CN116097332A - Dyed cellulose triacetate film, polarizing plate using the same, method for producing polarizing plate, polarizing plate with retardation layer, image display device, and method for adjusting image of image display device - Google Patents
Dyed cellulose triacetate film, polarizing plate using the same, method for producing polarizing plate, polarizing plate with retardation layer, image display device, and method for adjusting image of image display device Download PDFInfo
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- CN116097332A CN116097332A CN202180052958.3A CN202180052958A CN116097332A CN 116097332 A CN116097332 A CN 116097332A CN 202180052958 A CN202180052958 A CN 202180052958A CN 116097332 A CN116097332 A CN 116097332A
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- Prior art keywords
- polarizing plate
- layer
- retardation layer
- film
- polarizing
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
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Images
Classifications
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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
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
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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
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133553—Reflecting elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8793—Arrangements for polarized light emission
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
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- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- G02F2202/00—Materials and properties
- G02F2202/40—Materials having a particular birefringence, retardation
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- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/01—Number of plates being 1
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- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/02—Number of plates being 2
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- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/08—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates with a particular optical axis orientation
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Abstract
Provided are a polarizing plate capable of realizing a neutral reflection hue when applied to an image display device, and a polarizing plate with a retardation layer. The polarizing plate of the present invention includes a polarizing film and a protective layer disposed on a visual recognition side of the polarizing film. The polarizing film has a thickness of 8 μm or less, and the protective layer is formed of a cellulose triacetate film dyed with iodine, and has a transmittance of 65% or less at a wavelength of 400 nm. The polarizing plate with a retardation layer of the present invention includes the polarizing plate described above, and the retardation layer disposed on the opposite side of the polarizing plate from the visual recognition side. Re (550) of the retardation layer is 100-190 nm, re (450)/Re (550) is 0.8-1, and the angle between the slow axis of the retardation layer and the absorption axis of the polarizing film of the polarizing plate is 40-50 degrees.
Description
Technical Field
The present invention relates to a dyed cellulose triacetate film, a polarizing plate using the same, a method for producing a polarizing plate, a polarizing plate with a retardation layer, an image display device, and a method for adjusting an image of an image display device.
Background
In recent years, image display devices typified by liquid crystal display devices and Electroluminescent (EL) display devices (for example, organic EL display devices and inorganic EL display devices) have been rapidly spreading. In the image display device, a polarizing plate and a phase difference plate are typically used. In practical use, a polarizing plate with a retardation layer obtained by integrating a polarizing plate and a retardation plate is widely used (for example, patent document 1), but recently, as the desire for thinning of an image display device has been increasing, thinning of a polarizing plate and a polarizing plate with a retardation layer has also been strongly desired. One of the means for thinning the polarizing plate and the polarizing plate with the retardation layer is thinning of the polarizing film. However, when a polarizing plate including a thin polarizing film or a polarizing plate with a retardation layer is used for an image display device, there is a problem that the reflected color becomes blue.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 3325560
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above-described conventional problems, and a main object of the present invention is to provide a polarizing plate and a polarizing plate with a retardation layer capable of realizing a neutral reflection hue when applied to an image display device, and a dyed cellulose triacetate film capable of realizing such a polarizing plate and a polarizing plate with a retardation layer.
Solution for solving the problem
The dyed cellulose triacetate film according to the embodiment of the invention is dyed with iodine, and has a transmittance at a wavelength of 400nm of 65% or less and a transmittance Y corrected for visibility of 80% or more.
According to other aspects of the present invention, there is provided a polarizing plate. The polarizing plate includes a polarizing film and a protective layer disposed on at least one side of the polarizing film. The thickness of the polarizing film is 8 μm or less, and the protective layer is composed of the above-mentioned dyed cellulose triacetate film.
According to another aspect of the present invention, there is provided a method for manufacturing the above polarizing plate. The manufacturing method comprises the following steps: forming a polyvinyl alcohol resin layer on one side of a long thermoplastic resin substrate to form a laminate; dyeing and stretching the laminate to form a polarizing film from the polyvinyl alcohol resin layer; dyeing the cellulose triacetate film with iodine so that the transmittance at a wavelength of 400nm is 65% or less and so that the transmittance Y subjected to visibility correction is 80% or more; and bonding the dyed cellulose triacetate film to the polarizing film.
In one embodiment, the dyeing comprises: the cellulose triacetate film is immersed in an aqueous iodine solution having an iodine concentration of 0.1 wt% or more.
According to still another aspect of the present invention, there is provided a polarizing plate with a retardation layer. The polarizing plate with a retardation layer includes the polarizing plate described above, and a retardation layer disposed on the opposite side of the polarizing plate from the visual recognition side. Re (550) of the retardation layer is 100-190 nm, re (450)/Re (550) is 0.8-1, and the angle between the slow axis of the retardation layer and the absorption axis of the polarizing film of the polarizing plate is 40-50 degrees.
In one embodiment, the retardation layer is made of a polycarbonate resin film.
In one embodiment, the polarizing plate with a retardation layer further includes a different retardation layer on the outer side of the retardation layer, and the refractive index characteristics of the different retardation layer show a relationship of nz > nx=ny.
In one embodiment, the polarizing plate with the retardation layer is a long-strip polarizing plate, the polarizing film has an absorption axis along a long-strip direction, and the retardation layer is an obliquely stretched film having a slow axis in a direction at an angle of 40 ° to 50 ° with respect to the long-strip direction. In one embodiment, the polarizing plate with a retardation layer may be wound into a roll.
Another embodiment of the present invention provides a polarizing plate with a retardation layer, including the polarizing plate described above, and a retardation layer disposed on a side of the polarizing plate opposite to a visual recognition side. The retardation layer has a laminated structure of an alignment cured layer of a first liquid crystal compound and an alignment cured layer of a second liquid crystal compound. The Re (550) of the orientation curing layer of the first liquid crystal compound is 200-300 nm, and the angle formed by the slow axis and the absorption axis of the polarizing film is 10-20 degrees; the Re (550) of the orientation-cured layer of the second liquid crystal compound is 100-190 nm, and the angle between the slow axis and the absorption axis of the polarizing film is 70-80 degrees.
In one embodiment, the polarizing plate with a retardation layer further includes a conductive layer or an isotropic substrate with a conductive layer on the outer side of the retardation layer.
According to still another aspect of the present invention, there is provided an image display apparatus. The image display device includes the polarizing plate or the polarizing plate with a retardation layer.
In one embodiment, the image display device is an organic electroluminescent display device or an inorganic electroluminescent display device.
According to still another aspect of the present invention, there is provided an image adjustment method of an image display apparatus. The method comprises the following steps: the polarizing plate or the polarizing plate with the retardation layer is attached to the visual recognition side of the image display unit so that the reflection hue is nearly neutral.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polarizing plate capable of realizing a neutral reflection hue and a polarizing plate with a retardation layer when applied to an image display device can be realized by using a cellulose triacetate film which has a predetermined transmittance at a predetermined wavelength and a predetermined transmittance Y subjected to visibility correction and is dyed with iodine as a protective layer of the polarizing film.
Drawings
Fig. 1 is a schematic diagram showing an example of a drying shrinkage process using a heating roller in a method for producing a polarizing film used in a polarizing plate or a polarizing plate with a retardation layer according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
(definition of terms and symbols)
The definitions of terms and symbols in the present specification are as follows.
(1) Refractive index (nx, ny, nz)
"nx" is a refractive index in a direction in which the refractive index in the plane reaches the maximum (i.e., the slow axis direction), "ny" is a refractive index in a direction orthogonal to the slow axis in the plane (i.e., the fast axis direction), and "nz" is a refractive index in the thickness direction.
(2) In-plane phase difference (Re)
"Re (λ)" is the in-plane retardation measured at 23℃using light of wavelength λnm. For example, "Re (550)" is the in-plane retardation measured at 23℃with light having a wavelength of 550 nm. When the thickness of the layer (thin film) is denoted as d (nm), re (λ) is obtained by the formula Re (λ) = (nx-ny) ×d.
(3) Retardation in thickness direction (Rth)
"Rth (λ)" is a phase difference in the thickness direction measured at 23℃using light having a wavelength of λnm. For example, "Rth (550)" is a phase difference in the thickness direction measured at 23 ℃ with light having a wavelength of 550 nm. When the thickness of the layer (thin film) is denoted as d (nm), rth (λ) is obtained by the formula Rth (λ) = (nx-nz) ×d.
(4) Nz coefficient
The Nz coefficient was obtained by nz=rth/Re.
(5) Angle of
When referring to an angle in this specification, the angle includes both clockwise and counterclockwise with respect to a reference direction. Thus, for example, "45" means ± 45 °.
A. Polarizing plate
According to an embodiment of the present invention, a cellulose Triacetate (TAC) film dyed with iodine is provided. The dyed TAC film has a transmittance of 65% or less at a wavelength of 400nm, and a transmittance Y (hereinafter, also referred to as Y-value transmittance) subjected to visibility correction of 80% or more. The dyed TAC film can be suitably used for a protective layer of a polarizing plate. The polarizing plate according to an embodiment of the present invention includes a polarizing film and a protective layer disposed on at least one side of the polarizing film. That is, the protective layer may be provided on both sides of the polarizing film, may be provided only on the visual recognition side of the polarizing film, and may be provided only on the opposite side of the polarizing film from the visual recognition side. In an embodiment of the invention, at least one protective layer consists of a dyed TAC film. According to one embodiment, in a polarizing plate having a constitution of a visual recognition side protective layer/polarizing film, the visual recognition side protective layer is constituted by a dyed TAC film.
A-1 polarizing film
Typically, the polarizing film is composed of a polyvinyl alcohol (PVA) resin film containing iodine. Typically, the thickness of the polarizing film is 8 μm or less, preferably 7 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. In one embodiment, the lower limit of the thickness of the polarizing film may be 1 μm, and in another embodiment, the lower limit of the thickness of the polarizing film may be 2 μm.
The polarizing film preferably exhibits absorption dichroism at any wavelength of 380nm to 780 nm. The monomer transmittance of the polarizing film is preferably 42.0% or more, more preferably 42.5% or more, and even more preferably 43.0% or more. On the other hand, the monomer transmittance is preferably 47.0% or less, more preferably 46.0% or less. The polarization degree of the polarizing film is preferably 99.95% or more, more preferably 99.99% or more. On the other hand, the degree of polarization is preferably 99.998% or less. As described above, the polarizing film used in the embodiment of the present invention can achieve both high monomer transmittance and high polarization. Typically, the above-mentioned monomer transmittance is a Y value obtained by measurement with an ultraviolet-visible spectrophotometer and visibility correction. The monomer transmittance is a value obtained by converting the refractive index of one surface of the polarizing plate to 1.50 and converting the refractive index of the other surface to 1.53. Typically, the polarization degree is determined by the following equation based on the parallel transmittance Tp and the orthogonal transmittance Tc obtained by measuring with an ultraviolet-visible spectrophotometer and performing visibility correction.
Polarization (%) = { (Tp-Tc)/(tp+tc) } 1/2 ×100
In one embodiment, the transmittance of a thin polarizing film of 8 μm or less is typically measured by using an ultraviolet-visible spectrophotometer with a laminate of a polarizing film (refractive index of surface: 1.53) and a protective film (refractive index: 1.50) as the measurement target. The reflectance at the interface of each layer may vary depending on the refractive index of the surface of the polarizing film and/or the refractive index of the surface of the protective film in contact with the air interface, and as a result, the measured value of the transmittance may vary. Therefore, when a protective film having a refractive index other than 1.50 is used, for example, the measured value of the transmittance can be corrected based on the refractive index of the surface of the protective film that is in contact with the air interface. Specifically, the correction value C of the transmittance uses the reflectance R of the polarized light parallel to the transmission axis at the interface of the protective film and the air layer 1 (transmission axis reflectivity) and is expressed by the following formula.
C＝R 1 -R 0
R 0 ＝((1.50-1) 2 /(1.50+1) 2 )×(T 1 /100)
R 1 ＝((n 1 -1) 2 /(n 1 +1) 2 )×(T 1 /100)
Here, R is 0 Is the transmission axis reflectivity when a protective film with a refractive index of 1.50 is used, n 1 For use inRefractive index, T of the protective film of (2) 1 Is the transmittance of the polarizing film. For example, when a base material having a surface refractive index of 1.53 (cycloolefin film, hard-coated film, or the like) is used as the protective film, the correction amount C becomes about 0.2%. In this case, by adding 0.2% to the transmittance obtained by measurement, the polarizing film having a refractive index of 1.53 on the surface can be converted into a transmittance when a protective film having a refractive index of 1.50 is used. The transmittance T of the polarizing film was calculated based on the above formula 1 The amount of change of the correction value C at 2% change is 0.03% or less, and the influence of the transmittance of the polarizing film on the value of the correction value C is limited. In addition, when the protective film has absorption other than surface reflection, appropriate correction can be performed according to the absorption amount.
The polarizing film may be formed using a single resin film, or may be formed using a laminate of two or more layers.
Specific examples of the polarizing film obtained by using the laminate include a polarizing film obtained by using a laminate of a resin base material and a PVA-based resin layer formed on the resin base material. A polarizing film obtained by using a laminate of a resin base material and a PVA-based resin layer formed on the resin base material can be produced, for example, by the following operations: coating a PVA-based resin solution on a resin substrate and drying the same to form a PVA-based resin layer on the resin substrate, thereby obtaining a laminate of the resin substrate and the PVA-based resin layer; the laminate was stretched and dyed, and the PVA-based resin layer was formed into a polarizing film. In this embodiment, stretching typically includes immersing the laminate in an aqueous boric acid solution and stretching. Further, the stretching may further include, as needed: prior to stretching in the aqueous boric acid solution, the laminate is air-stretched at a high temperature (e.g., 95 ℃ or higher).
More specifically, the method for producing the polarizing film includes the steps of: forming a polyvinyl alcohol resin layer containing a halide and a polyvinyl alcohol resin on one side of a long thermoplastic resin substrate to form a laminate; and sequentially performing an air-assisted stretching treatment, a dyeing treatment, an in-water stretching treatment, and a drying shrinkage treatment for shrinking the laminate by 2% or more in the width direction by heating while carrying the laminate along the longitudinal direction. Thus, a polarizing film having a thickness of 8 μm or less and excellent optical characteristics can be provided. That is, even when PVA is coated on a thermoplastic resin by introducing auxiliary stretching, crystallinity of PVA can be improved, and high optical characteristics can be achieved. Further, by increasing the orientation of PVA in advance, problems such as decrease in orientation and dissolution of PVA can be prevented when immersed in water in the subsequent dyeing step and stretching step, and high optical characteristics can be achieved. Further, when the PVA-based resin layer is immersed in a liquid, disturbance of alignment and decrease of alignment properties of polyvinyl alcohol molecules can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This can improve the optical characteristics of the polarizing film obtained by the treatment step of immersing the laminate in a liquid, such as dyeing treatment or stretching treatment in water. Further, the optical characteristics can be improved by shrinking the laminate in the width direction by the drying shrinkage treatment. Details of the method of producing the polarizing film are described later in item B.
A-2 protective layer
As described above, in the embodiment of the present invention, at least one of the protective layer disposed on the visual recognition side (hereinafter referred to as a visual recognition side protective layer) and the protective layer disposed on the side opposite to the visual recognition side (hereinafter referred to as an inner protective layer) is constituted by the dyed TAC film. Since the inner protective layer is preferably omitted from the viewpoint of thickness reduction and weight reduction of the polarizing plate, according to one embodiment, in the polarizing plate having a constitution of the visual recognition side protective layer/polarizing film, the visual recognition side protective layer is constituted by a dyed TAC film. By using a dyed TAC film for the visual recognition side protective layer and/or the inner protective layer, even when a thin (for example, a thickness of 8 μm or less) polarizing film is used, bluing of the reflection hue of the image display device can be prevented, and as a result, a very excellent (neutral) reflection hue can be realized.
In the case where the visual recognition side protective layer and the inner protective layer are disposed and only one of them is constituted by a dyed TAC film, the other protective layer is formed of an arbitrary and appropriate film that can be used as a protective layer of a polarizing film. Specific examples of the material that is the main component of the film include cellulose resins such as Triacetylcellulose (TAC), transparent resins such as polyester resins, polyvinyl alcohol resins, polycarbonate resins, polyamide resins, polyimide resins, polyethersulfone resins, polysulfone resins, polystyrene resins, polynorbornene resins, polyolefin resins, (meth) acrylic resins, and acetate resins. Further, a thermosetting resin such as a (meth) acrylic resin, a urethane resin, a (meth) acrylic urethane resin, an epoxy resin, or a silicone resin, an ultraviolet curable resin, or the like can be mentioned. In addition, for example, a vitreous polymer such as a silicone polymer can be used. In addition, a polymer film described in Japanese patent application laid-open No. 2001-343529 (WO 01/37007) can also be used. As a material of the film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in a side chain and a thermoplastic resin having a nitrile group and a substituted or unsubstituted phenyl group in a side chain, for example, a resin composition having an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer can be used. The polymer film may be, for example, an extrusion molded product of the above-mentioned resin composition.
The transmittance of the dyed TAC film at a wavelength of 400nm is 65% or less, preferably 60% or less, more preferably 55% or less, further preferably 40% or less, particularly preferably 35% or less. The lower limit of the transmittance may be, for example, 0.1%. If the transmittance is in such a range, the reflected color phase can be made more excellent. The Y-value transmittance of the dyed TAC film is 80% or more, preferably 85% or more, and more preferably 90% or more. The higher the Y-value transmittance, the more preferable. The upper limit of the transmittance of the Y value may be, for example, 98%. The transmittance at the wavelength of 400nm is remarkably reduced, and on the other hand, the ability to maintain a high value of the Y-value transmittance is one feature of the dyed TAC film.
It is assumed that the above-described effects achieved by such a dyed TAC film are due to the following mechanism: the iodine content (absolute amount) of the thin polarizing film is small. The invention is thatThe polarizing film used in the embodiment(s) of (a) is produced by the method described in item B below, so that PVA-I contributing to visible light absorption can be obtained even if the iodine content (absolute amount) is small 5 - Complex and PVA-I 3 - Source of complex I 5 - Ion and I 3 - The total amount of ions is maintained to a desired range, and therefore, the monomer transmittance and the polarization degree can be maintained at a high level despite being thin. However, the light absorption of the thin polarizing film at a short wavelength (for example, 400nm or less) tends to be small due to the small iodine content (absolute amount). According to an embodiment of the present invention, by using a dyed TAC film as the protective layer, the protective layer can absorb short wavelength light. As a result, the entire polarizing plate can sufficiently absorb short-wavelength light, and the short-wavelength absorbability of the thin polarizing film can be filled. As a result, the reflection color of the image display device can be prevented from bluing while maintaining the excellent characteristics of the thin polarizing film used in the embodiment of the present invention, and as a result, a very excellent (neutral) reflection color can be realized. Further, if iodine is excessively contained in the thin polarizing film, a PVA-iodine complex is formed, and therefore, the Y-value transmittance is also reduced. On the other hand, in the TAC film, iodine does not undergo complexation, and therefore, absorption of iodine is limited to a short wavelength, and transmittance at a short wavelength can be suppressed while maintaining transmittance at a Y value.
The surface treatment such as hard coating treatment, antireflection treatment, anti-blocking treatment, and antiglare treatment may be applied to the visual recognition side protective layer as needed. And/or, if necessary, the visual recognition side protective layer may be subjected to a treatment (typically, an (elliptical) polarization function is given, and an ultra-high phase difference is given) for improving the visual recognition property when visually recognizing through polarized sunglasses. By performing such a treatment, even when the display screen is visually recognized through a polarized lens such as polarized sunglasses, excellent visual recognition can be achieved. Therefore, the polarizing plate or the polarizing plate with the retardation layer can be suitably applied to an image display device that can be used outdoors.
The thickness of the visual recognition side protective layer is preferably 5 μm to 80 μm, more preferably 10 μm to 40 μm, still more preferably 10 μm to 35 μm. When the surface treatment is performed, the thickness of the visual recognition side protective layer is a thickness including the thickness of the surface treatment layer.
In one embodiment, the inner protective layer is preferably optically isotropic. In the present specification, "optically isotropic" means: the in-plane retardation Re (550) is 0nm to 10nm, and the retardation Rth (550) in the thickness direction is-10 nm to +10nm. In one embodiment, the inner protective layer may be a phase difference layer having an arbitrary and appropriate phase difference value. In this case, the in-plane retardation Re (550) of the retardation layer is, for example, 110nm to 150nm. The thickness of the inner protective layer is preferably 5 μm to 80 μm, more preferably 10 μm to 40 μm, still more preferably 10 μm to 30 μm. As described above, the inner protective layer is preferably omitted from the viewpoint of thickness reduction and weight reduction.
B. Method for manufacturing polarizing plate
B-1 polarizing film production method
The polarizing film can be produced, for example, by a method comprising the steps of: forming a polyvinyl alcohol resin layer (PVA resin layer) containing a halide and a polyvinyl alcohol resin (PVA resin) on one side of a long thermoplastic resin substrate to form a laminate; and sequentially performing an air-assisted stretching treatment, a dyeing treatment, an in-water stretching treatment, and a drying shrinkage treatment for shrinking the laminate by 2% or more in the width direction by heating while carrying along the longitudinal direction. The content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA-based resin. The drying shrinkage treatment is preferably performed using a heated roller, and the temperature of the heated roller is preferably 60 to 120 ℃. The shrinkage in the width direction of the laminate by the drying shrinkage treatment is preferably 2% or more. According to this production method, the polarizing film described in the above item A-1 can be obtained. In particular, a laminate including a PVA-based resin layer containing a halide is produced, and stretching of the laminate is performed in multiple stages including air-assisted stretching and in-water stretching, and the stretched laminate is heated by a heating roller, whereby a polarizing film having excellent optical characteristics (typically, a monomer transmittance and an absorbance) can be obtained.
B-1-1. Preparation of laminate
As a method for producing a laminate of the thermoplastic resin base material and the PVA-based resin layer, any suitable method can be used. Preferably, it is: the PVA-based resin layer is formed on the thermoplastic resin substrate by coating a coating liquid containing a halide and a PVA-based resin on the surface of the thermoplastic resin substrate and drying. As described above, the content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA-based resin.
As a coating method of the coating liquid, any suitable method can be used. Examples thereof include roll coating, spin coating, bar coating, dip coating, die coating, curtain coating, spray coating, knife coating (comma coating, etc.), and the like. The coating/drying temperature of the coating liquid is preferably 50℃or higher.
The thickness of the PVA based resin layer is preferably 3 to 40. Mu.m, more preferably 3 to 20. Mu.m.
Before forming the PVA-based resin layer, the thermoplastic resin substrate may be subjected to a surface treatment (for example, corona treatment or the like), or an easy-to-adhere layer may be formed on the thermoplastic resin substrate. By performing such a treatment, the adhesion between the thermoplastic resin base material and the PVA-based resin layer can be improved.
B-1-1-1. Thermoplastic resin substrate
As the thermoplastic resin base material, any suitable thermoplastic resin film can be used. Details of the thermoplastic resin base material are described in, for example, japanese patent application laid-open No. 2012-73580 or japanese patent No. 6470455. The entire disclosures of these publications are incorporated by reference into the present specification.
B-1-1-2. Coating solution
As described above, the coating liquid contains the halide and the PVA-based resin. Typically, the coating liquid is a solution obtained by dissolving the halide and the PVA-based resin in a solvent. Examples of the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various diols, polyols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These may be used singly or in combination of two or more. Among these, water is preferable. The PVA-based resin concentration of the solution is preferably 3 to 20 parts by weight relative to 100 parts by weight of the solvent. If the resin concentration is such, a uniform coating film can be formed which adheres to the thermoplastic resin substrate. The content of the halide in the coating liquid is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin.
Additives may be compounded into the coating liquid. Examples of the additive include plasticizers and surfactants. Examples of the plasticizer include polyols such as ethylene glycol and glycerin. Examples of the surfactant include nonionic surfactants. They can be used for the purpose of further improving the uniformity, dyeing property, stretchability of the resulting PVA-based resin layer.
As the PVA-based resin, any suitable resin may be used. Details of PVA-based resins are described in, for example, japanese patent application laid-open No. 2012-73580 or japanese patent No. 6470455 (above).
Any suitable halide may be used as the halide. Examples thereof include iodide and sodium chloride. Examples of the iodide include potassium iodide, sodium iodide, and lithium iodide. Among these, potassium iodide is preferable.
The amount of the halide in the coating liquid is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA-based resin, and more preferably 10 to 15 parts by weight relative to 100 parts by weight of the PVA-based resin. If the amount of the halide exceeds 20 parts by weight relative to 100 parts by weight of the PVA-based resin, the halide may ooze out, and the finally obtained polarizing film may be clouded.
Generally, the orientation of the polyvinyl alcohol molecules in the PVA-based resin is increased by stretching the PVA-based resin layer, but when the PVA-based resin layer after stretching is immersed in a liquid containing water, the orientation of the polyvinyl alcohol molecules may be disturbed, and the orientation may be reduced. In particular, when a laminate of a thermoplastic resin substrate and a PVA-based resin layer is stretched in boric acid water, the degree of orientation tends to be significantly reduced when the laminate is stretched in boric acid water at a relatively high temperature in order to stably stretch the thermoplastic resin substrate. For example, stretching of a PVA film alone in boric acid water is usually performed at 60 ℃, whereas stretching of a laminate of a-PET (thermoplastic resin base material) and a PVA-based resin layer is performed at a high temperature of about 70 ℃, and in this case, the orientation of PVA at the initial stage of stretching may be reduced in a stage before the stretching in water is increased. In contrast, by producing a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin substrate and stretching the laminate in boric acid water at a high temperature in air (auxiliary stretching), crystallization of the PVA-based resin in the PVA-based resin layer of the laminate after the auxiliary stretching can be promoted. As a result, when the PVA-based resin layer is immersed in a liquid, disorder of alignment and decrease of alignment of polyvinyl alcohol molecules can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This can improve the optical characteristics of the polarizing film obtained by the treatment step of immersing the laminate in a liquid, such as dyeing treatment or stretching treatment in water.
B-1-2 air assisted stretching treatment
In particular, in order to obtain high optical characteristics, a two-stage stretching method in which dry stretching (auxiliary stretching) and stretching in boric acid water are combined is selected. By introducing the auxiliary stretching as in the two-stage stretching, the stretching can be performed while suppressing the crystallization of the thermoplastic resin base material, and the problem of the decrease in stretchability due to the excessive crystallization of the thermoplastic resin base material in the subsequent stretching in boric acid water can be solved, whereby the laminate can be stretched to a higher magnification. Further, when the PVA-based resin is coated on the thermoplastic resin substrate, in order to suppress the influence of the glass transition temperature of the thermoplastic resin substrate, it is necessary to lower the coating temperature as compared with the case of coating the PVA-based resin on a usual metal drum, and as a result, there is a possibility that crystallization of the PVA-based resin is relatively low and sufficient optical characteristics are not obtained. In contrast, by introducing the auxiliary stretching, even when the PVA-based resin is coated on the thermoplastic resin, crystallinity of the PVA-based resin can be improved, and high optical characteristics can be achieved. Further, by increasing the orientation of the PVA-based resin in advance, it is possible to prevent problems such as a decrease in orientation and dissolution of the PVA-based resin when immersed in water in the subsequent dyeing step and stretching step, and to realize high optical characteristics.
The stretching method of the air-assisted stretching may be fixed-end stretching (for example, stretching using a tenter), or free-end stretching (for example, uniaxial stretching by passing a laminate between rolls having different peripheral speeds), and free-end stretching may be positively employed in order to obtain high optical characteristics. In one embodiment, the air stretching process comprises: and a heated roll stretching step of stretching the laminate by using a peripheral speed difference between heated rolls while conveying the laminate along the longitudinal direction thereof. Typically, the air stretching process includes a zone stretching process and a heated roll stretching process. The order of the region stretching step and the heat roller stretching step is not limited, and the region stretching step may be performed first, or the heat roller stretching step may be performed first. The region stretching step may be omitted. In one embodiment, the zone stretching process and the heated roll stretching process are sequentially performed. In other embodiments, stretching is performed by holding the film ends in a tenter and expanding the distance between the tenters in the flow direction (the expansion of the distance between the tenters becomes the stretch ratio). At this time, the distance of the tenter in the width direction (the direction perpendicular to the flow direction) is set to be arbitrarily close. Preferably, it is: the stretching ratio in the flow direction is set so as to be closer to the free end stretching. In the case of free end stretching, the shrinkage in the width direction= (1/stretch ratio) 1/2 To calculate.
The air-assisted stretching may be performed in one stage or in a plurality of stages. When the stretching ratio is performed in a plurality of stages, the stretching ratio is a product of the stretching ratios of the respective stages. The stretching direction in the air-assisted stretching is preferably substantially the same as the stretching direction in the water stretching.
The stretching ratio in the air-assisted stretching is preferably 2.0 to 3.5 times. The maximum stretching ratio when the air-assist stretching and the in-water stretching are combined is preferably 5.0 times or more, more preferably 5.5 times or more, and still more preferably 6.0 times or more, relative to the original length of the laminate. In the present specification, "maximum stretch ratio" means a stretch ratio immediately before breaking of the laminate, and means: the stretch ratio at which the laminate breaks was also confirmed to be 0.2 less than this value.
The stretching temperature of the air-assisted stretching may be set to any suitable value depending on the material forming the thermoplastic resin base material, the stretching method, and the like. The stretching temperature is preferably not less than the glass transition temperature (Tg) of the thermoplastic resin substrate, more preferably not less than the glass transition temperature (Tg) +10 ℃ of the thermoplastic resin substrate, and particularly preferably not less than tg+15 ℃. On the other hand, the upper limit of the stretching temperature is preferably 170 ℃. By stretching at such a temperature, crystallization of the PVA-based resin can be suppressed from proceeding rapidly, and defects caused by the crystallization (e.g., inhibition of orientation of the PVA-based resin layer by stretching) can be suppressed. The crystallization index of the PVA based resin after the air-assisted stretching is preferably 1.3 to 1.8, more preferably 1.4 to 1.7. The crystallization index of the PVA-based resin can be measured using a fourier transform infrared spectrophotometer and by ATR method. Specifically, measurement was performed using polarized light as measurement light, and 1141cm of the obtained spectrum was used -1 And 1440cm -1 The crystallization index was calculated according to the following formula.
Crystallization index= (I) C /I R )
Wherein, the liquid crystal display device comprises a liquid crystal display device,
I C : 1141cm for incidence of measurement light and measurement -1 Strength of (2)
I R : 1440cm of light is measured and incident thereon -1 Is a strength of (a) is a strength of (b).
B-1-3 insolubilization treatment, dyeing treatment and crosslinking treatment
If necessary, the insolubilization treatment is performed after the air-assisted stretching treatment and before the underwater stretching treatment and dyeing treatment. Typically, the insolubilization treatment is performed by immersing the PVA-based resin layer in an aqueous boric acid solution. Typically, the dyeing treatment is performed by dyeing the PVA-based resin layer with a dichroic substance (typically iodine). If necessary, the crosslinking treatment is performed after the dyeing treatment and before the stretching treatment in water. Typically, the crosslinking treatment is performed by immersing the PVA-based resin layer in an aqueous boric acid solution. Details of the insolubilization treatment, dyeing treatment, and crosslinking treatment are described in, for example, japanese patent application laid-open No. 2012-73580 or japanese patent No. 6470455 (above).
B-1-4 in-water stretching treatment
The stretching treatment in water is performed by immersing the laminate in a stretching bath. According to the in-water stretching treatment, stretching can be performed at a temperature lower than the glass transition temperature (typically, about 80 ℃) of the thermoplastic resin base material and the PVA-based resin layer, and crystallization of the PVA-based resin layer can be suppressed while the stretching can be performed to a high magnification. As a result, a polarizing film having excellent optical characteristics can be produced.
Any suitable method may be used for stretching the laminate. Specifically, the stretching may be performed at a fixed end or at a free end (for example, a method of uniaxially stretching a laminate by passing the laminate between rolls having different peripheral speeds). The free end stretch is preferably selected. Stretching of the laminate may be performed in one stage or may be performed in a plurality of stages. When the stretching is performed in a plurality of stages, the stretching ratio (maximum stretching ratio) of the laminate to be described later is a product of the stretching ratios of the respective stages.
The stretching in water is preferably performed by immersing the laminate in an aqueous boric acid solution (stretching in boric acid water). By using an aqueous boric acid solution as the stretching bath, rigidity that can withstand tension applied at the time of stretching and water-insoluble water resistance can be imparted to the PVA-based resin layer. Specifically, boric acid is capable of generating a tetrahydroxyborate anion in an aqueous solution and crosslinking with the PVA-based resin via hydrogen bonds. As a result, rigidity and water resistance can be imparted to the PVA-based resin layer, and the PVA-based resin layer can be stretched well, so that a polarizing film having excellent optical characteristics can be produced.
The aqueous boric acid solution is preferably obtained by dissolving boric acid and/or a borate in water as a solvent. The boric acid concentration is preferably 1 to 10 parts by weight, more preferably 2.5 to 6 parts by weight, and particularly preferably 3 to 5 parts by weight, relative to 100 parts by weight of water. By setting the boric acid concentration to 1 part by weight or more, dissolution of the PVA-based resin layer can be effectively suppressed, and a polarizing film having higher characteristics can be produced. In addition to boric acid or borate, an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, or the like in a solvent may be used.
Preferably, iodide is added to the stretching bath (boric acid aqueous solution). By adding iodide, elution of iodine adsorbed to the PVA-based resin layer can be suppressed. Specific examples of iodides are described above. The concentration of iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight, relative to 100 parts by weight of water.
The stretching temperature (liquid temperature of the stretching bath) is preferably 40 to 85 ℃, more preferably 60 to 75 ℃. If the temperature is such, the PVA-based resin layer can be stretched to a high magnification while suppressing dissolution. Specifically, as described above, the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60 ℃ or higher, in terms of the relationship with the formation of the PVA-based resin layer. In this case, if the stretching temperature is lower than 40 ℃, there is a possibility that the thermoplastic resin base material may not be stretched satisfactorily even if plasticization by the water is considered. On the other hand, the higher the temperature of the stretching bath is, the higher the solubility of the PVA-based resin layer becomes, and there is a possibility that excellent optical characteristics cannot be obtained. The immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
The stretching ratio based on stretching in water is preferably 1.5 times or more, more preferably 3.0 times or more. The total stretch ratio of the laminate is preferably 5.0 times or more, more preferably 5.5 times or more, relative to the original length of the laminate. By realizing such a high stretching ratio, a polarizing film extremely excellent in optical characteristics can be produced. Such a high stretching ratio can be achieved by employing an in-water stretching method (boric acid in-water stretching).
B-1-5 drying shrinkage treatment
The drying shrinkage treatment may be performed by zone heating in which the entire zone is heated, or may be performed by heating a conveying roller (using a so-called heating roller) (heating roller drying method). Both are preferably used. By drying with the heating roller, the laminate can be effectively prevented from curling by heating, and a polarizing film excellent in appearance can be produced. Specifically, by drying the laminate in a state of being brought along the heating roller, crystallization of the thermoplastic resin base material can be effectively promoted, and the crystallinity can be increased, and even at a low drying temperature, the crystallinity of the thermoplastic resin base material can be satisfactorily increased. As a result, the rigidity of the thermoplastic resin base material increases, and the PVA-based resin layer is allowed to shrink due to drying, so that curling is suppressed. Further, since the laminate can be dried while being maintained in a flat state by using the heating roller, not only the occurrence of curling but also the occurrence of wrinkles can be suppressed. At this time, the laminate is shrunk in the width direction by the drying shrinkage treatment, whereby the optical characteristics can be improved. This is because: the orientation of PVA and PVA/iodine complex can be effectively improved. The shrinkage in the width direction of the laminate by the drying shrinkage treatment is preferably 1% to 10%, more preferably 2% to 8%, and particularly preferably 4% to 6%. By using the heating roller, the laminated body can be continuously contracted in the width direction while being conveyed, and high productivity can be achieved.
Fig. 1 is a schematic diagram showing an example of the drying shrinkage treatment. In the drying shrinkage process, the laminate 200 is dried while being conveyed by conveying rollers R1 to R6 and guide rollers G1 to G4 heated to predetermined temperatures. In the illustrated example, the conveyance rollers R1 to R6 are disposed so as to alternately and continuously heat the surface of the PVA resin layer and the surface of the thermoplastic resin substrate, or the conveyance rollers R1 to R6 may be disposed so as to continuously heat only one surface (for example, the surface of the thermoplastic resin substrate) of the laminate 200, for example.
The drying conditions can be controlled by adjusting the heating temperature of the conveying roller (temperature of the heating roller), the number of heating rollers, the time of contact with the heating roller, and the like. The temperature of the heating roller is preferably 60 to 120 ℃, more preferably 65 to 100 ℃, and particularly preferably 70 to 80 ℃. The crystallinity of the thermoplastic resin can be increased well, curling can be suppressed well, and an optical laminate extremely excellent in durability can be produced. The temperature of the heating roller can be measured by a contact thermometer. In the example shown in the figure, 6 conveying rollers are provided, but there is no particular limitation as long as there are a plurality of conveying rollers. The conveying rollers are usually provided in 2 to 40, preferably 4 to 30. The contact time (total contact time) between the laminate and the heating roller is preferably 1 to 300 seconds, more preferably 1 to 20 seconds, and even more preferably 1 to 10 seconds.
The heating roller may be provided in a heating furnace (for example, an oven) or may be provided in a general production line (in a room temperature environment). Preferably, the air supply device is arranged in a heating furnace provided with an air supply means. By using the drying by the heating roller and the hot air drying in combination, abrupt temperature changes between the heating rollers can be suppressed, and the shrinkage in the width direction can be easily controlled. The temperature of the hot air drying is preferably 30 to 100 ℃. The hot air drying time is preferably 1 to 300 seconds. The wind speed of the hot air is preferably about 10m/s to 30 m/s. The wind speed is the wind speed in the heating furnace, and can be measured by a micro blade type digital anemometer.
B-1-6. Other treatments
The washing treatment is preferably performed after the stretching treatment in water and before the drying shrinkage treatment. Typically, the washing treatment is performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution.
In this way, a laminate of the thermoplastic resin substrate and the polarizing film can be produced.
Dyeing of TAC films
On the other hand, TAC films were dyed with iodine. Dyeing may be performed in any and suitable manner. Dyeing is performed by, for example, immersing an elongated TAC film in a dyeing liquid (typically, an aqueous iodine solution) while carrying it by rollers. The dyeing is performed such that the transmittance of the obtained dyed TAC film at a wavelength of 400nm becomes 65% or less and the transmittance of the Y value becomes 80% or more. The transmittance and the Y-value transmittance can be controlled by appropriately adjusting the iodine concentration of the aqueous iodine solution, the temperature of the aqueous iodine solution, and the dyeing time (dipping time). The iodine concentration of the iodine aqueous solution may vary depending on the dyeing time (dipping time). The iodine concentration of the aqueous iodine solution is preferably 0.1 wt% or more, more preferably 0.5 wt% to 5.0 wt%, and still more preferably 1.0 wt% to 3.0 wt%. If the iodine concentration is too low, the desired transmittance may not be obtained even if the dyeing treatment is performed for a long period of time. The temperature of the aqueous iodine solution is preferably 20 to 30 ℃. The dyeing time may vary depending on the iodine concentration of the aqueous iodine solution. The dyeing time is preferably 30 seconds or more, more preferably 50 seconds to 400 seconds. If the dyeing time is too short, the desired transmittance may not be obtained. On the other hand, if the production efficiency is considered, it is not effective to prolong the dyeing time.
B-3 preparation of polarizing plate
The dyed TAC film obtained in item B-2 is bonded to the polarizing film surface of the laminate of the thermoplastic resin substrate and the polarizing film obtained in item B-1 with an optional and appropriate adhesive. Examples of the adhesive include an aqueous adhesive and an active energy ray-curable adhesive. In this way, a laminate of a thermoplastic resin substrate/a polarizing film/a dyed TAC film can be produced. The laminate can be used as a polarizing plate as it is. In this case, the thermoplastic resin base material can function as an inner protective layer. Alternatively, the thermoplastic resin substrate may be peeled from the laminate of thermoplastic resin substrate/polarizing film/dyed TAC film, and the laminate of dyed TAC film/polarizing film may be used as a polarizing plate. Alternatively, the thermoplastic resin substrate may be peeled from the laminate of thermoplastic resin substrate/polarizing film/dyed TAC film, the resin film may be bonded to the peeled surface as the inner protective layer, and the laminate of dyed TAC film/polarizing film/inner protective layer may be used as the polarizing plate.
C. Polarizing plate with phase difference layer
C-1. Integral Structure of polarizing plate with retardation layer
Fig. 2 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention. The polarizing plate 100 with a retardation layer of the present embodiment includes a polarizing plate 10 and a retardation layer 20. The polarizing plate described in the above items A and B. The polarizing plate 10 of the example of the drawing includes a polarizing film 11, a visual recognition side protective layer 12, and an inner protective layer 13. As described above, the inner protective layer 13 is preferably omitted. In the polarizing plate with the retardation layer, the retardation layer is typically disposed on the opposite side of the polarizing plate from the viewing side.
As shown in fig. 3, the polarizing plate 101 with a retardation layer according to another embodiment may be provided with another retardation layer 50 and/or a conductive layer or an isotropic substrate 60 with a conductive layer. Typically, the other retardation layer 50 and the conductive layer or the isotropic substrate with conductive layer 60 are disposed on the opposite side (opposite side to the visual recognition side) of the retardation layer 20 from the polarizing plate 10. In the other retardation layer, the refractive index characteristics typically show a relationship of nz > nx=ny. Typically, another retardation layer 50 and a conductive layer or an isotropic substrate 60 with a conductive layer are provided in this order from the retardation layer 20 side. Typically, the other retardation layer 50 and the conductive layer or the isotropic substrate with conductive layer 60 are optional layers provided as needed, and either or both may be omitted. For convenience, the phase difference layer 20 may be referred to as a first phase difference layer, and the other phase difference layer 50 may be referred to as a second phase difference layer. In the case of providing a conductive layer or an isotropic substrate with a conductive layer, the polarizing plate with a retardation layer can be applied to a so-called in-cell touch panel type input display device in which a touch sensor is incorporated between an image display unit (for example, an organic EL unit) and the polarizing plate.
In the embodiment of the present invention, re (550) of the first retardation layer 20 is 100nm to 190nm, and Re (450)/Re (550) is 0.8 or more and less than 1. The angle between the slow axis of the first retardation layer 20 and the absorption axis of the polarizing film 11 is 40 ° to 50 °.
The above embodiments may be appropriately combined, and the constituent elements in the above embodiments may be modified as known in the art. For example, the structure of the isotropic base material 60 having the conductive layer provided on the outer side of the second phase difference layer 50 may be replaced with an optically equivalent structure (for example, a laminate of the second phase difference layer and the conductive layer).
The polarizing plate with a retardation layer may further include other retardation layers. The optical characteristics (for example, refractive index characteristics, in-plane retardation, nz coefficient, photoelastic coefficient), thickness, arrangement position, and the like of the other retardation layers can be appropriately set according to the purpose.
The polarizing plate with the retardation layer may be monolithic or elongated. In the present specification, "elongated shape" means an elongated shape having a length sufficiently longer than a width, and includes, for example, an elongated shape having a length 10 times or more, preferably 20 times or more, than a width. The polarizing plate with the retardation layer in the form of a long strip can be rolled up. In the case where the polarizing plate with the retardation layer is long, the polarizing plate and the retardation layer are also long. In this case, the polarizing film preferably has an absorption axis along the longitudinal direction. The first retardation layer is preferably an obliquely stretched film having a slow axis in a direction at an angle of 40 ° to 50 ° with respect to the longitudinal direction. If the polarizing film and the first retardation layer have such a constitution, a polarizing plate with a retardation layer can be manufactured by roll-to-roll.
In practical terms, an adhesive layer (not shown) may be provided on the opposite side of the retardation layer from the polarizing plate, and the polarizing plate with the retardation layer may be attached to the image display unit. Further, it is preferable that a release film is temporarily bonded to the surface of the pressure-sensitive adhesive layer until the polarizing plate with the retardation layer is used. By temporarily attaching the release film, a roll can be formed while protecting the adhesive layer.
The total thickness of the polarizing plate with the retardation layer is preferably 140 μm or less, more preferably 120 μm or less, further preferably 100 μm or less, further preferably 90 μm or less, further preferably 85 μm or less. The lower limit of the total thickness may be 80 μm, for example. According to the embodiment of the present invention, an extremely thin polarizing plate with a retardation layer can be realized in this way. Such a polarizing plate with a retardation layer can have extremely excellent flexibility and bending durability. Such a polarizing plate with a retardation layer can be particularly suitably applied to a curved image display device and/or an image display device capable of being curved or bent. The total thickness of the polarizing plate with the retardation layer is: the total thickness of all layers constituting the polarizing plate with a retardation layer (i.e., the total thickness of the polarizing plate with a retardation layer does not include the thickness of the adhesive layer for attaching the polarizing plate with a retardation layer to an adjacent member such as an image display unit and the thickness of the release film temporarily adhered to the surface thereof) except for the adhesive layer for adhering the polarizing plate with a retardation layer to an external adherend such as a panel, glass, or the like.
Hereinafter, the first retardation layer, the second retardation layer, and the conductive layer or the isotropic substrate with the conductive layer will be specifically described. The first retardation layer may be an alignment cured layer of a liquid crystal compound (hereinafter referred to as a liquid crystal alignment cured layer). The liquid crystal alignment cured layer will be described in item C-4 as a modification of the first retardation layer.
C-2. First phase difference layer
The first retardation layer 20 may have any and appropriate optical and/or mechanical properties depending on the purpose. Typically, the first retardation layer 20 has a slow axis. In one embodiment, as described above, the angle θ between the slow axis of the first retardation layer 20 and the absorption axis of the polarizing film 11 is 40 ° to 50 °, preferably 42 ° to 48 °, and more preferably about 45 °. If the angle θ is in this range, as will be described later, a polarizing plate with a retardation layer having very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics) can be obtained by setting the first retardation layer to a λ/4 plate.
The first retardation layer preferably has refractive index characteristics exhibiting a relationship of nx > ny.gtoreq.nz. Typically, the first retardation layer is provided to impart an antireflection property to the polarizing plate, and in one embodiment, can function as a λ/4 plate. In this case, as described above, the in-plane retardation Re (550) of the first retardation layer is 100nm to 190nm, preferably 110nm to 170nm, and more preferably 130nm to 160nm. Here, "ny=nz" includes not only the case where ny is exactly equal to nz but also the case where ny is substantially equal to nz. Therefore, ny < nz may be present within a range that does not impair the effects of the present invention.
The Nz coefficient of the first retardation layer is preferably 0.9 to 3, more preferably 0.9 to 2.5, still more preferably 0.9 to 1.5, and particularly preferably 0.9 to 1.3. By satisfying such a relationship, when the obtained polarizing plate with a retardation layer is used for an image display device, a very excellent reflection hue can be achieved.
The first phase difference layer may exhibit an inverse wavelength dispersion characteristic in which a phase difference value becomes large according to the wavelength of the measurement light, a positive wavelength dispersion characteristic in which a phase difference value becomes small according to the wavelength of the measurement light, or a flat wavelength dispersion characteristic in which a phase difference value hardly changes according to the wavelength of the measurement light. In one embodiment, the first phase difference layer exhibits inverse wavelength dispersion characteristics. In this case, re (450)/Re (550) of the retardation layer is 0.8 or more and less than 1 as described above, and preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection characteristics can be achieved.
The absolute value of the photoelastic coefficient of the first phase difference layer is preferably 2×10 -11 m 2 N or less, more preferably 2.0X10 -13 m 2 /N～1.5×10 -11 m 2 N, further preferably 1.0X10 -12 m 2 /N～1.2×10 -11 m 2 Resin of/N. If the absolute value of the photoelastic coefficient is in such a range, it is difficult for the phase difference to change when shrinkage stress occurs during heating. As a result, thermal unevenness of the obtained image display device can be prevented well.
Typically, the first retardation layer is formed of a stretched film of a resin film. The thickness of the first retardation layer is preferably 70 μm or less, more preferably 45 μm to 60 μm. If the thickness of the first retardation layer is in such a range, warpage upon heating can be well suppressed, and warpage upon bonding can be well adjusted.
The first retardation layer 20 is made of any appropriate resin film capable of satisfying the above characteristics. Typical examples of such resins include polycarbonate resins, polyester carbonate resins, polyester resins, polyvinyl acetal resins, polyarylate resins, cyclic olefin resins, cellulose resins, polyvinyl alcohol resins, polyamide resins, polyimide resins, polyether resins, polystyrene resins, and acrylic resins. These resins may be used alone or in combination (e.g., blending, copolymerization). In the case where the first retardation layer is formed of a resin film exhibiting inverse wavelength dispersion characteristics, a polycarbonate-based resin or a polyester carbonate-based resin (hereinafter, may be simply referred to as a polycarbonate-based resin) may be suitably used.
As the polycarbonate resin, any suitable polycarbonate resin may be used as long as the effects of the present invention can be obtained. For example, the polycarbonate resin includes: structural units derived from fluorene-based dihydroxy compounds; structural units derived from isosorbide-based dihydroxy compounds; and a structural unit derived from at least one dihydroxy compound selected from the group consisting of alicyclic diol, alicyclic dimethanol, diethylene glycol, triethylene glycol or polyethylene glycol, and alkylene glycol or spiro glycol. The polycarbonate resin preferably comprises: structural units derived from fluorene-based dihydroxy compounds; structural units derived from isosorbide-based dihydroxy compounds; structural units derived from alicyclic dimethanol and/or structural units derived from diethylene glycol, triethylene glycol or polyethylene glycol; further preferably comprises: structural units derived from fluorene-based dihydroxy compounds; structural units derived from isosorbide-based dihydroxy compounds; and structural units derived from diethylene glycol, triethylene glycol or polyethylene glycol. The polycarbonate resin may contain structural units derived from other dihydroxy compounds as needed. Details of the polycarbonate resin that can be suitably used for the first retardation layer and the method of forming the first retardation layer are described in, for example, japanese patent application laid-open publication nos. 2014-10291, 2014-2666, 2015-212816, 2015-212817, and 2015-212818, which are incorporated herein by reference.
C-3 second phase difference layer
As described above, the second phase difference layer may be a so-called positive C plate whose refractive index characteristics show a relationship of nz > nx=ny. By using the positive C plate as the second phase difference layer, reflection in the oblique direction can be satisfactorily prevented, and a wide angle of view of the antireflection function can be achieved. In this case, the retardation Rth (550) in the thickness direction of the second phase difference layer is preferably-50 nm to-300 nm, more preferably-70 nm to-250 nm, still more preferably-90 nm to-200 nm, particularly preferably-100 nm to-180 nm. Here, "nx=ny" includes not only the case where nx and ny are exactly equal but also the case where nx and ny are substantially equal. That is, the in-plane phase difference Re (550) of the second phase difference layer may be less than 10nm.
The second phase difference layer having refractive index characteristics of nz > nx=ny is formed of an arbitrary and appropriate material. The second phase difference layer is preferably formed of a thin film containing a liquid crystal material fixed in a vertical alignment. The liquid crystal material (liquid crystal compound) capable of vertical alignment may be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the method for forming the liquid crystal compound and the retardation layer include those described in [0020] to [0028] of JP-A-2002-333642 and methods for forming the retardation layer. In this case, the thickness of the second phase difference layer is preferably 0.5 μm to 10 μm, more preferably 0.5 μm to 8 μm, and still more preferably 0.5 μm to 5 μm.
C-4 modification of the first phase-difference layer
The first retardation layer 20 may have a laminated structure of a first liquid crystal alignment cured layer and a second liquid crystal alignment cured layer. In this case, either one of the first liquid crystal alignment cured layer and the second liquid crystal alignment cured layer may function as a λ/4 plate, and the other may function as a λ/2 plate. Therefore, the thicknesses of the first liquid crystal alignment cured layer and the second liquid crystal alignment cured layer are adjusted in such a manner that a desired in-plane retardation of the λ/4 plate or the λ/2 plate can be obtained. For example, when the first liquid crystal alignment cured layer functions as a λ/2 plate and the second liquid crystal alignment cured layer functions as a λ/4 plate, the thickness of the first liquid crystal alignment cured layer is, for example, 2.0 μm to 3.0 μm, and the thickness of the second liquid crystal alignment cured layer is, for example, 1.0 μm to 2.0 μm. In this case, the in-plane phase difference Re (550) of the first liquid crystal alignment cured layer is preferably 200nm to 300nm, more preferably 230nm to 290nm, and still more preferably 250nm to 280nm. The in-plane phase difference Re (550) of the second liquid crystal alignment cured layer is preferably 100nm to 190nm, more preferably 110nm to 170nm, and still more preferably 130nm to 160nm. The angle between the slow axis of the first liquid crystal alignment cured layer and the absorption axis of the polarizing film is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and still more preferably about 15 °. The angle between the slow axis of the second liquid crystal alignment cured layer and the absorption axis of the polarizing film is preferably 70 ° to 80 °, more preferably 72 ° to 78 °, and still more preferably about 75 °. With such a configuration, characteristics similar to the ideal inverse wavelength dispersion characteristics can be obtained, and as a result, extremely excellent antireflection characteristics can be realized. Typically, both the first liquid crystal alignment cured layer and the second liquid crystal alignment cured layer exhibit a relationship in which refractive index characteristics are nx > ny=nz. The Nz coefficient of each of the first liquid crystal alignment cured layer and the second liquid crystal alignment cured layer is preferably 0.9 to 1.5, more preferably 0.9 to 1.3. For example, JP-A2006-163343 discloses a method for forming a liquid crystal compound constituting a first liquid crystal alignment cured layer and a second liquid crystal alignment cured layer and a method for forming a first liquid crystal alignment cured layer and a second liquid crystal alignment cured layer. The description of this publication is incorporated by reference into the present specification. In the case where the first phase difference layer has such a laminated structure, the second phase difference layer may be omitted.
C-5 conductive layer or Isotropic substrate with conductive layer
The conductive layer can be formed by forming a metal oxide film on an arbitrary and appropriate substrate by an arbitrary and appropriate film forming method (for example, vacuum evaporation method, sputtering method, CVD method, ion plating method, spray method, or the like). Examples of the metal oxide include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. Among them, indium-tin composite oxide (ITO) is preferable.
In the case where the conductive layer contains a metal oxide, the thickness of the conductive layer is preferably 50nm or less, more preferably 35nm or less. The lower limit of the thickness of the conductive layer is preferably 10nm.
The conductive layer may be transferred from the base material to the first retardation layer (or to the second retardation layer, if present), and may be formed as a separate conductive layer as a constituent layer of the polarizing plate with the retardation layer, or may be laminated on the first retardation layer (or on the second retardation layer, if present) in the form of a laminate with the base material (base material with the conductive layer). The substrate is preferably optically isotropic, and thus the conductive layer can be used as an isotropic substrate with a conductive layer for a polarizing plate with a retardation layer.
As the optically isotropic substrate (isotropic substrate), any suitable isotropic substrate can be used. Examples of the material constituting the isotropic substrate include materials having, as a main skeleton, a resin having no conjugated system such as a norbornene-based resin or an olefin-based resin; and materials having a cyclic structure such as a lactone ring or a glutarimide ring in the main chain of the acrylic resin. When such a material is used, the expression of the retardation associated with the orientation of the molecular chains can be suppressed to be small when an isotropic substrate is formed. The thickness of the isotropic substrate is preferably 50 μm or less, more preferably 35 μm or less. The lower limit of the thickness of the isotropic substrate is, for example, 20 μm.
The conductive layer and/or the conductive layer of the isotropic substrate with conductive layer may be patterned as desired. The conductive portion and the insulating portion are formed by patterning. As a result, an electrode can be formed. The electrode may function as a touch sensor electrode that senses contact with the touch panel. As the patterning method, any and appropriate method may be employed. Specific examples of the patterning method include a wet etching method and a screen printing method.
D. Image display device
The polarizing plate according to item A and item B or the polarizing plate with a retardation layer according to item C may be applied to an image display device. Accordingly, an embodiment of the present invention includes an image display device obtained using such a polarizing plate or a polarizing plate with a retardation layer. As typical examples of the image display device, a liquid crystal display device and an Electroluminescence (EL) display device (for example, an organic EL display device and an inorganic EL display device) are cited. The image display device according to the embodiment of the present invention includes a polarizing plate or a polarizing plate with a retardation layer on the visual recognition side. The polarizing plate with the retardation layer is laminated such that the retardation layer is on the side of the image display unit (e.g., liquid crystal unit, organic EL unit, inorganic EL unit) (such that the polarizing film is on the side of visual recognition). In one embodiment, the image display device has a curved shape (substantially curved display screen), and/or is capable of buckling or bending. By using the polarizing plate or the polarizing plate with a retardation layer as described above, the reflection hue of the image display device can be made nearly neutral. Therefore, according to an embodiment of the present invention, an image adjustment method of such an image display device can also be provided.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The measurement methods of the respective characteristics are as follows. Unless otherwise specifically noted, "parts" and "%" in examples and comparative examples are based on weight.
(1) Thickness of (L)
The thickness of 10 μm or less was measured by an interferometric film thickness meter (product name "MCPD-3000" manufactured by Otsuka electronics Co., ltd.). The thickness exceeding 10 μm was measured using a digital micrometer (manufactured by ANRITSU Co., ltd., product name "KC-351C").
(2) Transmittance of monomer and degree of polarization
The polarizing plates used in examples and comparative examples were measured using an ultraviolet-visible spectrophotometer (V-7100 manufactured by japan spectroscopy), and the resulting single transmittance Ts, parallel transmittance Tp, and orthogonal transmittance Tc were used as Ts, tp, and Tc of the polarizing film, respectively. These Ts, tp, and Tc are Y values obtained by measurement and visibility correction using a 2 degree field of view (C light source) of JIS Z8701. The protective layers of the polarizing plates used in examples and comparative examples had a Hard Coat (HC) layer on the surface, the refractive index of the protective layer was 1.50, and the refractive index of the HC layer was 1.53. The refractive index of the surface of the polarizing film opposite to the protective layer was 1.53.
From the obtained Tp and Tc, the polarization degree P was determined by the following equation.
The polarization degree P (%) = { (Tp-Tc)/(tp+tc) } 1/2 ×100
The spectrophotometer can also perform equivalent measurement using LPF-200 manufactured by Otsuka electronics, inc.
In either case, the transmittance of the protective layer and the transmittance of the polarizing plate are values at which the refractive index of the surface is 1.50/1.53, and when the combination of the refractive indices of the surfaces constituting the protective layer is measured to be different from that, theoretical correction is performed based on the magnitude of the amount of change in the reflection (surface reflection) of the air interface due to the change in the refractive index of the surface. For example, when the TAC/polarizing film with HC layer (transmittance is 40%) is measured, the combination of the surface refractive indices is 1.53/1.53, and therefore, the transmittance of the polarizing plate can be converted to 1.50/1.53 by setting the measured value to +0.2%. Since the combination of refractive indexes is 1.50/1.53, the transmittance of the TAC film monomer with HC layer is not corrected.
(3) Front reflection hue
The polarizing plates with retardation layers obtained in examples and comparative examples were adhered to a reflecting plate (trade name "DMS-X42", manufactured by Toli film Co., ltd.; reflectance was 86%, and reflection hue a under the condition of no polarizing plate) using an acrylic adhesive having no ultraviolet absorbing function * ＝-0.22、b * =0.32), a measurement sample was prepared. At this time, the polarizing plate with the retardation layer is attached so that the retardation layer side of the polarizing plate faces the reflecting plate. The measurement sample was measured by the SCE method using a spectrocolorimeter (CM-2600 d manufactured by KONICA MINOLTA Co., ltd.), and a * And b * Value substitution of- *2 +b *2 ) In (3), the front reflection hue is obtained.
Examples 1 to 1
1. Manufacture of polarizing film
As the thermoplastic resin base material, an amorphous isophthalic acid copolymerized polyethylene terephthalate film (thickness: 100 μm) having a long water absorption of 0.75% and a Tg of about 75℃was used. Corona treatment is performed on one side of the resin base material.
To 100 parts by weight of a PVA-based resin obtained by mixing polyvinyl alcohol (polymerization degree: 4200, saponification degree: 99.2 mol%) and acetoacetyl-modified PVA (trade name "gossifimer Z410" manufactured by japan chemical industries, inc.) at 9:1, 13 parts by weight of potassium iodide was added and dissolved in water to prepare a PVA aqueous solution (coating liquid).
The PVA aqueous solution was applied to the corona treated surface of the resin substrate, and dried at 60 ℃ to form a PVA-based resin layer having a thickness of 13 μm, thereby producing a laminate.
The resulting laminate was uniaxially stretched to 2.4 times along the longitudinal (lengthwise) free end between rolls having different peripheral speeds in an oven at 130 c (air-assisted stretching treatment).
Next, the laminate was immersed in an insolubilization bath (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (insolubilization treatment).
Next, the film was immersed in a dyeing bath (aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ℃ for 60 seconds while adjusting the concentration so that the monomer transmittance (Ts) of the finally obtained polarizing film became a desired value (dyeing treatment).
Then, the resultant solution was immersed in a crosslinking bath (aqueous boric acid solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40℃for 30 seconds (crosslinking treatment).
Thereafter, the laminate was immersed in an aqueous solution (boric acid concentration: 4.0 wt% and potassium iodide: 5.0 wt%) at a liquid temperature of 70 ℃ and uniaxially stretched (in-water stretching treatment) between rolls having different peripheral speeds so that the total stretching ratio in the machine direction (longitudinal direction) became 5.5 times.
Thereafter, the laminate was immersed in a washing bath (aqueous solution obtained by mixing 100 parts by weight of water with 4 parts by weight of potassium iodide) at a liquid temperature of 20 ℃.
Thereafter, drying was performed in an oven maintained at 90 ℃ while being in contact with a SUS heated roller maintained at a surface temperature of 75 ℃ for about 2 seconds (drying shrinkage treatment). The shrinkage in the width direction of the laminate based on the drying shrinkage treatment was 5.2%.
In this way, a polarizing film having a thickness of 5 μm was formed on the resin substrate.
Dyeing of TAC films
HC-TAC film having a HC layer of 7 μm thickness and a refractive index of 1.53 formed on a long TAC film (trade name "KC-2UA", manufactured by KONICA MINOLTA Co., ltd.) was immersed in a dyeing bath (iodine aqueous solution of 1.0 wt% iodine concentration) at a liquid temperature of 25℃while being transported by a roller. The immersion time was 60 seconds. The resultant dyed TAC film had a transmittance of 59.8% at a wavelength of 400nm and a transmittance Y value of 90.1%.
3. Manufacture of polarizing plate
The dyed TAC film with HC layer obtained in 2) above was adhered to the surface (the surface opposite to the resin substrate) of the polarizing film obtained in 1) above via an ultraviolet-curable adhesive. Specifically, the cured adhesive was applied so that the total thickness of the cured adhesive became 1.0 μm, and the cured adhesive was bonded by using a roll press. Thereafter, UV light is irradiated from the TAC film side to cure the adhesive. Then, the resin base material was peeled off after cutting the both end portions, to obtain a polarizing plate in the form of a long strip (width: 1300 mm) having a configuration of a protective layer (dyed TAC film)/adhesive layer/polarizing film. The single body transmittance of the polarizing plate (substantially polarizing film) was 43.0%, and the polarization degree was 99.995%.
4. Production of retardation film constituting retardation layer
4-1 polymerization of polyester carbonate resin
The polymerization was carried out using a batch polymerization apparatus comprising two vertical reactors, having stirring blades and a reflux condenser controlled to 100 ℃. Adding bis [9- (2-phenoxycarbonylethyl) fluoren-9-yl]29.60 parts by mass (0.046 mol) of methane, 29.21 parts by mass (0.200 mol) of Isosorbide (ISB), 42.28 parts by mass (0.139 mol) of Spiroglycol (SPG), 63.77 parts by mass (0.298 mol) of diphenyl carbonate (DPC) and 1.19X10 of calcium acetate monohydrate as a catalyst -2 Parts by mass (6.78X10) -5 mol). After the reduced pressure nitrogen gas was replaced in the reactor, the reactor was heated by a heat medium, and stirring was started at the time when the internal temperature reached 100 ℃. After 40 minutes from the start of the temperature increase, the internal temperature was controlled to 220℃and the pressure was reduced so as to maintain the temperature, and after reaching 220℃it took 90 minutes to reach 13.3kPa. The phenol vapor by-produced during the polymerization reaction was introduced into a reflux condenser at 100 ℃, a certain amount of monomer components contained in the phenol vapor was returned to the reactor, and uncondensed phenol vapor was introduced into a condenser at 45 ℃ and recovered. After nitrogen gas was introduced into the first reactor and the pressure was once returned to the atmospheric pressure, the oligomerization reaction liquid in the first reactor was transferred to the second reactor. Then, the temperature rise and the pressure reduction in the second reactor were started, and it took 50 minutes to set the internal temperature to 240℃and the pressure to 0.2kPa. Thereafter, polymerization is performed until a predetermined stirring power is reached. At the time of reaching the predetermined power, nitrogen gas was introduced into the reactor to restore the pressure, the polyester carbonate resin produced was extruded into water, and the strands were cut to obtain pellets.
4-2 preparation of retardation film
After the obtained polyester-carbonate resin (pellet) was dried under vacuum at 80℃for 5 hours, a long resin film having a thickness of 135 μm was produced by using a film-forming apparatus comprising a single screw extruder (manufactured by Toshiba machinery Co., ltd., cylinder set temperature: 250 ℃), T die (width: 200mm, set temperature: 250 ℃), cooling roll (set temperature: 120 to 130 ℃) and a winder. The obtained long resin film was stretched at a stretching temperature of 133℃and a stretching ratio of 2.8 times in the width direction to obtain a retardation film having a thickness of 48. Mu.m. The Re (550) of the obtained retardation film was 144nm, re (450)/Re (550) was 0.82, and the nz coefficient was 1.12.
5. Manufacturing of polarizing plate with phase difference layer
The retardation film obtained in the above 4 was adhered to the polarizing film surface of the polarizing plate obtained in the above 3 via an acrylic adhesive (thickness: 5 μm). At this time, the film was bonded so that the absorption axis of the polarizing film and the slow axis of the retardation film form an angle of 45 °. In this way, a polarizing plate with a retardation layer having a structure of a protective layer, an adhesive layer, a polarizing film, an adhesive layer, and a retardation layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 84. Mu.m. The obtained polarizing plate with a retardation layer was subjected to the evaluation of (3) above. The results are shown in Table 1.
Examples 1 to 2
A TAC film was dyed in the same manner as in example 1-1 except that the dyeing time was set to 120 seconds. The resultant dyed TAC film had a transmittance of 52.8% at a wavelength of 400nm and a transmittance Y value of 89.2%. A polarizing plate with a retardation layer was produced in the same manner as in example 1-1, except that the dyed TAC film was used. The obtained polarizing plate with the retardation layer was subjected to the same evaluation as in example 1-1. The results are shown in Table 1.
Examples 1 to 3
A TAC film was dyed in the same manner as in example 1-1 except that the dyeing time was set to 300 seconds. The resultant dyed TAC film had a transmittance of 31.9% at a wavelength of 400nm and a transmittance Y value of 88.4%. A polarizing plate with a retardation layer was produced in the same manner as in example 1-1, except that the dyed TAC film was used. The obtained polarizing plate with the retardation layer was subjected to the same evaluation as in example 1-1. The results are shown in Table 1.
Comparative example 1
A polarizing plate with a retardation layer was produced in the same manner as in example 1-1, except that an undyed TAC film was used. The undyed TAC film had a transmittance of 68.5% at a wavelength of 400nm and a transmittance Y value of 92.1%. The obtained polarizing plate with the retardation layer was subjected to the same evaluation as in example 1-1. The results are shown in Table 1.
Examples 2 to 1
The dyeing conditions were adjusted to prepare a polarizing film having a monomer transmittance of 44.0%. A polarizing plate with a retardation layer was produced in the same manner as in example 1-1, except that the polarizing film was used. The obtained polarizing plate with the retardation layer was subjected to the same evaluation as in example 1-1. The results are shown in Table 1.
Examples 2 to 2
A polarizing plate with a retardation layer was produced in the same manner as in example 1-2, except that the polarizing film produced in example 2-1 was used. The obtained polarizing plate with the retardation layer was subjected to the same evaluation as in example 1-1. The results are shown in Table 1.
Examples 2 to 3
A polarizing plate with a retardation layer was produced in the same manner as in example 1-3, except that the polarizing film produced in example 2-1 was used. The obtained polarizing plate with the retardation layer was subjected to the same evaluation as in example 1-1. The results are shown in Table 1.
Comparative example 2
A polarizing plate with a retardation layer was produced in the same manner as in comparative example 1, except that the polarizing film produced in example 2-1 was used. The obtained polarizing plate with the retardation layer was subjected to the same evaluation as in example 1-1. The results are shown in Table 1.
TABLE 1
[ evaluation ]
From table 1, it can be seen that: according to the embodiment of the present invention, by using a dyed TAC film as the protective layer, the reflected color phase can be brought close to a neutral state as compared with the comparative example.
Industrial applicability
The polarizing plate with a retardation layer of the present invention can be suitably used as a circularly polarizing plate for liquid crystal display devices, organic EL display devices and inorganic EL display devices.
Description of the reference numerals
10. Polarizing plate
11. Polarizing film
12. Visual identification side protection layer
13. Inner protective layer
20. Phase difference layer
100. Polarizing plate with phase difference layer
101. Polarizing plate with phase difference layer
Claims (15)
1. A dyed cellulose triacetate film is dyed with iodine, and has a transmittance at a wavelength of 400nm of 65% or less and a transmittance Y corrected for visibility of 80% or more.
2. A polarizing plate comprising a polarizing film and a protective layer disposed on at least one side of the polarizing film,
the thickness of the polarizing film is 8 μm or less,
the protective layer is composed of the dyed cellulose triacetate film of claim 1.
3. The method for manufacturing a polarizing plate according to claim 2, comprising:
forming a polyvinyl alcohol resin layer on one side of a long thermoplastic resin substrate to form a laminate;
dyeing and stretching the laminate to form a polarizing film from the polyvinyl alcohol resin layer;
dyeing the cellulose triacetate film with iodine so that the transmittance at a wavelength of 400nm is 65% or less and so that the transmittance Y subjected to visibility correction is 80% or more; and
And bonding the dyed cellulose triacetate film to the polarizing film.
4. The method of manufacturing a polarizing plate according to claim 3, wherein the dyeing comprises: the cellulose triacetate film is immersed in an aqueous iodine solution having an iodine concentration of 0.1 wt% or more.
5. A polarizing plate with a retardation layer comprising the polarizing plate according to claim 2, and a retardation layer disposed on the opposite side of the polarizing plate from the side for visual recognition,
re (550) of the retardation layer is 100nm to 190nm, re (450)/Re (550) is 0.8 or more and less than 1,
the angle between the slow axis of the retardation layer and the absorption axis of the polarizing film of the polarizing plate is 40 DEG to 50 deg.
6. The polarizing plate with a retardation layer as claimed in claim 5, wherein the retardation layer is composed of a polycarbonate-based resin film.
7. The polarizing plate with a retardation layer as claimed in claim 5 or 6, wherein a further retardation layer is further provided on the outer side of the retardation layer, and refractive index characteristics of the further retardation layer show a relationship of nz > nx=ny.
8. The polarizing plate with a retardation layer as claimed in any one of claims 5 to 7, which is in the form of an elongated shape,
the polarizing film has an absorption axis along the long-strip direction,
The retardation layer is an obliquely stretched film having a slow axis in a direction at an angle of 40 DEG to 50 DEG with respect to the longitudinal direction.
9. The polarizing plate with a retardation layer as claimed in claim 8, which is capable of being rolled up.
10. A polarizing plate with a retardation layer comprising the polarizing plate according to claim 2, and a retardation layer disposed on the opposite side of the polarizing plate from the side for visual recognition,
the retardation layer has a laminated structure of an alignment cured layer of a first liquid crystal compound and an alignment cured layer of a second liquid crystal compound,
the Re (550) of the orientation curing layer of the first liquid crystal compound is 200-300 nm, the angle between the slow axis and the absorption axis of the polarizing film is 10-20 degrees,
the Re (550) of the orientation-cured layer of the second liquid crystal compound is 100-190 nm, and the angle between the slow axis and the absorption axis of the polarizing film is 70-80 degrees.
11. The polarizing plate with a retardation layer as claimed in any one of claims 5 to 10, further comprising a conductive layer or an isotropic substrate with a conductive layer on the outer side of the retardation layer.
12. An image display device provided with the polarizing plate according to claim 2.
13. An image display device comprising the polarizing plate with a retardation layer according to any one of claims 5 to 11.
14. The image display device according to claim 12 or 13, which is an organic electroluminescent display device or an inorganic electroluminescent display device.
15. An image adjustment method of an image display device, comprising: the polarizing plate according to claim 2 or the polarizing plate with a retardation layer according to any one of claims 5 to 11 is attached to the visual recognition side of the image display unit so that the reflection hue is near neutral.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020143530A JP7240363B2 (en) | 2020-08-27 | 2020-08-27 | Dyed triacetylcellulose film, polarizing plate using the film, method for producing polarizing plate, polarizing plate with retardation layer, image display device, and image adjustment method for image display device |
| JP2020-143530 | 2020-08-27 | ||
| PCT/JP2021/026718 WO2022044604A1 (en) | 2020-08-27 | 2021-07-16 | Dyed triacetyl cellulose film, polarizing plate using said film, method for producing polarizing plate, polarizing plate with retardation layer, image display device and image adjustment method for image display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116097332A true CN116097332A (en) | 2023-05-09 |
| CN116097332B CN116097332B (en) | 2023-10-27 |
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| CN202180052958.3A Active CN116097332B (en) | 2020-08-27 | 2021-07-16 | Dyed cellulose triacetate film, polarizing plate using the same, method for producing polarizing plate, polarizing plate with retardation layer, image display device, and method for adjusting image of image display device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7240363B2 (en) |
| KR (1) | KR102563131B1 (en) |
| CN (1) | CN116097332B (en) |
| TW (1) | TW202212436A (en) |
| WO (1) | WO2022044604A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54114100A (en) * | 1978-02-24 | 1979-09-05 | Citizen Watch Co Ltd | Liquid crystal display unit |
| JP2002221618A (en) * | 2001-01-24 | 2002-08-09 | Nitto Denko Corp | Polarizing plate and liquid crystal display device using the same |
| JP2020064277A (en) * | 2018-10-15 | 2020-04-23 | 日東電工株式会社 | Polarizing plate with phase difference layer and image display device using the same |
| JP2020064290A (en) * | 2018-10-15 | 2020-04-23 | 日東電工株式会社 | Polarizing plate with phase difference layer and image display device using the same |
| JP2020076968A (en) * | 2018-10-15 | 2020-05-21 | 日東電工株式会社 | Polarizing plate with retardation layer and image display using the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624701U (en) * | 1985-03-07 | 1987-01-12 | ||
| TW424154B (en) | 1998-10-30 | 2001-03-01 | Teijin Ltd | Phase film and optical device using same |
| JP3877176B2 (en) * | 2005-01-20 | 2007-02-07 | 日東電工株式会社 | Manufacturing method of polarizing plate |
| JP6365257B2 (en) * | 2014-11-18 | 2018-08-01 | Jsr株式会社 | Retardation film laminate, polarizing plate, and method for producing retardation film laminate |
| JP6714808B2 (en) * | 2015-09-08 | 2020-07-01 | 三菱ケミカル株式会社 | Film for polarizing film, polarizing film using the same, and method for producing the same |
| TWI748108B (en) * | 2017-09-13 | 2021-12-01 | 日商日東電工股份有限公司 | Polarizing film, polarizing plate, and manufacturing method of polarizing film |
| JP6890161B2 (en) | 2018-10-15 | 2021-06-18 | 日東電工株式会社 | Polarizing plate with retardation layer and image display device using it |
| KR20200092884A (en) * | 2019-01-25 | 2020-08-04 | 스미또모 가가꾸 가부시끼가이샤 | Laminate for organic electroluminescent display and circularly polarizing plate used in the laminate |
-
2020
- 2020-08-27 JP JP2020143530A patent/JP7240363B2/en active Active
-
2021
- 2021-07-16 KR KR1020237005140A patent/KR102563131B1/en active IP Right Grant
- 2021-07-16 CN CN202180052958.3A patent/CN116097332B/en active Active
- 2021-07-16 WO PCT/JP2021/026718 patent/WO2022044604A1/en active Application Filing
- 2021-08-04 TW TW110128744A patent/TW202212436A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54114100A (en) * | 1978-02-24 | 1979-09-05 | Citizen Watch Co Ltd | Liquid crystal display unit |
| JP2002221618A (en) * | 2001-01-24 | 2002-08-09 | Nitto Denko Corp | Polarizing plate and liquid crystal display device using the same |
| JP2020064277A (en) * | 2018-10-15 | 2020-04-23 | 日東電工株式会社 | Polarizing plate with phase difference layer and image display device using the same |
| JP2020064290A (en) * | 2018-10-15 | 2020-04-23 | 日東電工株式会社 | Polarizing plate with phase difference layer and image display device using the same |
| JP2020076968A (en) * | 2018-10-15 | 2020-05-21 | 日東電工株式会社 | Polarizing plate with retardation layer and image display using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022038844A (en) | 2022-03-10 |
| KR102563131B1 (en) | 2023-08-07 |
| WO2022044604A1 (en) | 2022-03-03 |
| KR20230030662A (en) | 2023-03-06 |
| JP7240363B2 (en) | 2023-03-15 |
| CN116097332B (en) | 2023-10-27 |
| TW202212436A (en) | 2022-04-01 |
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