2% by mass or more, more preferably 4% by mass or more.
  • the volatile content of the PVA film when brought into contact with the initial heat treatment roll is preferably 15% by mass or less, more preferably 12% by mass or less.
  • the surface temperature of the heat treatment roll for heat treatment is preferably 80°C or higher, more preferably 90°C or higher.
  • the surface temperature of the heat treatment roll for heat treatment is preferably 140° C. or lower, more preferably 130° C. or lower.
  • the PVA film thus produced is further subjected to humidity control treatment, cutting of both ends (edges) of the film, etc., if necessary, and then wound into a roll on a cylindrical core. , moisture-proof packaging to become a product.
  • the volatile content of the PVA film finally obtained by a series of treatments is not necessarily limited, it is preferably 1% by mass or more, more preferably 2% by mass or more. Although the volatile content of the finally obtained PVA film is not necessarily limited, it is preferably 5% by mass or less, more preferably 4% by mass or less.
  • optical film By using the PVA film of the present invention as the original film of the optical film, it is possible to produce an optical film having excellent polarizing performance and moisture and heat resistance, and therefore it is suitable as a film for producing an optical film.
  • the optical film include a polarizing film, a viewing angle improving film, a retardation film, and a brightness improving film, and the polarizing film is preferable.
  • the manufacturing method of a polarizing film is mentioned and demonstrated concretely as an example of the manufacturing method of an optical film.
  • the method for manufacturing the polarizing film is not particularly limited, and any conventionally used method may be adopted.
  • a polarizing film can be produced by subjecting the PVA film of the present invention to swelling treatment, dyeing treatment, uniaxial stretching, and, if necessary, cross-linking treatment, fixing treatment, drying treatment, heat treatment, and the like.
  • the order of each treatment such as swelling treatment, dyeing treatment, uniaxial stretching, and fixing treatment is not particularly limited, and one or more treatments can be performed simultaneously. Also, one or more of each treatment can be performed two or more times.
  • the swelling treatment can be performed by immersing the PVA film in water.
  • the lower limit of the temperature of water when immersed in water is preferably 20°C, more preferably 22°C, and even more preferably 25°C.
  • the upper limit is preferably 40°C, more preferably 38°C, and even more preferably 35°C.
  • the time for immersion in water is preferably 0.1 minute or more and 5 minutes or less.
  • the water used for immersion in water is not limited to pure water, and may be an aqueous solution in which various components are dissolved, or a mixture of water and an aqueous medium.
  • the dyeing process is performed using a dichroic dye such as an iodine-based dye or a dye, and the dyeing stage may be before uniaxial stretching, during uniaxial stretching, or after uniaxial stretching.
  • Dyeing is generally carried out by immersing the PVA film in a solution (particularly an aqueous solution) containing iodine-potassium iodide as a dyeing bath.
  • the concentration of iodine in the dyeing bath is preferably 0.01% by mass or more.
  • the concentration of iodine in the dyeing bath is preferably 0.5% by mass or less.
  • the concentration of potassium iodide is preferably 0.01% by mass or more.
  • the concentration of potassium iodide is preferably 10% by mass or less.
  • the temperature of the dyeing bath is preferably 20° C. or higher.
  • the temperature of the dyeing bath is preferably 60° C. or lower.
  • the cross-linking treatment can be performed by immersing the PVA film in an aqueous solution containing a cross-linking agent.
  • a cross-linking agent to be used, one or more of boron compounds such as borate salts such as boric acid and borax can be used.
  • the concentration of the cross-linking agent in the aqueous solution containing the cross-linking agent is preferably 1% by mass or more, more preferably 2% by mass or more.
  • the concentration of the cross-linking agent in the aqueous solution containing the cross-linking agent is preferably 15 mass % or less, more preferably 7 mass % or less.
  • the temperature of the aqueous solution containing the cross-linking agent is preferably 20° C. or higher.
  • the temperature of the aqueous solution containing the cross-linking agent is preferably 60° C. or less.
  • Uniaxial stretching may be performed by either a wet stretching method or a dry stretching method.
  • the wet stretching method it can be carried out in an aqueous solution containing boric acid, or it can be carried out in the dyeing bath described above or in the fixing treatment bath described later.
  • the dry stretching method it can be carried out in the air.
  • the wet stretching method is preferable, and uniaxial stretching in an aqueous solution containing boric acid is more preferable.
  • the concentration of boric acid in the boric acid aqueous solution is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more.
  • the concentration of boric acid in the boric acid aqueous solution is preferably 6.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 4.0% by mass or less.
  • the boric acid aqueous solution may contain potassium iodide, and its concentration is preferably 0.01% by mass or more.
  • the concentration of potassium iodide is preferably 10% by mass or less.
  • the stretching temperature in uniaxial stretching is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher.
  • the stretching temperature in the uniaxial stretching is preferably 90° C. or lower, more preferably 80° C. or lower, and even more preferably 70° C. or lower.
  • the draw ratio in uniaxial stretching is preferably 5 times or more, more preferably 5.5 times or more, from the viewpoint of the polarizing performance of the obtained polarizing film.
  • the upper limit of the draw ratio is not particularly limited, the draw ratio is preferably 8 times or less.
  • a fixing treatment in order to strengthen the adsorption of the dichroic dye to the PVA film.
  • An aqueous solution containing one or more of boron compounds such as boric acid and borax can be used as the fixing treatment bath used for the fixing treatment.
  • an iodine compound or a metal compound may be added to the fixing treatment bath.
  • the concentration of the boron compound in the fixing treatment bath is generally preferably 2% by mass or more, more preferably 3% by mass or more.
  • the concentration of the boron compound in the fixing treatment bath is generally preferably 15% by mass or less, more preferably 10% by mass or less.
  • the temperature of the fixing treatment bath is preferably 15° C. or higher, more preferably 25° C. or higher.
  • the temperature of the fixing treatment bath is preferably 60° C. or lower, more preferably 40° C. or lower.
  • the drying treatment is preferably carried out at 30°C or higher, more preferably at 50°C or higher.
  • the drying treatment is preferably performed at 150° C. or lower, more preferably 130° C. or lower.
  • the polarizing film obtained as described above is preferably used as a polarizing plate by laminating an optically transparent protective film having mechanical strength on one or both sides thereof.
  • a cellulose triacetate (TAC) film, a cycloolefin polymer (COP) film, a cellulose acetate/butyrate (CAB) film, an acrylic film, a polyester film, or the like is used.
  • the adhesive for bonding PVA-based adhesives, urethane-based adhesives, and the like can be used, but PVA-based adhesives are preferable.
  • the polarizing plate obtained as described above can be used as an LCD component by laminating an acrylic adhesive or the like and then bonding it to a glass substrate. At the same time, it may be attached to a retardation film, a viewing angle improving film, a brightness improving film, or the like.
  • the composite elastic modulus is Er1 when measuring the area within 5 ⁇ m from the first surface toward the center in the thickness direction, and the area within 5 ⁇ m from the second surface toward the center in the thickness direction.
  • Er2 is the composite elastic modulus when measuring
  • Er3 is the composite elastic modulus of the central region in the thickness direction.
  • Er1, Er2, and Er3 are calculated from the load-displacement curve at the time of insertion using analysis software attached to the device described below. In the measurement, an average value of 10 arbitrary points was adopted. Detailed measurement conditions are as follows.
  • Measuring device Multifunctional SPM device (manufactured by Hitachi High-Tech), TriboScope (manufactured by HYSITRON) Analysis software: Analysis software attached to the device Measurement temperature: 23°C Measured relative humidity: 40% Indentation conditions: 200 ⁇ N for 3 seconds, 3 seconds for withdrawal (indentation depth: about 250 nm) Indenter: Berkovich indenter (model number: TI-0039, manufactured by HYSITRON)
  • Measuring device Nicolet iS 10 (manufactured by Thermo Fisher) Measurement conditions: Single reflection ATR method Incident angle 45° Resolution: 4.0 cm -1 Cumulative number of times: 32 times Measurement temperature: 25°C (environmental temperature) Measurement humidity: 45% RH (environmental relative humidity) ATR Prism: Germanium Prism
  • the crystallinity index Fg1 of the first surface of the PVA film and the crystallinity index Fg2 of the second surface of the PVA film were calculated by the method described above.
  • the crystallinity index Fg3 of the central portion in the thickness direction of the PVA film was calculated by the method described above.
  • Ts1 and Ts2 were averaged by the following formula (11) to obtain the transmittance Ts (%) of the polarizing film.
  • Ts (Ts1+Ts2)/2 (11)
  • the dyeing conditions were adjusted to prepare samples so that the transmittance Ts was 44.0%, and the degree of polarization V was measured as follows.
  • the polarization performance was determined according to the following criteria. In addition, A and B were judged to be good because they could be used practically without problems, and C was judged to be unsatisfactory.
  • ⁇ Moisture and heat resistance test> A polarizing plate obtained in each of the following examples or comparative examples was cut into 4 cm squares, and the light transmittance Ts(I) before the moisture and heat resistance test was measured by the method described above. After that, it was placed in a thermo-hygrostat at 60° C. and 90% RH for 24 hours, and the light transmittance Ts(II) after the moisture-heat resistance test was measured. Then, as an index of the resistance to heat and humidity, the amount of change ⁇ Ts in the light transmittance before and after the resistance to heat and humidity test was determined by the following formula (13).
  • ⁇ Ts Ts(I) - Ts(II) (13)
  • a and B were judged to be good because they could be used practically without problems, and C was judged to be unsatisfactory.
  • the heat treatment was performed using two heat treatment rolls, and the surface temperature of the heat treatment rolls was 105°C.
  • the resulting PVA film (thickness 60 ⁇ m, width 1200 mm) was subjected to nanoindentation test and FT-IR measurement by the above method, and the composite elastic modulus (Er1, Er2, Er3) and the crystallinity index (Fg1, Fg2 , Fg3) were calculated. Table 1 shows the results.
  • the obtained PVA film was slit to a width of 650 mm, and the film was subjected to swelling treatment, dyeing treatment, cross-linking treatment, stretching treatment, washing treatment and drying treatment in this order to continuously produce a polarizing film.
  • the swelling treatment was carried out by uniaxially stretching the film 2.00 times in the length direction while immersing it in pure water (swelling treatment liquid) at 25°C.
  • the dyeing treatment is performed by immersing in a potassium iodide / iodine dyeing solution (dyeing treatment solution) (potassium iodide / iodine (mass ratio) 23, iodine concentration 0.03 to 0.05% by mass) at a temperature of 32 ° C. It was uniaxially stretched 1.26 times in the direction.
  • the iodine concentration in the dyeing treatment solution is adjusted to 0.02% by mass or more and 0.05% by mass or less so that the single transmittance of the polarizing film obtained after uniaxial stretching in the stretching treatment is 44%. It was adjusted.
  • the cross-linking treatment was carried out by uniaxial stretching by 1.19 times in the length direction while being immersed in an aqueous boric acid solution (cross-linking treatment liquid) (boric acid concentration: 2.6% by mass) at 32°C.
  • cross-linking treatment liquid aqueous boric acid solution
  • the film was uniaxially stretched 2.00 times in the length direction while being immersed in a boric acid/potassium iodide aqueous solution (stretching treatment liquid) (boric acid concentration: 2.8% by mass, potassium iodide concentration: 5% by mass). went.
  • the temperature of the stretching treatment is a stretching temperature at which the stretching stress in the stretching bath (stretching tension (N)/(PVA film width (mm) ⁇ PVA film thickness (mm)) is 10 N/mm 2 or more and 12 N/mm 2 or less.
  • the cleaning treatment was immersed in a potassium iodide/boric acid aqueous solution (cleaning treatment solution) (potassium iodide concentration of 3 to 6% by mass, boric acid concentration of 1.5% by mass) at 22°C for 12 seconds without stretching.
  • the drying treatment was carried out by drying with hot air at 80° C. for 1.5 minutes without stretching, to obtain a polarizing film.
  • the polarization performance was evaluated and the results are shown in Table 1.
  • a polarizing plate was manufactured by laminating a triacetyl cellulose film on both sides of the obtained polarizing film using a PVA-based adhesive (3.5% by mass aqueous solution of PVA) and drying at 70°C.
  • the PVA in the PVA-based adhesive used was a saponified product of a homopolymer of vinyl acetate, the degree of polymerization of PVA was 2400, and the degree of saponification of PVA was 99 mol %.
  • Example 2 A PVA film, a polarizing film and a polarizing plate were prepared in the same manner as in Example 1 except that the PVA used in the film-forming stock solution was changed to PVA (degree of saponification 99 mol%, degree of polymerization 2400, ethylene modification 2.5 mol%). got The obtained polarizing film and polarizing plate were measured and evaluated in the same manner as in Example 1. Table 1 shows the results.
  • Example 3 The volatile content of the membrane-forming stock solution was 72% by mass (adjusted by changing the water content from Example 1), the temperature of the support was 85°C, the peripheral speed of the support was 19.0 m/min, and the The volatile content of the PVA film when peeled is 13% by mass, the volatile content of the PVA film when peeled from the final drying roll is 5% by mass, the surface temperature of the heat treatment roll is 120 ° C., and the thickness of the obtained PVA film is A PVA film, a polarizing film and a polarizing plate were obtained in the same manner as in Example 1, except that the thickness was changed to 30 ⁇ m. The obtained polarizing film and polarizing plate were measured and evaluated in the same manner as in Example 1. Table 1 shows the results.
  • the PVA used in the membrane-forming stock solution is PVA (degree of saponification 99 mol%, degree of polymerization 4000), the volatile content of the membrane-forming stock solution is 72% by mass (adjusted by changing the water content from Example 1), and the support temperature of 85 ° C., the peripheral speed of the support is 19.0 m / min, the volatile content of the PVA film when peeled from the support is 12% by mass, and the volatile content of the PVA film when peeled from the final drying roll
  • a PVA film, a polarizing film and a polarizing plate were obtained in the same manner as in Example 1 except that the content was changed to 5% by mass, the surface temperature of the heat treatment roll was changed to 120 ° C., and the thickness of the obtained PVA film was changed to 30 ⁇ m.
  • the obtained polarizing film and polarizing plate were measured and evaluated in the same manner as in Example 3. Table 1 shows the results.
  • Example 5 The temperature of the support is 95 ° C., the temperature of the hot air blown to the entire non-contact surface of the liquid coating with the support is 95 ° C., the volatile content of the PVA film when peeled from the support is 18% by mass, and the The surface temperature of each drying roll from the drying roll after peeling to the final drying roll is 60 ° C., the volatile content of the PVA film when peeled from the final drying roll is 10% by mass, and the surface temperature of the heat treatment roll is 120 ° C.
  • a PVA film, a polarizing film and a polarizing plate were obtained in the same manner as in Example 1 except for the changes. The obtained polarizing film and polarizing plate were measured and evaluated in the same manner as in Example 1. Table 1 shows the results.
  • Example 6> The temperature of the support is 80 ° C., the temperature of the hot air blown over the entire non-contact surface of the liquid coating with the support is 80 ° C., the volatile content of the PVA film when peeled from the support is 27% by mass, and the The PVA film, the polarizing film and the A polarizing plate was obtained. The obtained polarizing film and polarizing plate were measured and evaluated in the same manner as in Example 1. Table 1 shows the results.
  • Example 1 The temperature of the support is 80°C, the peripheral speed of the support is 9.0 m/min, the temperature of the hot air blown to the entire non-contact surface of the liquid coating with the support is 80°C, and the PVA film is peeled off from the support.
  • the volatile content of 17% by mass the volatile content of the PVA film when peeled from the final drying roll was changed to 5% by mass, and the surface temperature of the heat treatment roll was changed to 90 ° C.
  • a PVA film, a polarizing film and a polarizing plate were obtained. The obtained polarizing film and polarizing plate were measured and evaluated in the same manner as in Example 1. Table 1 shows the results.
  • Example 2 A PVA film, a polarizing film, and a polarizing plate were obtained in the same manner as in Example 1, except that heat treatment was performed by blowing hot air at 120° C. with a floating dryer instead of using a heat treatment roll. The obtained polarizing film and polarizing plate were measured and evaluated in the same manner as in Example 1. Table 1 shows the results.
  • Example 3 The temperature of the support is 95° C., the peripheral speed of the support is 22.0 m/min, the temperature of the hot air blown over the entire non-contact surface of the liquid coating with the support is 95° C., and the PVA film is peeled off from the support.
  • a PVA film, a polarizing film and a polarizing plate were obtained in the same manner as in Example 1, except that the volatile content of was changed to 32% by mass and the surface temperature of the heat treatment roll was changed to 120°C.
  • the obtained polarizing film and polarizing plate were measured and evaluated in the same manner as in Example 1. Table 1 shows the results.

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