CN115004067A - Polarizing plate with phase difference layer and image display device using same - Google Patents
Polarizing plate with phase difference layer and image display device using same Download PDFInfo
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- CN115004067A CN115004067A CN202080094209.2A CN202080094209A CN115004067A CN 115004067 A CN115004067 A CN 115004067A CN 202080094209 A CN202080094209 A CN 202080094209A CN 115004067 A CN115004067 A CN 115004067A
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- polarizing plate
- retardation layer
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- 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
-
- 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
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Abstract
The present invention provides a thin polarizing plate with a retardation layer, which has excellent reliability under a high-temperature and high-humidity environment when applied to an image display device, and can inhibit the increase of reflectivity. The polarizing plate with a retardation layer of the present invention comprises a polarizing plate comprising a polarizer, a retardation layer and an adhesive layer in this order from the side of visual recognition. The retardation layer is an alignment cured layer of a liquid crystal compound having a circular polarization function or an elliptical polarization function. The polarizing plate with the phase difference layer is provided with an iodine transmission inhibiting layer between the polarizer and the adhesive layer, wherein the iodine transmission inhibiting layer is a solid or thermosetting product of a coating film of an organic solvent solution of resin; the iodine absorption index of the iodine permeation inhibitor layer is 0.015 or less.
Description
Technical Field
The present invention relates to a polarizing plate with a retardation layer and an image display device using the same.
Background
In recent years, image display devices typified by liquid crystal display devices and Electroluminescence (EL) display devices (for example, organic EL display devices and inorganic EL display devices) have rapidly spread. Typically, an image display device uses a polarizing plate and a phase difference plate. In practical applications, a polarizing plate with a retardation layer in which a polarizing plate and a retardation plate are integrated is widely used (for example, patent document 1), but recently, with the increasing demand for the thinning of an image display device, the demand for the thinning of a polarizing plate with a retardation layer is also increasing. For the purpose of reducing the thickness of a polarizing plate with a retardation layer, reduction (or omission) of a protective layer of a polarizing plate having a large influence on the thickness and reduction of a retardation film have been advanced. However, when a thin polarizing plate with a retardation layer is applied to an image display device, the reliability may be insufficient in a high-temperature and high-humidity environment. More specifically, a polarizing plate with a retardation layer is typically used as an antireflection film, but the reflectance of an image display device may increase in a high-temperature and high-humidity environment. When the thin polarizing plate with a retardation layer is applied to an image display device, metal members (for example, electrodes, sensors, wirings, and metal layers) of the image display device may be corroded.
Documents of the prior art
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 thin polarizing plate with a retardation layer, which has excellent reliability under a high-temperature and high-humidity environment and can suppress an increase in reflectance when applied to an image display device.
Means for solving the problems
The polarizing plate with a retardation layer of the present invention comprises, in order from the side of visual recognition, a polarizing plate comprising a polarizer, a retardation layer which is an alignment cured layer of a liquid crystal compound having a circular polarization function or an elliptical polarization function, and an adhesive layer. The polarizing plate with the phase difference layer is provided with an iodine transmission inhibiting layer between the polarizer and the adhesive layer, wherein the iodine transmission inhibiting layer is a solid or thermosetting substance of a coating film of an organic solvent solution of resin; the iodine absorption index of the iodine permeation inhibiting layer is 0.015 or less.
In one embodiment, the iodine permeation suppressing layer is provided between the polarizer and the retardation layer. In another embodiment, the iodine permeation suppressing layer is provided between the retardation layer and the pressure-sensitive adhesive layer.
In one embodiment, the iodine permeation inhibiting layer is provided with 2 or more layers between the polarizer and the adhesive layer.
In one embodiment, the iodine permeation prevention layer has a potassium absorption index of 0.015 or less.
In one embodiment, the resin constituting the iodine permeation inhibiting layer has a glass transition temperature of 85 ℃ or higher and a weight average molecular weight Mw of 25000 or higher.
In one embodiment, the resin constituting the iodine permeation inhibiting layer includes a copolymer obtained by polymerizing a monomer mixture including more than 50 parts by weight of a (meth) acrylic monomer and more than 0 part by weight and less than 50 parts by weight of a monomer represented by formula (1):
(wherein X represents a functional group containing a reactive group, and the reactive group is at least 1 reactive group selected from the group consisting of a vinyl group, a (meth) acryloyl group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group, and R 1 And R 2 Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group or an optionally substituted heterocyclic group, R 1 And R 2 Optionally linked to each other to form a ring).
In one embodiment, the retardation layer is a single layer, and the retardation layer has an Re (550) of 100nm to 190nm, and the slow axis of the retardation layer forms an angle of 40 ° to 50 ° with the absorption axis of the polarizer.
In one embodiment, the retardation layer has a laminated structure of a 1 st alignment cured layer of a liquid crystal compound and a 2 nd alignment cured layer of a liquid crystal compound; the Re (550) of the oriented cured layer of the 1 st liquid crystal compound is 200 to 300nm, and the angle formed by the slow axis and the absorption axis of the polarizer is 10 to 20 degrees; the Re (550) of the alignment cured layer of the 2 nd liquid crystal compound is 100 to 190nm, and the angle formed by the slow axis and the absorption axis of the polarizer is 70 to 80 degrees.
In one embodiment, the polarizing plate with a retardation layer further includes a retardation layer between the retardation layer and the pressure-sensitive adhesive layer, and the refractive index characteristic of the retardation layer is represented by nz > nx ═ ny.
In one embodiment, the polarizing plate with a retardation layer further includes a conductive layer or an isotropic base with a conductive layer between the iodine permeation inhibiting layer and the adhesive layer.
In one embodiment, the total thickness of the polarizing plate with a retardation layer is 60 μm or less.
According to another aspect of the present invention, there is provided an image display device. The image display device comprises the polarizing plate with the phase difference layer.
In one embodiment, the image display device is an organic electroluminescence display device or an inorganic electroluminescence display device.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the embodiment of the present invention, the iodine permeation inhibiting layer having a predetermined iodine absorption index is provided at a predetermined position of the thin polarizing plate having a retardation layer, and thus, when the polarizing plate having a retardation layer is applied to an image display device, an increase in reflectance in a high-temperature and high-humidity environment can be inhibited.
Drawings
Fig. 1A is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention.
Fig. 1B is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to still another embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to still another embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to still another embodiment of the present invention.
Fig. 5 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to still another embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.
(definitions of terms and symbols)
The terms and symbols in the present specification are defined as follows.
(1) Refractive index (nx, ny, nz)
"nx" is a refractive index in a direction in which an in-plane refractive index is maximized (i.e., a slow axis direction), "ny" is a refractive index in a direction orthogonal to a slow axis in a plane (i.e., a fast axis direction), and "nz" is a refractive index in a thickness direction.
(2) In-plane retardation (Re)
"Re (λ)" is an in-plane retardation measured at 23 ℃ with light of wavelength λ nm. For example, "Re (550)" is an in-plane retardation measured at 23 ℃ with light having a wavelength of 550 nm. When the thickness of the layer (thin film) is d (nm), Re (λ) is represented 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 ℃ with light having a wavelength of λ nm. 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 (film) is d (nm), Rth (λ) is expressed by the following formula: rth (λ) ═ n x-nz × d.
(4) Coefficient of Nz
The Nz coefficient can be obtained by Nz ═ Rth/Re.
(5) Angle of rotation
When an angle is referred to in this specification, the angle includes both a clockwise direction and a counterclockwise direction with respect to a reference direction. Thus, for example, "45" means ± 45 °.
A. Integral structure of polarizing plate with phase difference layer
FIG. 1A is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the present invention; fig. 1B is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention. The polarizing plates 100 and 101 with a retardation layer in fig. 1A and 1B each have a polarizing plate 10, a retardation layer 20, and an adhesive layer 30 in this order from the visible side. The polarizing plate 10 typically includes a polarizer 11 and a protective layer 12 disposed on the viewing side of the polarizer 11. Depending on the purpose, another protective layer (not shown) may be provided on the side of the polarizer 11 opposite to the viewing side (protective layer 12). The retardation layer 20 is an alignment cured layer of a liquid crystal compound having a circular polarization function or an elliptical polarization function (hereinafter, may be simply referred to as a liquid crystal alignment cured layer). The adhesive layer 30 is provided as the outermost layer, and the polarizing plate with a phase difference layer may be attached to an image display device (substantially, an image display unit).
In the embodiment of the present invention, the iodine permeation inhibiting layer 40 is provided between the polarizer 11 and the adhesive layer 30. The iodine permeation inhibiting layer 40 may be provided between the polarizer 11 and the retardation layer 20 (i.e., adjacent to the polarizer 11) as shown in fig. 1A, or may be provided between the retardation layer 20 and the adhesive layer 30 as shown in fig. 1B. When the iodine permeation inhibiting layer is provided between the polarizer and the retardation layer (particularly when the iodine permeation inhibiting layer is adjacent to the polarizer), the iodine can be inhibited from moving from the polarizer in a high-temperature and high-humidity environment, and the reliability can be improved. When the iodine permeation-inhibiting layer is provided between the retardation layer and the pressure-sensitive adhesive layer (particularly when the iodine permeation-inhibiting layer is adjacent to the pressure-sensitive adhesive layer), it is possible to prevent components other than iodine, which may affect metal corrosion (for example, a residual monomer component in the ultraviolet-curable adhesive and a decomposition product of the photoinitiator), from moving into the pressure-sensitive adhesive, and therefore, there is an advantage in that the effect of inhibiting metal corrosion is further enhanced.
In the polarizing plate with a retardation layer, 2 or more iodine permeation inhibiting layers may be provided between the polarizer and the adhesive layer (for example, fig. 4 and 5). The polarizing plate with a retardation layer has 2 or more iodine permeation inhibiting layers, and thus corrosion of a metal member can be significantly inhibited when the polarizing plate with a retardation layer is applied to an image display device.
In the polarizing plate with retardation layer shown in fig. 4, 2 iodine permeation inhibiting layers were provided between the polarizer and the adhesive layer. In the example shown in fig. 4, 2 iodine transmission suppressing layers are provided between the polarizer 11 and the retardation layer 20 and between the retardation layer 20 and the pressure-sensitive adhesive layer 30. In one embodiment, the iodine permeation inhibiting layer is provided adjacent to the polarizer. In another embodiment, the iodine permeation suppressing layer is provided adjacent to the retardation layer. The term "adjacent" in the present specification means that the layers are directly laminated without an adhesive layer or the like.
In the polarizing plate with retardation layer shown in fig. 5, 3 iodine permeation inhibiting layers were provided between the polarizer and the adhesive layer. In the example shown in fig. 5, the iodine permeation inhibiting layer is provided with 2 layers between the polarizer 11 and the retardation layer 20, and 1 layer between the retardation layer 20 and the adhesive layer 30. One of the 2 iodine transmission inhibiting layers between the polarizer 11 and the retardation layer 20 is provided adjacent to the polarizer, and the other is provided adjacent to the retardation layer.
In the polarizing plate with a retardation layer, the iodine permeation inhibiting layer may be 4 or more (e.g., 4, 5, 6 layers). The greater the number of iodine permeation inhibiting layers, the greater the metal corrosion inhibiting effect. The number of the iodine permeation inhibiting layers can be set in consideration of cost, manufacturing efficiency, layer thickness of the polarizing plate with a retardation layer, and the like.
The iodine absorption index of the iodine permeation inhibitor layer is 0.015 or less. By providing such an iodine permeation suppressing layer at a predetermined position of the polarizing plate with a retardation layer, when the polarizing plate with a retardation layer is applied to an image display device, iodine in the polarizer can be significantly suppressed from moving to the image display device (substantially, an image display unit). As a result, when the polarizing plate with a retardation layer is applied to an image display device, the decrease in reliability due to iodine under a high-temperature and high-humidity environment can be suppressed, and thus the increase in reflectance can be suppressed. Further, the potassium absorption index of the iodine permeation inhibiting layer is preferably 0.015 or less. The iodine permeation prevention layer can further prevent a decrease in reliability due to iodine in a high-temperature and high-humidity environment by having not only an iodine absorption index of a predetermined value or less but also a potassium absorption index of a predetermined value or less, and thus can further prevent an increase in reflectance.
Such an effect is a characteristic effect of a thin polarizing plate with a retardation layer (typically, a polarizing plate with a retardation layer in which the retardation layer is a liquid crystal alignment cured layer). Namely, the present inventors have newly found the following problems: when a thin polarizing plate with a retardation layer is applied to an image display device, the reflectance may increase in a high-temperature and high-humidity environment, and it has been found that such a problem may be caused by iodine. As a result of extensive studies, it has been found that an iodine permeation inhibiting layer having an iodine adsorption index as described above is useful as a means for preventing iodine from moving to an image display device (substantially, an image display unit), and the present invention has been completed. That is, such an effect solves a new problem which has not been known in the past, and is an unexpected excellent effect. Further, as described later, the iodine permeation inhibiting layer can be formed very thin, and the protective layer on the side opposite to the visual recognition side can be omitted by providing the iodine permeation inhibiting layer, and therefore, by the synergistic effect of these, it is possible to contribute to further thinning of the polarizing plate with a retardation layer. Such an iodine permeation inhibiting layer can also have an effect of significantly inhibiting corrosion of metal members (for example, electrodes, sensors, wirings, and metal layers) of the image display device.
As shown in fig. 2, in the polarizing plate with retardation layer 102 according to the further embodiment, another retardation layer 50 and/or a conductive layer or an isotropic substrate with conductive layer 60 may be provided. The additional retardation layer 50 is typically provided between the retardation layer 20 and the pressure-sensitive adhesive layer 30 (i.e., outside the retardation layer 20). The other retardation layer is typically one having refractive index characteristics showing a relationship of nz > nx ═ ny. The conductive layer or the isotropic substrate with a conductive layer 60 is typically provided between the iodine permeation inhibiting layer 40 and the pressure-sensitive adhesive layer 30 (i.e., outside the iodine permeation inhibiting layer 40). The retardation layer 50 and the conductive layer or the isotropic substrate with conductive layer 60 are typically provided in this order from the side of the retardation layer 20. In the illustrated example, the iodine permeation-suppressing layer 40, the phase difference layer 20, the other phase difference layer 50, and the conductive layer or conductive layer-attached isotropic base material 60 are provided in this order from the visually recognizable side, but any suitable arrangement order may be adopted as long as the other phase difference layer 50 is provided between the phase difference layer 20 and the pressure-sensitive adhesive layer 30, and the conductive layer or conductive layer-attached isotropic base material 60 is provided between the iodine permeation-suppressing layer 40 and the pressure-sensitive adhesive layer 30. The retardation layer 50 and the conductive layer or the isotropic substrate with conductive layer 60 are typically optional layers provided as needed, and either or both of them may be omitted. For convenience, the retardation layer 20 may be referred to as a 1 st retardation layer, and the other retardation layer 50 may be referred to as a 2 nd retardation 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 a polarizing plate. In the embodiment of the present invention, the conductive layer or the isotropic substrate with a conductive layer 60 is provided outside the iodine permeation inhibiting layer 40, whereby corrosion of the conductive layer can be significantly inhibited.
As described above, the 1 st retardation layer 20 is a liquid crystal alignment cured layer. The 1 st retardation layer 20 may be a single layer as shown in fig. 1A, 1B and 2, or may have a laminated structure of a 1 st liquid crystal alignment cured layer 21 and a 2 nd liquid crystal alignment cured layer 22 as shown in fig. 3.
The above embodiments may be combined as appropriate, and obvious modifications in the art may be added to the components of the above embodiments. For example, the 2 nd retardation layer 50 and/or the conductive layer or the isotropic substrate 60 with a conductive layer may be disposed on the polarizing plate 101 with a retardation layer of fig. 1B; the retardation layer 20 of the retardation layer-equipped polarizing plate 101 of fig. 1B may also have a 2-layer structure as shown in fig. 3; the 2 nd retardation layer 50 and/or the conductive layer or the isotropic substrate 60 with a conductive layer may be disposed on the polarizing plate with retardation layer 103 of fig. 3; the iodine permeation inhibiting layer 40 of the retardation layer-equipped polarizing plate 102 of fig. 2 may be provided between the retardation layer 20 and the conductive layer or the conductive layer-equipped isotropic substrate 60.
The polarizing plate with a retardation layer according to the embodiment of the present invention may further include another retardation layer. The optical properties (e.g., refractive index properties, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, arrangement position, and the like of the other retardation layer can be appropriately set according to the purpose.
The polarizing plate with a retardation layer according to the embodiment of the present invention may be either a single sheet or a long sheet. The term "elongated shape" as used herein means an elongated shape having a length sufficiently long with respect to the width, and includes, for example, an elongated shape having a length 10 times or more, preferably 20 times or more with respect to the width. The long polarizing plate with the retardation layer may be rolled up in a roll.
The total thickness of the polarizing plate with a retardation layer is preferably 60 μm or less, more preferably 55 μm or less, still more preferably 50 μm or less, and particularly preferably 40 μm or less. The lower limit of the total thickness may be, for example, 28 μm. According to the embodiments of the present invention, it is possible to realize such an extremely thin polarizing plate with a retardation layer, and further, even when such an extremely thin polarizing plate with a retardation layer is applied to an image display device, it is possible to suppress a decrease in reliability due to iodine under a high-temperature and high-humidity environment, and therefore, it is possible to suppress an increase in reflectance. Further, corrosion of metal members (e.g., electrodes, sensors, wirings, metal layers) of the image display device can be significantly suppressed. In addition, such a polarizing plate with a retardation layer can have extremely excellent flexibility and bending durability. Therefore, such a polarizing plate with a retardation layer is particularly suitable for application to a curved image display device and/or a foldable or foldable image display device. The total thickness of the polarizing plate with a retardation layer means the total thickness of the polarizing plate, the retardation layer (the 1 st retardation layer and the 2 nd retardation layer when the 2 nd retardation layer is present), the iodine permeation-inhibiting layer, and the adhesive layer or the adhesive layer for laminating them (that is, the total thickness of the polarizing plate with a retardation layer does not include the conductive layer or the isotropic substrate 60 with a conductive layer, and the adhesive layer 30 and the release film which can be temporarily bonded to the surface thereof).
In practical use, it is preferable to temporarily adhere a release film to the surface of the pressure-sensitive adhesive layer 30 until the polarizing plate with a retardation layer is used. By temporarily adhering the release film, a roll of the polarizing plate with the retardation layer can be formed while protecting the pressure-sensitive adhesive layer.
The following describes the components of the polarizing plate with a retardation layer in more detail. Since the pressure-sensitive adhesive layer 30 can have a structure known in the art, the detailed description of the pressure-sensitive adhesive layer is omitted.
B. Polarizing plate
B-1. polarizer
The polarizer is typically made of a polyvinyl alcohol (PVA) resin film containing a dichroic material. The thickness of the polarizer is preferably 1 μm to 8 μm, more preferably 1 μm to 7 μm, and still more preferably 2 μm to 5 μm. If the thickness of the polarizer is within such a range, it can greatly contribute to the reduction in thickness of the polarizing plate with a retardation layer. Further, the present invention is effective in a thin polarizing plate with a retardation layer using such a polarizing element.
The boric acid content of the polarizer is preferably 10 wt% or more, more preferably 13 to 25 wt%. When the boric acid content of the polarizer is within such a range, the appearance durability during heating can be improved while maintaining the ease of curl adjustment during adhesion and suppressing curl during heating satisfactorily by the synergistic effect with the iodine content described later. The boric acid content can be calculated as the amount of boric acid contained per unit weight of the polarizer by a neutralization method using the following formula, for example.
The iodine content of the polarizer is preferably 2% by weight or more, and more preferably 2% by weight to 10% by weight. When the iodine content of the polarizer is in such a range, the curl adjustment at the time of bonding can be favorably maintained and the curl at the time of heating can be favorably suppressed and the appearance durability at the time of heating can be improved by the synergistic effect with the boric acid content described above. In the present specification, the "iodine content" refers to the amount of all iodine contained in the polarizer (PVA-based resin film). More specifically, in the polarizer, iodine is represented by iodide ion (I) - ) Iodine molecule (I) 2 ) Polyiodide (I) 3 - 、I 5 - ) The iodine content in the present specification means the amount of iodine including all of these forms when they exist. The iodine content can be calculated, for example, by a standard curve method of fluorescent X-ray analysis. Note that, in the polarizing plate, polyiodide exists in a state of forming a PVA-iodine complex. By forming such a complex, it can be expressed in the wavelength range of visible lightAbsorption dichroism. Specifically, a complex of PVA and triiodide ion (PVA. I) 3 - ) A complex of PVA and a pentaiodide ion (PVA. I) having an absorption peak at about 470nm 5 - ) Has an absorption peak around 600 nm. As a result, the polyiodide can absorb light in a wide range of visible light depending on its form. On the other hand, iodide ion (I) - ) Has an absorption peak around 230nm, and does not substantially interfere with absorption of visible light. Thus, the presence of multiple iodide ions in a complex with PVA primarily interferes with the absorptive properties of the pre-polarizer.
The polarizing element preferably exhibits dichroism of absorption at any wavelength of 380nm to 780 nm. The single transmittance Ts of the polarizer is preferably 40% to 48%, more preferably 41% to 46%. The degree of polarization P of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and still more preferably 99.9% or more. The monomer transmittance is typically a Y value measured by an ultraviolet-visible spectrophotometer and corrected for visual sensitivity. The polarization degree is typically 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 a visual sensitivity correction.
Polarization degree (%) { (Tp-Tc)/(Tp + Tc) } 1/2 ×100
The polarizer is typically produced using a laminate of two or more layers. Specific examples of the polarizing plate obtained using the laminate include a polarizing plate obtained using a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate by coating. A polarizer obtained by using a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate by coating can be produced, for example, by: coating a PVA-based resin solution on a resin base material and drying the coating to form a PVA-based resin layer on the resin base material, thereby obtaining a laminate of the resin base material and the PVA-based resin layer; the laminate is stretched and dyed to form a polarizing plate from the PVA resin layer. The stretching typically comprises immersing the laminate in an aqueous solution of boric acid and stretching. Further, the stretching may further include, if necessary, in-air stretching the laminate at a high temperature (e.g., 95 ℃ or higher) before the stretching in the aqueous boric acid solution. The obtained resin base material/polarizer laminate may be used as it is (that is, the resin base material may be used as a protective layer for the polarizer), or the resin base material may be peeled from the resin base material/polarizer laminate and an arbitrary appropriate protective layer may be laminated on the peeled surface according to the purpose. The details of the method for producing such a polarizer are described in, for example, japanese unexamined patent publication No. 2012 and 73580 and japanese patent No. 6470455. The entire disclosures of these publications are incorporated herein by reference.
The method of manufacturing the polarizing plate typically includes: forming a polyvinyl alcohol resin layer containing a halide and a polyvinyl alcohol resin on one side of a long thermoplastic resin base material to form a laminate; and subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in this order, wherein the laminate is shrunk by 2% or more in the width direction by heating while being conveyed in the longitudinal direction. Thus, a polarizer which is extremely thin, has excellent optical characteristics, and is suppressed in variation of optical characteristics can be provided. That is, by introducing the auxiliary stretching, the crystallinity of the PVA can be improved even when the PVA is coated on the thermoplastic resin, and high optical characteristics can be achieved. Further, by simultaneously improving the orientation of the PVA in advance, it is possible to prevent problems such as a decrease in the orientation or dissolution of the PVA when immersed in water in the subsequent dyeing step or stretching step, and to achieve high optical characteristics. Further, when the PVA-based resin layer is immersed in a liquid, disturbance of orientation of polyvinyl alcohol molecules and reduction of orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This can improve the optical properties of the polarizer obtained through a treatment step of immersing the laminate in a liquid, such as dyeing treatment and underwater stretching treatment. Further, the optical characteristics can be improved by shrinking the laminate in the width direction by the drying shrinkage treatment.
B-2 protective layer
The protective layer 12 is formed of any suitable thin film that can be used as a protective layer of a polarizer. Specific examples of the material as the main component of the film include cellulose resins such as Triacetylcellulose (TAC), and transparent resins such as polyester resins, polyvinyl alcohol resins, polycarbonate resins, polyamide resins, polyimide resins, polyether sulfone resins, polysulfone resins, polystyrene resins, polynorbornene resins, polyolefin resins, (meth) acrylic resins, and acetate resins. Further, thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, and silicone resins, ultraviolet-curable resins, and the like can be mentioned. Further, for example, a glassy polymer such as a siloxane polymer can be given. Further, the polymer film described in Japanese patent application laid-open No. 2001-343529 (WO01/37007) may 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 substituted or unsubstituted phenyl group and a nitrile group in a side chain can be used, and for example, a resin composition containing an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer can be mentioned. The polymer film may be, for example, an extrusion molded product of the resin composition.
As described later, the polarizing plate with a retardation layer is typically disposed on the viewing side of the image display device, and the protective layer 12 is typically disposed on the viewing side thereof. Therefore, the protective layer 12 may be subjected to surface treatment such as hard coating treatment, antireflection treatment, adhesion prevention treatment, and antiglare treatment as needed. Further, the protective layer 12 may be subjected to a treatment for improving the visibility when viewed through polarized sunglasses (typically, imparting a (elliptical) polarization function and imparting a super-high retardation) as necessary. By performing such a process, even when the display screen is visually recognized through a polarizing lens such as a polarizing sunglass, excellent visual recognition can be achieved. Therefore, the polarizing plate with a retardation layer can be suitably used for an image display device which can be used outdoors.
The thickness of the protective layer is preferably 10 μm to 50 μm, and more preferably 10 μm to 30 μm. When the surface treatment is performed, the thickness of the outer protective layer is a thickness including the thickness of the surface treatment layer.
C. 1 st phase difference layer
The 1 st retardation layer 20 is a liquid crystal alignment cured layer as described above. By using the liquid crystal compound, the difference between nx and ny of the resulting retardation layer can be made significantly larger than that of the non-liquid crystal material, and therefore the thickness of the retardation layer for obtaining a desired in-plane retardation can be made significantly small. As a result, the polarizing plate with a retardation layer can be further thinned. In the present specification, the term "liquid crystal alignment cured layer" refers to a layer in which a liquid crystal compound is aligned in a predetermined direction within the layer and the alignment state is fixed. The "alignment cured layer" is a concept including an alignment cured layer obtained by curing a liquid crystal monomer as described below. In this embodiment, the rod-like liquid crystal compound is typically aligned in a state of being aligned in the slow axis direction of the 1 st retardation layer (parallel alignment).
Examples of the liquid crystal compound include a liquid crystal compound having a nematic phase (nematic liquid crystal). As such a liquid crystal compound, for example, a liquid crystal polymer or a liquid crystal monomer can be used. The mechanism of manifestation of liquid crystallinity of the liquid crystal compound may be either lyotropic or thermotropic. The liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.
When the liquid crystal compound is a liquid crystal monomer, the liquid crystal monomer is preferably a polymerizable monomer or a crosslinkable monomer. This is because the alignment state of the liquid crystal monomer can be fixed by polymerizing or crosslinking (i.e., curing) the liquid crystal monomer. After the liquid crystal monomers are aligned, for example, when the liquid crystal monomers are polymerized or cross-linked with each other, the above-described alignment state can be thereby fixed. Here, the polymer is formed by polymerization, and the 3-dimensional network structure is formed by crosslinking, but these are non-liquid crystalline. Therefore, the 1 st retardation layer formed does not undergo transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change, which is typical of liquid crystal compounds, for example. As a result, the 1 st retardation layer is a retardation layer having extremely excellent stability without being affected by temperature change.
The temperature range in which the liquid crystal monomer exhibits liquid crystallinity varies depending on the kind thereof. Specifically, the temperature range is preferably 40 to 120 ℃, more preferably 50 to 100 ℃, and most preferably 60 to 90 ℃.
As the liquid crystal monomer, any suitable liquid crystal monomer can be used. For example, polymerizable mesogen compounds described in Japanese patent application laid-open No. 2002-533742(WO00/37585), EP358208(US5211877), EP66137(US4388453), WO93/22397, EP0261712, DE19504224, DE4408171, GB2280445 and the like can be used. Specific examples of such polymerizable mesogen compounds include trade name LC242 manufactured by BASF corporation, trade name E7 manufactured by Merck corporation, and trade name LC-Sillicon-CC3767 manufactured by Wacker-Chem corporation. The liquid crystal monomer is preferably, for example, a nematic liquid crystal monomer.
The liquid crystal alignment cured layer may be formed as follows: the liquid crystal display device is formed by applying an alignment treatment to the surface of a predetermined substrate, applying a coating solution containing a liquid crystal compound to the surface to align the liquid crystal compound in a direction corresponding to the alignment treatment, and fixing the aligned state. In one embodiment, the substrate is any suitable resin film, and the liquid crystal alignment cured layer formed on the substrate may be transferred to the surface of an adjacent layer (e.g., polarizer, iodine permeation inhibitor layer).
As the alignment treatment, any appropriate alignment treatment may be adopted. Specific examples thereof include mechanical alignment treatment, physical alignment treatment, and chemical alignment treatment. Specific examples of the mechanical orientation treatment include rubbing treatment and stretching treatment. Specific examples of the physical alignment treatment include magnetic field alignment treatment and electric field alignment treatment. Specific examples of the chemical alignment treatment include oblique vapor deposition and photo-alignment treatment. The treatment conditions for the various alignment treatments may be any suitable conditions according to the purpose.
The alignment of the liquid crystal compound may be performed by performing a treatment at a temperature at which a liquid crystal phase is displayed, depending on the kind of the liquid crystal compound. By performing such temperature treatment, the liquid crystal compound is brought into a liquid crystal state, and the liquid crystal compound is aligned in accordance with the alignment treatment direction of the surface of the substrate.
In one embodiment, the fixing of the alignment state is performed by cooling the liquid crystal compound aligned as described above. When the liquid crystal compound is a polymerizable monomer or a crosslinkable monomer, the alignment state is fixed by subjecting the liquid crystal compound aligned as described above to polymerization treatment or crosslinking treatment.
Specific examples of the liquid crystal compound and the method for forming the alignment cured layer are described in jp 2006-163343 a. The description of this publication is incorporated herein by reference.
In one embodiment, the 1 st retardation layer 20 is a single layer as shown in fig. 1A, 1B and 2. When the 1 st retardation layer 20 is composed of a single layer, the thickness thereof is preferably 0.5 to 7 μm, more preferably 1 to 5 μm. By using the liquid crystal compound, an in-plane retardation equivalent to that of the resin film can be realized with a thickness significantly thinner than that of the resin film.
The 1 st retardation layer has a circular polarization function or an elliptical polarization function as described above. The 1 st retardation layer is representative of a retardation layer having a refractive index characteristic showing a relationship of nx > ny ═ nz. The 1 st retardation layer is typically provided to impart antireflection characteristics to the polarizing plate, and when the 1 st retardation layer is a single layer, it functions as a λ/4 plate. In this case, the in-plane retardation Re (550) of the 1 st retardation layer is preferably 100nm to 190nm, more preferably 110nm to 170nm, and still more preferably 130nm to 160 nm. Here, "ny ═ nz" includes not only the case where ny and nz are completely equal but also the case where ny and nz are substantially equal. Therefore, ny > nz or ny < nz may be present within a range not detrimental to the effects of the present invention.
The Nz coefficient of the 1 st retardation layer is preferably 0.9 to 1.5, more preferably 0.9 to 1.3. When the obtained polarizing plate with a retardation layer is used in an image display device, the obtained polarizing plate with a retardation layer satisfies such a relationship, and a very excellent reflection hue can be obtained.
The 1 st phase difference layer may exhibit anomalous dispersion wavelength characteristics in which a phase difference value becomes larger with the wavelength of the measurement light, may exhibit normal wavelength dispersion characteristics in which a phase difference value becomes smaller with the wavelength of the measurement light, and may also exhibit flat wavelength dispersion characteristics in which a phase difference value hardly changes with the wavelength of the measurement light. In one embodiment, the 1 st phase difference layer shows anomalous dispersion wavelength characteristics. In this case, Re (450)/Re (550) of the retardation layer is preferably 0.8 or more and less than 1, and more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection characteristics can be achieved.
The angle θ formed by the slow axis of the 1 st retardation layer 20 and the absorption axis of the polarizer 11 is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and still more preferably about 45 °. If the angle θ is within such a range, the polarizing plate with a retardation layer having very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics) can be obtained by forming the 1 st retardation layer into a λ/4 plate as described above.
In another embodiment, the 1 st retardation layer 20 has a laminated structure of a 1 st liquid crystal alignment cured layer 21 and a 2 nd liquid crystal alignment cured layer 22 as shown in fig. 3. In this case, either one of the 1 st liquid crystal alignment cured layer 21 and the 2 nd liquid crystal alignment cured layer 22 may function as a λ/4 plate, and the other may function as a λ/2 plate. Therefore, the thicknesses of the 1 st liquid crystal alignment cured layer 21 and the 2 nd liquid crystal alignment cured layer 22 can be adjusted so as to obtain a desired in-plane retardation of the λ/4 plate or the λ/2 plate. For example, when the 1 st liquid crystal alignment cured layer 21 functions as a λ/2 plate and the 2 nd liquid crystal alignment cured layer 22 functions as a λ/4 plate, the thickness of the 1 st liquid crystal alignment cured layer 21 is, for example, 2.0 μm to 3.0 μm, and the thickness of the 2 nd liquid crystal alignment cured layer 22 is, for example, 1.0 μm to 2.0 μm. In this case, the in-plane retardation Re (550) of the 1 st cured liquid crystal alignment layer is preferably 200nm to 300nm, more preferably 230nm to 290nm, and still more preferably 250nm to 280 nm. The in-plane retardation Re (550) of the 2 nd liquid crystal alignment cured layer is as described above with respect to a single layer. The angle formed by the slow axis of the 1 st liquid crystal alignment cured layer and the absorption axis of the polarizer is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and still more preferably about 15 °. The angle formed by the slow axis of the 2 nd liquid crystal alignment cured layer and the absorption axis of the polarizer is preferably 70 ° to 80 °, more preferably 72 ° to 78 °, and still more preferably about 75 °. With such a configuration, characteristics close to ideal anomalous wavelength dispersion characteristics can be obtained, and as a result, very excellent antireflection characteristics can be realized. The liquid crystal compounds constituting the 1 st and 2 nd liquid crystal alignment cured layers, the methods for forming the 1 st and 2 nd liquid crystal alignment cured layers, the optical characteristics, and the like are as described above with respect to a single layer.
D. Iodine permeation inhibitor
The iodine permeation inhibiting layer has an iodine absorption index of 0.015 or less, as described above. The iodine absorption index is preferably 0.012 or less, more preferably 0.009 or less, further preferably 0.007 or less, and particularly preferably 0.005 or less. The iodine adsorption index is preferably as small as possible, and is desirably zero, and the lower limit thereof may be 0.001, for example. The iodine absorption index is an index of the iodine permeation inhibiting ability of the iodine permeation inhibiting layer, and a smaller index indicates that iodine is more difficult to be absorbed by the iodine permeation inhibiting layer (i.e., iodine is easily blocked by the iodine permeation inhibiting layer). Therefore, if the iodine absorption index is within such a range, when the polarizing plate with a retardation layer is applied to an image display device, iodine in the polarizing plate can be significantly suppressed from moving to the image display device (substantially, an image display unit). As a result, when the polarizing plate with a retardation layer is applied to an image display device, the decrease in reliability due to iodine under a high-temperature and high-humidity environment can be suppressed, and thus the increase in reflectance can be suppressed. Further, as described above, the iodine permeation inhibiting layer preferably has a potassium absorption index of 0.015 or less. The potassium absorption index is more preferably 0.013 or less, still more preferably 0.011 or less, and particularly preferably 0.009 or less. The smaller the potassium absorption index is, the more preferable the potassium absorption index is, and the lower limit thereof may be, for example, 0.002. The potassium absorption index is an index of the potassium permeation inhibiting ability of the iodine permeation inhibiting layer, and a smaller index indicates that potassium is less likely to be absorbed by the iodine permeation inhibiting layer, and as a result, iodine and potassium polyiodide (I) in the form of potassium iodide 3 - K + ) The more the iodine in the form of (2) is less likely to be absorbed by the iodine permeation inhibiting layer. Therefore, if the potassium absorption index is within such a range, the movement of iodine can be suppressed not only in the form of iodine but also in the form of potassium iodide or potassium polyiodide. The iodine absorption index can be defined as the iodine intensity (kcps) obtained by analyzing the iodine permeation inhibiting layer with a fluorescent X-ray, and the potassium absorption index can be defined as the potassium intensity (kcps) obtained by analyzing the iodine permeation inhibiting layer with a fluorescent X-ray.
The iodine permeation prevention layer is typically a solid or a thermoset of a coating film of an organic solvent solution of a resin. A solid or a thermoset of a coating film of an organic solvent solution of the resin. With such a configuration, the thickness can be made very thin (for example, 10 μm or less). The thickness of the iodine permeation prevention layer is preferably 0.05 to 10 μm, more preferably 0.08 to 5 μm, still more preferably 0.1 to 1 μm, and particularly preferably 0.2 to 0.7. mu.m. Further, with such a configuration, the iodine permeation inhibiting layer can be formed directly (i.e., without the use of an adhesive layer or an adhesive layer) on the adjacent layer (e.g., polarizer or retardation layer). According to the embodiments of the present invention, as described above, the polarizing plate, the retardation layer, and the iodine transmission suppressing layer are extremely thin, and the adhesive layer or the adhesive for laminating the iodine transmission suppressing layer can be omitted, so that the total thickness of the polarizing plate with the retardation layer can be extremely thin. Further, such an iodine permeation prevention layer has an advantage of excellent humidification durability because the iodine permeation prevention layer has a smaller moisture absorption and moisture permeability than a solid material of an aqueous coating film such as an aqueous solution or an aqueous dispersion. As a result, a polarizing plate with a retardation layer having excellent durability and capable of maintaining optical characteristics even under a high-temperature and high-humidity environment can be realized. Further, such an iodine permeation inhibiting layer can inhibit the polarizing plate (polarizer) from being adversely affected by ultraviolet irradiation, for example, as compared with a cured product of an ultraviolet curable resin. The iodine permeation prevention layer is preferably a solid product of a coating film of an organic solvent solution of the resin. Since the cured product has a smaller shrinkage during film formation than a cured product, and contains no residual monomer, etc., it is possible to suppress deterioration of the film itself and to suppress adverse effects of the residual monomer, etc., on the polarizing plate (polarizer).
Further, the glass transition temperature (Tg) of the resin constituting the iodine permeation inhibiting layer is, for example, 85 ℃ or higher, and the weight average molecular weight Mw is, for example, 25000 or higher. If the Tg and Mw of the resin are within such ranges, the migration of iodine in the polarizer to the image display unit can be significantly suppressed even when the thickness is very thin, by the synergistic effect with the effect of the iodine permeation suppressing layer formed of a solid or thermally cured product of the coating film of the organic solvent solution of the resin. As a result, when the polarizing plate with a retardation layer is applied to an image display device, a decrease in reliability due to iodine under a high-temperature and high-humidity environment can be suppressed, and thus an increase in reflectance can be suppressed. Further, corrosion of the metal member can be significantly suppressed. The Tg of the resin is preferably 90 ℃ or higher, more preferably 100 ℃ or higher, still more preferably 110 ℃ or higher, and particularly preferably 120 ℃ or higher. The upper limit of Tg may be, for example, 200 ℃. The Mw of the resin is preferably 30000 or more, more preferably 35000 or more, and still more preferably 40000 or more. The upper limit of Mw may be, for example, 150000.
As the resin constituting the iodine permeation inhibiting layer, any suitable thermoplastic resin or thermosetting resin can be used as long as it can form a solid or a thermoset of a coating film of an organic solvent solution and has Tg and Mw as described above. Preferably a thermoplastic resin. Examples of the thermoplastic resin include acrylic resins and epoxy resins. An acrylic resin and an epoxy resin may be used in combination. Representative examples of acrylic resins and epoxy resins that can be used for the iodine permeation inhibiting layer are described below.
The acrylic resin typically contains, as a main component, a repeating unit derived from a (meth) acrylate monomer having a linear or branched structure. In the present specification, (meth) acrylic acid means acrylic acid and/or methacrylic acid. The acrylic resin may contain a repeating unit derived from any suitable comonomer used according to the purpose. Examples of the comonomer (monomer) include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, an aromatic ring-containing (meth) acrylate, and a heterocyclic ring-containing vinyl monomer. By appropriately setting the kind, number, combination, copolymerization ratio, and the like of the monomer units, an acrylic resin having the above-mentioned predetermined Mw can be obtained.
< boron-containing acrylic resin >
The acrylic resin includes, in 1 embodiment, a copolymer (hereinafter, sometimes referred to as a boron-containing acrylic resin) obtained by polymerizing a monomer mixture including more than 50 parts by weight of a (meth) acrylic monomer and more than 0 part by weight and less than 50 parts by weight of a monomer represented by formula (1) (hereinafter, sometimes referred to as a comonomer).
(wherein X represents a functional group containing a reactive group of at least 1 kind selected from the group consisting of a vinyl group, a (meth) acryloyl group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group, and R 1 And R 2 Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group or an optionally substituted heterocyclic group, R 1 And R 2 Optionally linked to each other to form a ring).
The boron-containing acrylic resin typically has a repeating unit represented by the following formula. The boron-containing acrylic resin has a substituent containing boron (for example, a repeating unit of k in the following formula) in a side chain by polymerizing a monomer mixture containing a comonomer represented by formula (1) and a (meth) acrylic monomer. Thus, when the iodine permeation inhibiting layer is disposed adjacent to the polarizer, the adhesion to the polarizer is improved. The substituent containing boron may be contained continuously (i.e., in a block form) in the boron-containing acrylic resin or may be contained randomly in the boron-containing acrylic resin.
(wherein R is 6 Represents an arbitrary functional group, and j and k represent an integer of 1 or more).
[ meth (acrylic) monomer ]
As the (meth) acrylic monomer, any appropriate (meth) acrylic monomer can be used. Examples thereof include a (meth) acrylate monomer having a linear or branched structure and a (meth) acrylate monomer having a cyclic structure.
Examples of the (meth) acrylate monomer having a linear or branched structure include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Methyl (meth) acrylate is preferably used. The (meth) acrylate monomer may be used in a single amount of 1 kind, or may be used in combination of 2 or more kinds.
Examples of the (meth) acrylate-based monomer having a cyclic structure include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) acrylate, m-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) acrylate, and mixtures thereof, Biphenyl group-containing monomers such as N- (meth) acryloyloxyethyl-o-biphenyl ═ carbamate, N- (meth) acryloyloxyethyl-p-biphenyl ═ carbamate, N- (meth) acryloyloxyethyl-m-biphenyl ═ carbamate, and o-phenylphenol glycidyl ether acrylate, terphenyl (meth) acrylate, and o-terphenyl oxyethyl (meth) acrylate. 1-adamantyl (meth) acrylate and dicyclopentyl (meth) acrylate are preferably used. By using these monomers, a polymer having a high glass transition temperature can be obtained. These monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
In addition, a silsesquioxane compound having a (meth) acryloyl group may be used instead of the (meth) acrylate monomer. By using the silsesquioxane compound, an acrylic polymer having a high glass transition temperature is obtained. Silsesquioxane compounds having various skeleton structures, for example, a cage structure, a ladder structure, a random structure, and the like are known. The silsesquioxane compound may have only 1 of these structures, or may have 2 or more of these structures. The silsesquioxane compound may be used in 1 kind alone, or in combination of 2 or more kinds.
Examples of the (meth) acryloyl group-containing silsesquioxane compound include MAC grade and AC grade of SQ series of tokyo synthesis corporation. The MAC-grade is a silsesquioxane compound containing a methacryloyl group, and specific examples thereof include MAC-SQ TM-100, MAC-SQ SI-20, and MAC-SQ HDM. The AC-grade is a silsesquioxane compound containing an acryloyl group, and specific examples thereof include AC-SQ TA-100 and AC-SQ SI-20.
The (meth) acrylic monomer is used in an amount of more than 50 parts by weight relative to 100 parts by weight of the monomer mixture.
< comonomers >
As the comonomer, a monomer represented by the above formula (1) is used. By using such a comonomer, a substituent containing boron is introduced into the side chain of the obtained polymer. The comonomer may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the aliphatic hydrocarbon group in the formula (1) include a linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent, a cyclic alkyl group having 3 to 20 carbon atoms, which may have a substituent, and an alkenyl group having 2 to 20 carbon atoms. Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms which may have a substituent, a naphthyl group having 10 to 20 carbon atoms which may have a substituent, and the like. Examples of the heterocyclic group include a 5-membered cyclic group or a 6-membered cyclic group containing at least 1 hetero atom, which may be substituted. In addition, R is 1 And R 2 Optionally linked to each other to form a ring. R is 1 And R 2 Preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
The reactive group included in the functional group represented by X is at least 1 selected from the group consisting of a vinyl group, a (meth) acryloyl group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group. Preferably, the reactive group is a (meth) acryloyl group and/or a (meth) acrylamide group. By having these reactive groups, when the iodine permeation inhibiting layer is disposed adjacent to the polarizer, the adhesion to the polarizer is further improved.
In 1 embodiment, the functional group represented by X is preferably a functional group represented by Z-Y-. Here, Z represents a functional group containing at least 1 reactive group selected from the group consisting of a vinyl group, (meth) acryloyl group, styryl group, (meth) acrylamide group, vinyl ether group, epoxy group, oxetanyl group, hydroxyl group, amino group, aldehyde group, and carboxyl group, and Y represents phenylene or alkylene group.
As the comonomer, specifically, the following compounds can be used.
The comonomer is used in a content of more than 0 parts by weight and less than 50 parts by weight with respect to 100 parts by weight of the monomer mixture. Preferably 0.01 to less than 50 parts by weight, more preferably 0.05 to 20 parts by weight, still more preferably 0.1 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight.
< acrylic resin containing lactone Ring Or the like >
In another embodiment, the acrylic resin has a repeating unit comprising a ring structure selected from the group consisting of a lactone ring unit, a glutaric anhydride unit, a glutarimide unit, a maleic anhydride unit, and a maleimide (N-substituted maleimide) unit. The repeating unit of the acrylic resin may include only 1 type of repeating unit including a ring structure, or may include 2 or more types.
The lactone ring unit is preferably represented by the following general formula (2):
in the general formula (2), R 2 、R 3 And R 4 Each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may also contain an oxygen atom. The acrylic resin may contain only a single lactone ring unit, or may contain R in the above general formula (2) 2 、R 3 And R 4 Different multiple lactone ring units. Acrylic resins having a lactone ring unit are described in, for example, Japanese patent application laid-open No. 2008-181078, the disclosure of which is incorporated herein by reference.
The glutarimide unit is preferably represented by the following general formula (3):
in the general formula (3), R 11 And R 12 Each independently represents hydrogen or C1-C8 alkyl, R 13 Represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms. In the general formula (3), R is preferably 11 And R 12 Each independently is hydrogen or methyl, R 13 Is hydrogen, methyl, butyl or cyclohexyl. More preferably, R 11 Is methyl, R 12 Is hydrogen, R 13 Is methyl. The acrylic resin may contain only a single glutarimide unit, or may contain R in the above general formula (3) 11 、R 12 And R 13 Different glutarimide units. Acrylic resins having a glutarimide unit are described in, for example, Japanese patent laid-open Nos. 2006-309033, 2006-317560, 2006-328334, 2006-337491, 2006-337492, 2006-337493 and 2006-337569, the disclosures of which are incorporated herein by reference. Here, regarding the glutaric anhydride unit, in addition to the above general formula (3)In (b) is represented by R 13 The above description of the glutarimide units applies except that the substituted nitrogen atom is an oxygen atom.
Since the structure of the maleic anhydride unit and the maleimide (N-substituted maleimide) unit is determined by name, detailed description thereof will be omitted.
The content ratio of the repeating unit including a ring structure in the acrylic resin is preferably 1 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, and still more preferably 20 mol% to 30 mol%. The acrylic resin contains, as a main repeating unit, a repeating unit derived from the above-mentioned (meth) acrylic monomer.
< epoxy resin >
As the epoxy resin, an epoxy resin having an aromatic ring is preferably used. By using an epoxy resin having an aromatic ring as the epoxy resin, adhesion to the polarizer can be improved when the iodine permeation inhibiting layer is disposed adjacent to the polarizer. Further, when the adhesive layer is disposed adjacent to the iodine permeation inhibiting layer, the anchoring force of the adhesive layer can be increased. Examples of the epoxy resin having an aromatic ring include bisphenol type epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; novolac type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin, and the like; and polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, epoxidized polyvinyl phenol, naphthol-type epoxy resins, naphthalene-type epoxy resins, biphenyl-type epoxy resins, and the like. Bisphenol a type epoxy resin, biphenyl type epoxy resin, bisphenol F type epoxy resin are preferably used. The epoxy resin may be used in combination of 2 or more than 1 kind.
The iodine permeation inhibiting layer can be formed by forming a coating film by applying an organic solvent solution of the resin as described above, and solidifying or thermally curing the coating film. As the organic solvent, any suitable organic solvent that can dissolve or uniformly disperse the acrylic resin can be used. Specific examples of the organic solvent include ethyl acetate, toluene, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone. The resin concentration of the solution is preferably 3 to 20 parts by weight with respect to 100 parts by weight of the solvent. If the resin concentration is such, a uniform coating film can be formed.
The solution can be applied to any suitable substrate, as well as to adjacent layers (e.g., polarizers, phase difference layers). When the solution is applied to a substrate, a solid substance (iodine permeation inhibiting layer) of a coating film formed on the substrate is transferred to an adjacent layer. When the solution is applied to the adjacent layer, the coating film is dried (solidified), whereby a protective layer is directly formed on the adjacent layer. Preferably, the solution is applied to the adjacent layer, and the protective layer is formed directly on the adjacent layer. With such a configuration, the adhesive layer or the pressure-sensitive adhesive layer required for transfer can be omitted, and thus the polarizing plate with the retardation layer can be made thinner. As a method of applying the solution, any appropriate method can be adopted. Specific examples thereof include roll coating, spin coating, wire bar coating, dip coating, die coating, curtain coating, spray coating, and doctor blade coating (comma coating).
The iodine permeation inhibiting layer can be formed by solidifying or thermally curing the coating film of the solution. The heating temperature for solidification or thermosetting is preferably 100 ℃ or lower, more preferably 50 to 70 ℃. If the heating temperature is within such a range, the polarizer can be prevented from being adversely affected. The heating time may vary depending on the heating temperature. The heating time may be, for example, 1 minute to 10 minutes.
The iodine permeation inhibiting layer (substantially, an organic solvent solution of the resin) may contain any appropriate additive according to the purpose. Specific examples of the additive include an ultraviolet absorber; leveling agent; hindered phenol-based, phosphorus-based, sulfur-based antioxidants; stabilizers such as light-resistant stabilizers, weather-resistant stabilizers and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; a near infrared ray absorber; flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, and antimony oxide; antistatic agents such as anionic, cationic and nonionic surfactants; colorants such as inorganic pigments, organic pigments, and dyes; an organic filler or an inorganic filler; a resin modifier; organic fillers and inorganic fillers; a plasticizer; a lubricant; an antistatic agent; a flame retardant; and the like. The kind, amount, combination, addition amount, and the like of the additives can be appropriately set according to the purpose.
E. Phase difference layer 2
As described above, the 2 nd retardation layer may be a so-called Positive C-plate (Positive C-plate) having refractive index characteristics showing a relationship of nz > nx ═ ny. By using the positive C plate as the 2 nd retardation layer, the oblique reflection can be prevented well, and the antireflection function can be made wide in viewing angle. In this case, the retardation Rth (550) in the thickness direction of the 2 nd retardation layer is preferably from-50 nm to-300 nm, more preferably from-70 nm to-250 nm, still more preferably from-90 nm to-200 nm, and particularly preferably from-100 nm to-180 nm. Here, "nx ═ ny" includes not only a case where nx and ny are strictly equal but also a case where nx and ny are substantially equal. That is, the in-plane retardation Re (550) of the 2 nd retardation layer may be less than 10 nm.
The 2 nd retardation layer having a refractive index characteristic of nz > nx ═ ny may be formed of any suitable material. The 2 nd retardation layer is preferably formed of a film containing a liquid crystal material fixed in homeotropic alignment. The liquid crystal material (liquid crystal compound) which can be homeotropically aligned may be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the liquid crystal compound and the method for forming the retardation layer include the liquid crystal compounds and the methods for forming the retardation layer described in paragraphs [0020] to [0028] of Japanese patent laid-open No. 2002-333642. In this case, the thickness of the 2 nd retardation layer is preferably 0.5 to 10 μm, more preferably 0.5 to 8 μm, and still more preferably 0.5 to 5 μm.
F. Conductive layer or isotropic substrate with conductive layer
The conductive layer can be formed by forming a metal oxide film on any suitable substrate by any suitable film forming method (for example, vacuum deposition, sputtering, CVD, ion plating, spraying, 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.
When the conductive layer contains a metal oxide, the thickness of the conductive layer is preferably 50nm or less, and more preferably 35nm or less. The lower limit of the thickness of the conductive layer is preferably 10 nm.
The conductive layer may be a constituent layer of the polarizing plate with a retardation layer by itself by transferring the substrate to the 1 st retardation layer (or the iodine permeation inhibiting layer or the 2 nd retardation layer in the case where the 2 nd retardation layer is present), or may be a laminate with the substrate (substrate with a conductive layer) laminated on the 1 st retardation layer (or the iodine permeation inhibiting layer or the 2 nd retardation layer in the case where the 2 nd retardation layer is present). Preferably, the substrate is optically isotropic, and therefore, 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 appropriate isotropic substrate can be used. Examples of the material constituting the isotropic base include a material having a resin not having a conjugated system such as a norbornene-based resin or an olefin-based resin as a main skeleton, and a material having a cyclic structure such as a lactone ring or a glutarimide ring in a main chain of an acrylic resin. When such a material is used, the retardation accompanying the molecular chain orientation can be suppressed to a small level when forming an isotropic base material. The thickness of the isotropic base material is preferably 50 μm or less, more preferably 35 μm or less. The lower limit of the thickness of the isotropic base material is, for example, 20 μm.
The conductive layer and/or the conductive layer of the isotropic substrate with a conductive layer may be patterned as necessary. By patterning, the conductive portion and the insulating portion can be formed. As a result, an electrode can be formed. The electrodes may function as touch sensor electrodes for sensing contact with the touch panel. As the patterning method, any appropriate method may be adopted. Specific examples of the patterning method include a wet etching method and a screen printing method.
G. Image display device
The polarizing plate with a retardation layer described in the above items A to F can be applied to an image display device. Therefore, embodiments of the present invention include an image display device using such a polarizing plate with a retardation layer. Typical examples of the image display device include a liquid crystal display device and an Electroluminescence (EL) display device (for example, an organic EL display device and an inorganic EL display device). The image display device according to the embodiment of the present invention includes the polarizing plate with a retardation layer described in the above items a to F on the viewing side. The polarizing plate with a retardation layer is laminated such that the retardation layer is on the image display unit (for example, liquid crystal unit, organic EL unit, inorganic EL unit) (polarizer is on the visual recognition side). Such an image display device is very thin, but has excellent reliability under a high-temperature and high-humidity environment, and an increase in reflectance is suppressed. Further, corrosion of the metal member is significantly suppressed. In one embodiment, the image display device has a curved shape (essentially a curved display screen) and/or is bendable or foldable.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The measurement method of each property is as follows. In the examples and comparative examples, "part(s)" and "%" are based on weight unless otherwise specified.
(1) Thickness of
The thickness of 10 μm or less was measured using an interferometric film thickness gauge (manufactured by tsukamur electronics co., ltd., product name "MCPD-3000"). The thickness of more than 10 μm was measured using a digital micrometer (product name "KC-351C" manufactured by Anritsu Co., Ltd.).
(2) Iodine and potassium absorption indices
The resin solutions used in examples and comparative examples were applied onto a 38 μm polyethylene terephthalate (PET) film so that the thickness after drying became 1 μm, and dried to obtain a resin layer/PET film test sample. The test sample thus obtained was immersed in a 10% aqueous solution of potassium iodide (90 parts by weight of pure water, 10 parts by weight of potassium iodide) adjusted to 23 ℃ for 24 hours. After the immersion, the test sample was taken out from the aqueous solution, and the water droplets on the surface were wiped off, and then the intensities (kcps) of iodine and potassium were obtained by fluorescent X-ray measurement of the surface of the resin layer. The intensity of the obtained iodine was taken as an iodine absorption index, and the intensity of potassium was taken as a potassium absorption index. The conditions for the fluorescent X-ray analysis are as follows.
An analysis device: fluorescent X-ray analysis apparatus (XRF) manufactured by Shikoku Motor industries, Ltd., product name "ZSX 100 e"
Test samples: round test specimen with diameter of 10mm
For the cathode: rhodium
Spectroscopic crystal: lithium fluoride
Excitation light energy: 40kV-90mA
Iodine measurement beam: I-LA
Quantitative method: FP method
2 θ angular peaks: 103.078deg (iodine), 136.847deg (potassium)
Measurement time: 40 seconds
(3) Increase in reflectivity
The polarizing plates with retardation layers obtained in examples and comparative examples were bonded to alkali-free glass as test samples. The test sample was placed on a reflecting plate having a reflectance of 80%, and the reflectance (%) was measured as a value at 550nm in SCI mode using a spectrophotometer (CM 700D manufactured by Konica Minolta Co., Ltd.) to obtain an initial reflectance. Further, the test sample was subjected to a reliability test (left to stand in an environment of 60 ℃ C. 90% RH for 500 hours, and then left to stand in an environment of 23 ℃ C. 55% RH for 24 hours), and then the reflectance was measured in the same manner as described above. The reflectance rise was calculated by the following equation.
Reflectance increase (%) -initial reflectance (%) -reflectance after reliability test (%)
Further, evaluation was performed according to the following criteria.
Good: the reflectivity rise is less than 0.50 percent
The allowable: the reflectivity is increased by more than 0.50 percent and less than 1.00 percent
Poor: the reflectivity is increased to more than 1.00%
(4) Corrosiveness of Metal (48 hours)
A silver nanowire solution (isopropyl alcohol (IPA) solution having a nanowire size of 115nm in diameter, a nanowire length of 20 to 50 μm, and a solid content of 0.5%) was coated on one surface of a 50 μm polyethylene terephthalate (PET) film by a wire bar so that the wet film thickness became 15 μm, and the film was dried in an oven at 100 ℃ for 5 minutes to form a silver nanowire coating film. Next, an overcoat liquid (solid content concentration: about 1%) containing 99 parts of methyl isobutyl ketone (MIBK), 1 part of pentaerythritol tetraacrylate (PETA) and 0.03 part of a photopolymerization initiator (product name "IRGACURE 907" manufactured by BASF corporation) was applied to the surface of the silver nanowire coating film with a wire bar so that the wet film thickness became 10 μm, and the resultant was dried in an oven at 100 ℃ for 5 minutes. Subsequently, the overcoat film was cured by irradiation with an active energy beam, thereby producing a metal thin film having a structure of PET thin film/silver nanowire layer/overcoat layer (thickness 100 nm). The metal thin film was bonded to a glass plate having a thickness of 0.5mm using an adhesive (15 μm) to obtain a metal thin film/adhesive/glass plate laminate. The electric resistance of the obtained laminate was measured by a non-contact resistance measuring instrument (product name "EC-80" manufactured by Napson corporation), and the result was 50. omega./□.
The polarizing plates with retardation layers obtained in examples and comparative examples were attached to the top coat surface of the metal thin film of the laminate to prepare test samples. The resistance value of the test sample was measured by a noncontact resistance meter and used as an initial resistance value. Further, after the test was subjected to a reliability test (48 hours of standing in an environment of 85 ℃ C. 85% RH, and then 2 hours of standing in an environment of 23 ℃ C. 55% RH), the resistance value was measured in the same manner as described above. The rate of increase in resistance was calculated by the following equation. When the measured value (resistance value) is larger than the measurement limit (1000 Ω/□) of the noncontact resistance measuring device, the measured value is assumed to be 1500 Ω/□.
The resistance value increase rate (%) { (resistance value after reliability test-initial resistance value)/initial resistance value } × 100
Further, evaluation was performed according to the following criteria.
Good: the rise rate of the resistance value is less than 200 percent
Poor: the rate of increase of the resistance value is more than 200%
(5) Corrosiveness of metal (200 hours)
The polarizing plates with retardation layers obtained in examples and comparative examples were bonded to the overcoat layer-formed surface of the metal thin film of the laminate obtained in (2) to prepare a test sample. The resistance value of the test sample was measured with a noncontact resistance meter and used as an initial resistance value. Further, the test sample was subjected to a reliability test (after leaving the test sample in an atmosphere of 85 ℃. 85% RH for 200 hours, then in an atmosphere of 23 ℃. 55% RH for 2 hours), and then the resistance value was measured in the same manner as described above. The rate of increase in the resistance value was calculated by the following equation. When the measured value (resistance value) is larger than the measurement limit (1000 Ω/□) of the noncontact resistance measuring device, the measured value is assumed to be 1500 Ω/□.
The rate of increase (%) in resistance value { (resistance value after reliability test-initial resistance value)/initial resistance value } × 100
Further, evaluation was performed according to the following criteria.
And (3) excellent: the rise rate of the resistance value is less than 200 percent
Good: the rise rate of the resistance value is more than 200 percent and less than 2000 percent
Poor: the rate of increase of the resistance value is more than 2000%
[ example 1]
1. Fabrication of polarizing elements
As the thermoplastic resin substrate, a long-sized amorphous ethylene terephthalate isophthalate copolymer film (thickness: 100 μm) having a water absorption of 0.75% and a Tg of about 75 ℃ was used. One surface of the resin substrate is subjected to corona treatment.
In the following, with 9: 1A PVA resin composition comprising 100 parts by weight of a PVA resin containing polyvinyl alcohol (having a polymerization degree of 4200 and a saponification degree of 99.2 mol%) and an acetoacetyl-modified PVA (trade name "GOHSEFIMER Z410" manufactured by Nippon synthetic chemical Co., Ltd.) was dissolved in water to prepare an aqueous PVA solution (coating solution).
The aqueous PVA 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 obtained laminate was subjected to uniaxial stretching with the free end in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ℃ (air-assisted stretching treatment).
Next, the laminate was immersed in an insolubilization bath (aqueous boric acid solution prepared by adding 4 parts by weight of boric acid to 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (insolubilization treatment).
Next, 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 ℃, the resultant polarizer was immersed for 60 seconds while adjusting the concentration so that the monomer transmittance (Ts) of the polarizer finally obtained became 43.0% or more (dyeing treatment).
Next, the substrate was immersed for 30 seconds in a crosslinking bath (aqueous boric acid solution prepared by adding 3 parts by weight of potassium iodide to 100 parts by weight of water and 5 parts by weight of boric acid) at a liquid temperature of 40 ℃ (crosslinking treatment).
Thereafter, while immersing the laminate in an aqueous boric acid solution (boric acid concentration of 4.0 wt%, potassium iodide concentration of 5 wt%) having a liquid temperature of 70 ℃, uniaxial stretching was performed so that the total stretching ratio became 5.5 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds (underwater stretching treatment).
Thereafter, the laminate was immersed in a cleaning bath (aqueous solution prepared by adding 4 parts by weight of potassium iodide to 100 parts by weight of water) at a liquid temperature of 20 ℃ (cleaning treatment).
Thereafter, the sheet was dried in an oven maintained at 90 ℃ and contacted with a heated roll made of SUS maintained at a surface temperature of 75 ℃ for about 2 seconds (drying shrinkage treatment). The shrinkage in the width direction of the laminate due to the drying shrinkage treatment was 5.2%.
Thus, a polarizing element having a thickness of 5 μm was formed on the resin substrate.
2. Manufacture of polarizing plate
An HC-COP film was bonded as a protective layer to the surface (the surface opposite to the resin substrate) of the polarizer obtained above via an ultraviolet-curable adhesive. Specifically, the coating was performed so that the total thickness of the curable adhesive became 1.0 μm, and the lamination was performed using a roll mill. Then, the adhesive is cured by irradiating UV light from the protective layer side. The HC-COP film was a Cycloolefin (COP) film (product name "ZF 12" manufactured by ZEON corporation, japan, thickness 25 μm) on which a Hard Coat (HC) layer (thickness 2 μm) was formed, and was laminated so that the COP film was on the polarizer side. Next, the resin substrate was peeled off to obtain a polarizing plate having a structure of a protective layer (HC layer/COP film)/adhesive layer/polarizing material.
3. Production of 1 st oriented cured layer and 2 nd oriented cured layer constituting phase difference layer
A liquid crystal composition (coating liquid) was prepared by dissolving 10g of a polymerizable liquid crystal (product name: Paliocolor LC242 manufactured by BASF) exhibiting a nematic liquid crystal phase and 3g of a photopolymerization initiator (product name: IRGACURE 907 manufactured by BASF) for the polymerizable liquid crystal compound in 40g of toluene.
The surface of a polyethylene terephthalate (PET) film (38 μm in thickness) was rubbed with a rubbing cloth to carry out an orientation treatment. The orientation treatment was performed in a direction of 15 ° with respect to the absorption axis direction of the polarizer when viewed from the visual recognition side when the polarizing plate was laminated. The liquid crystal coating liquid was applied to the alignment-treated surface by a bar coater, and heated and dried at 90 ℃ for 2 minutes, thereby aligning the liquid crystal compound. Using a metal halide lamp at 1mJ/cm 2 The liquid crystal layer thus formed is irradiated with light and cured, thereby forming a liquid crystal alignment cured layer a on the PET film. The thickness of the liquid crystal alignment cured layer A was 2.5 μm, and the in-plane retardation Re (550) was 270 nm. Further, the liquid crystal alignment cured layer a has a refractive index distribution of nx > ny ═ nz.
A liquid crystal alignment cured layer B was formed on the PET film in the same manner as described above, except that the coating thickness was changed and the alignment treatment direction was set to a direction of 75 ° with respect to the absorption axis direction of the polarizer when viewed from the viewing side. The thickness of the liquid crystal alignment cured layer B was 1.5 μm, and the in-plane retardation Re (550) was 140 nm. Further, the liquid crystal alignment cured layer B has a refractive index distribution of nx > ny ═ nz.
4. Formation of retardation layer
The liquid crystal alignment cured layer a and the liquid crystal alignment cured layer B obtained in the above 3 were sequentially transferred onto the polarizer surface of the polarizing plate obtained in the above 2. At this time, transfer (bonding) was performed so that the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal alignment cured layer a became 15 ° and the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal alignment cured layer B became 75 °. The respective transfer (bonding) was performed by using the ultraviolet curing adhesive (thickness 1.0 μm) used in the above 2. In this way, a laminate having a structure of a protective layer (HC layer/COP film)/adhesive layer/polarizer/adhesive layer/retardation layer (1 st liquid crystal alignment cured layer/adhesive layer/2 nd liquid crystal alignment cured layer) was produced.
5. Manufacture of polarizing plate with phase difference layer
20 parts of an acrylic resin (product name "B-811", Tg: 110 ℃ C., Mw: 40000, manufactured by Nanhima chemical Co., Ltd.) was dissolved in 80 parts of methyl ethyl ketone to obtain a resin solution (20%). The resin solution was applied to the surface of the 2 nd liquid crystal alignment cured layer of the laminate obtained in the above 4. by a wire bar, and the coated film was dried at 60 ℃ for 5 minutes to form an iodine permeation-inhibiting layer (thickness 0.5 μm) as a solid of the coated film of the organic solvent solution of the resin. The iodine absorption index of the iodine permeation inhibiting layer was 0.0046, and the potassium absorption index was 0.0087. Then, a pressure-sensitive adhesive layer (thickness: 15 μm) was provided on the surface of the iodine permeation inhibitor layer to obtain a retardation layer-equipped polarizing plate having a structure of a protective layer (HC layer/COP film)/pressure-sensitive adhesive layer/polarizing plate/pressure-sensitive adhesive layer/retardation layer (1 st liquid crystal alignment cured layer/pressure-sensitive adhesive layer/2 nd liquid crystal alignment cured layer)/iodine permeation inhibitor layer/pressure-sensitive adhesive layer. The total thickness of the obtained polarizing plate with a retardation layer was 39.5. mu.m. The obtained polarizing plate with a retardation layer was subjected to the evaluations (3) to (5) above. Further, the metal corrosion was compared with comparative example 1 (described later) in which no iodine permeation inhibiting layer was formed. The results are shown in tables 1 and 2.
[ example 2]
97.0 parts of methyl methacrylate (MMA, product name "methyl methacrylate monomer" manufactured by Fuji film and Wako pure chemical industries, Ltd.), 3.0 parts of a comonomer represented by the above general formula (1e), and 0.2 part of a polymerization initiator (Fuji film and Wako pure chemical industries, Ltd.; product name "2, 2' -azobis (isobutyronitrile)") were dissolved in 200 parts of toluene. Then, the mixture was heated to 70 ℃ under a nitrogen atmosphere and subjected to a polymerization reaction for 5.5 hours to obtain a boron-containing acrylic resin solution (solid content concentration: 33%). The resulting boron-containing acrylic polymer had a Tg of 110 ℃ and a Mw of 80000. A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the boron-containing acrylic polymer was used in place of the acrylic resin "B-811" and the thickness of the iodine permeation inhibiting layer was set to 0.3 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
[ example 3]
A polarizing plate with a retardation layer was produced in the same manner as in example 2, except that the thickness of the iodine permeation inhibiting layer was 0.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
[ example 4]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that a thermoplastic epoxy resin (product name "jER (registered trademark) 1256B 40", Tg: 100 ℃, Mw: 45000, manufactured by Mitsubishi Chemical Co.) was used in place of the acrylic resin "B-811". The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
[ example 5]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that a thermoplastic epoxy resin (product name "jER (registered trademark) YX7200B 35", Tg: 150 ℃, Mw: 30000, manufactured by Mitsubishi Chemical co.) was used in place of the acrylic resin "B-811" and the thickness of the iodine permeation inhibiting layer was set to 0.3 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
[ example 6]
A polarizing plate with a retardation layer was produced in the same manner as in example 5, except that the thickness of the iodine permeation inhibiting layer was 0.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
[ example 7]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that a blend of 15 parts of "B-811" and 85 parts (in solid content conversion) of a thermoplastic epoxy resin (product name "jER (registered trademark) YX6954BH30, manufactured by Mitsubishi Chemical co.) was used instead of the acrylic resin" B-811 ". The blend had a Tg of 125 ℃ and a Mw of 38000. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
[ example 8]
The polarizing plate having the composition of the protective layer (HC layer/COP film)/adhesive layer/polarizing material obtained in example 1 was coated with the resin blend used in example 7 on the polarizing material side and dried to form an iodine permeation-inhibiting layer (thickness 0.5 μm) in the form of a solid of a coating film of an organic solvent solution of the resin. The liquid crystal alignment cured layer a and the liquid crystal alignment cured layer B were sequentially transferred onto the surface of the iodine permeation-inhibiting layer in the same manner as in example 1, and a retardation layer-equipped polarizing plate having a structure of a protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine permeation-inhibiting layer/adhesive layer/retardation layer (1 st liquid crystal alignment cured layer/adhesive layer/2 nd liquid crystal alignment cured layer)/adhesive layer was obtained. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 2.
[ example 9]
A laminate having a configuration of a protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine permeation prevention layer was produced in the same manner as in example 8, except that the boron-containing acrylic polymer in example 2 was used. Next, a polarizing plate with a retardation layer having a configuration of protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine permeation inhibiting layer/adhesive layer/retardation layer (1 st liquid crystal alignment cured layer/adhesive layer/2 nd liquid crystal alignment cured layer)/iodine permeation inhibiting layer/adhesive layer was obtained in the same manner as in example 1, except that a blend of 15 parts of the boron-containing acrylic polymer in example 2 and 85 parts (in solid content conversion) of thermoplastic epoxy resin (product name "jER (registered trademark) YX6954BH30, manufactured by Mitsubishi Chemical co. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 2.
[ example 10]
A polarizing plate with a retardation layer was obtained in the same manner as in example 9 except that a blend of 15 parts of the boron-containing acrylic polymer obtained in example 2 and 85 parts (in terms of solid content) of a thermoplastic epoxy resin (product of Mitsubishi Chemical co, product name "jER (registered trademark) YX6954BH 30") was used as the iodine permeation suppressing layer provided between the polarizing plate and the retardation layer and in a position adjacent to the polarizing plate. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 2.
[ example 11]
A polarizing plate with a retardation layer having a configuration of protective layer (HC layer/COP film)/adhesive layer/polarizing material/adhesive layer/iodine permeation inhibiting layer/retardation layer (1 st liquid crystal alignment cured layer/adhesive layer/2 nd liquid crystal alignment cured layer)/iodine permeation inhibiting layer/adhesive layer was obtained in the same manner as in example 10, except that an iodine permeation inhibiting layer formed between the polarizer and the retardation layer at a position adjacent to the polarizer was formed at a position between the polarizer and the retardation layer adjacent to the retardation layer. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 2.
[ example 12]
A polarizing plate with a retardation layer having a structure of a protective layer (HC layer/COP film)/adhesive layer/polarizing material/iodine permeation inhibiting layer/adhesive layer/iodine permeation inhibiting layer/retardation layer (1 st liquid crystal alignment cured layer/adhesive layer/2 nd liquid crystal alignment cured layer)/iodine permeation inhibiting layer/pressure-sensitive adhesive layer was obtained in the same manner as in example 11, except that an iodine permeation inhibiting layer was further formed between the polarizer and the retardation layer at a position adjacent to the polarizer. The total thickness of the obtained polarizing plate with a retardation layer was 40.5. mu.m. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 2.
Comparative example 1
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the iodine permeation-inhibiting layer was not formed. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
Comparative example 2
A polarizing plate with a retardation layer was produced in the same manner as in example 1 except that an acrylic resin "B-723" (Tg: 54 ℃ C., Mw: 200000, manufactured by Nanhima chemical Co., Ltd.) was used in place of the acrylic resin "B-811". The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
Comparative example 3
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that a photocurable epoxy resin (product name "jER (registered trademark) 828", manufactured by Mitsubishi Chemical co., ltd.) was used as a photopolymerization initiator instead of the acrylic resin "B-811", and "CPI 100P", manufactured by San-Apro ltd. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
Comparative example 4
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that a PVA-based resin (product name "GOHSENOL Z200", Tg: 80 ℃, Mw: 8800, manufactured by Mitsubishi Chemical Co.) was used in place of the acrylic resin "B-811". The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
[ reference example 1]
1. Manufacture of polarizing plate
A polarizing plate having a constitution of a protective layer (HC layer/COP film)/polarizer was obtained in the same manner as in example 1.
2. Production of retardation film constituting retardation layer
2-1 polymerization of polyester carbonate-based resin
Polymerization was carried out using a batch polymerization apparatus composed of 2 vertical reactors each equipped with a stirring blade and a reflux condenser controlled to 100 ℃. Adding bis [9- (2-phenoxycarbonylethyl) fluoren-9-yl]29.60 parts by mass (0.046mol) of methane, 29.21 parts by mass (0.200mol) of Isosorbide (ISB), 42.28 parts by mass (0.139mol) of Spiroglycol (SPG), 63.77 parts by mass (0.298mol) of diphenyl carbonate (DPC), and 1.19 × 10 parts by mass of calcium acetate monohydrate as a catalyst -2 Parts by mass (6.78X 10) -5 mol). After the inside of the reactor was replaced with nitrogen under reduced pressure, the reactor was heated with a heat medium, and stirring was started at a point when the internal temperature reached 100 ℃. After 40 minutes from the start of the temperature increase, the internal temperature was set to 220 ℃ and the pressure reduction was started while controlling the temperature so as to be maintained, so that the pressure became 13.3kPa after 90 minutes from the time when the temperature reached 220 ℃. Phenol vapor by-produced in association with the polymerization reaction was introduced into a reflux condenser at 100 ℃ to return a small amount of monomer components contained in the phenol vapor to the reactor, and the phenol vapor that was not condensed was introduced into a condenser at 45 ℃ to be recovered. After nitrogen gas was introduced into the 1 st reactor and the pressure was once returned to atmospheric pressure, the reaction liquid after oligomerization in the 1 st reactor was transferred to the 2 nd reactor. Subsequently, the temperature and pressure in the 2 nd reactor were increased to 240 ℃ for 50 minutes, and the internal temperature and the pressure were 0.2 kPa. Thereafter, the polymerization was carried out until a predetermined stirring power was reached. At the time point when the predetermined power was reached, nitrogen gas was introduced into the reactor to recover the pressure, and the polyester carbonate-based resin thus produced was extruded into water, and strands were cut to obtain pellets.
2-2. production of retardation film
After the obtained polyester carbonate resin (pellets) was dried under vacuum at 80 ℃ for 5 hours, a long resin film having a thickness of 135 μm was produced using a film forming apparatus equipped with a single screw extruder (manufactured by Toshiba machine Co., Ltd., cylinder set temperature: 250 ℃), a T-die (width 200mm, set temperature: 250 ℃), a cooling roll (set temperature: 120 to 130 ℃) and a winder. The resulting 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 53 μm. The obtained retardation film had Re (550) of 141nm, Re (450)/Re (550) of 0.82, and an Nz coefficient of 1.12.
3. Manufacture of polarizing plate with phase difference layer
The retardation film obtained in item 2 above was bonded to the surface of the polarizer of the polarizing plate obtained in item 1 above via an acrylic adhesive (thickness 5 μm). At this time, the polarizer and the retardation film were bonded so that the absorption axis of the polarizer and the slow axis of the retardation film form an angle of 45 °. Further, the same adhesive layer as in example 1 was provided on the surface of the retardation layer. Thus, a polarizing plate with a retardation layer having a structure of protective layer/adhesive layer/polarizing material/adhesive layer/retardation layer (stretched film of resin film)/adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 91 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in tables 1 and 2.
[ Table 1]
[ Table 2]
The blend is a blend of acrylic resin and epoxy resin
Position a indicates a position between the retardation layer and the adhesive layer, position B indicates a position between the polarizing member and the retardation layer and adjacent to the polarizing member,
the position C indicates a position between the polarizer and the retardation layer and adjacent to the retardation layer.
[ evaluation ]
As is clear from table 1, in the polarizing plate with a retardation layer according to the example of the present invention, the iodine permeation inhibiting layer having an iodine absorption index of a predetermined value or less was formed, and thus the increase in reflectance in a high-temperature and high-humidity environment was significantly inhibited. In addition, by forming such an iodine permeation inhibiting layer, the metal corrosion under a high-temperature and high-humidity environment can be significantly inhibited. Further, as is clear from reference example 1, such a problem is unique to a polarizing plate with a retardation layer having a very thin thickness, which is increased in reflectance and has metal corrosiveness.
As is clear from table 2, in the polarizing plates with retardation layers of examples 9 to 12 of the present invention, the iodine permeation inhibiting layers were 2 or 3, and the metal corrosion was significantly inhibited even when the polarizing plates were exposed to a high-temperature and high-humidity environment for a long period of time (200 hours). Therefore, it is understood that the polarizing plates with retardation layers according to examples 9 to 12 of the present invention significantly suppressed corrosion of metal members when applied to image display devices.
Industrial applicability
The polarizing plate with a retardation layer of the present invention can be suitably used as a circular 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 piece
12: protective layer
20: retardation layer
30: adhesive layer
40: iodine permeation inhibitor
100: polarizing plate with phase difference layer
101: polarizing plate with phase difference layer
102: polarizing plate with phase difference layer
103: polarizing plate with phase difference layer
104: polarizing plate with phase difference layer
105: polarizing plate with phase difference layer
Claims (14)
1. A polarizing plate with a retardation layer comprises a polarizing plate comprising a polarizer, a retardation layer and an adhesive layer in this order from a visual recognition side;
the phase difference layer is an orientation curing layer of a liquid crystal compound with a circular polarization function or an elliptical polarization function;
an iodine permeation inhibiting layer which is a solid or heat-cured product of a coating film of an organic solvent solution of a resin is provided between the polarizer and the adhesive layer;
the iodine absorption index of the iodine permeation inhibiting layer is 0.015 or less.
2. The polarizing plate with a retardation layer according to claim 1, wherein the iodine permeation suppression layer is provided between the polarizing material and the retardation layer.
3. The polarizing plate with a retardation layer according to claim 1, wherein the iodine permeation suppression layer is provided between the retardation layer and the adhesive layer.
4. The polarizing plate with a retardation layer according to claim 1, wherein the iodine permeation inhibitor layer comprises 2 or more layers between the polarizer and the adhesive layer.
5. The polarizing plate with a retardation layer according to any one of claims 1 to 4, wherein the iodine permeation suppression layer has a potassium absorption index of 0.015 or less.
6. The polarizing plate with a retardation layer according to any one of claims 1 to 5, wherein a glass transition temperature of a resin constituting the iodine permeation suppression layer is 85 ℃ or more, and a weight average molecular weight Mw is 25000 or more.
7. The polarizing plate with a retardation layer according to claim 6, wherein the resin constituting the iodine permeation inhibiting layer comprises a copolymer obtained by polymerizing a monomer mixture comprising more than 50 parts by weight of a (meth) acrylic monomer and more than 0 part by weight and less than 50 parts by weight of a monomer represented by formula (1),
wherein X represents a functional group containing a reactive group of at least 1 kind selected from the group consisting of a vinyl group, a (meth) acryloyl group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group and a carboxyl group, and R 1 And R 2 Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group or an optionally substituted heterocyclic group, R 1 And R 2 Optionally joined to each other to form a ring.
8. The polarizing plate with a retardation layer according to any one of claims 1 to 7, wherein the retardation layer is a single layer,
the Re (550) of the phase difference layer is 100 nm-190 nm,
the slow axis of the phase difference layer and the absorption axis of the polarizer form an angle of 40-50 degrees.
9. The polarizing plate with a phase difference layer according to any one of claims 1 to 7, wherein the phase difference layer has a laminated structure of an alignment cured layer of a 1 st liquid crystal compound and an alignment cured layer of a 2 nd liquid crystal compound;
the Re (550) of the orientation cured layer of the 1 st liquid crystal compound is 200nm to 300nm, and the angle formed by the slow axis and the absorption axis of the polarizer is 10 DEG to 20 DEG;
the Re (550) of the alignment cured layer of the 2 nd liquid crystal compound is 100 to 190nm, and the angle formed by the slow axis and the absorption axis of the polarizer is 70 to 80 degrees.
10. The polarizing plate with a retardation layer according to any one of claims 1 to 9, wherein an additional retardation layer having a refractive index characteristic exhibiting a relationship of nz > nx ═ ny is further provided between the retardation layer and the adhesive layer.
11. The polarizing plate with a retardation layer according to any one of claims 1 to 10, further comprising a conductive layer or an isotropic substrate with a conductive layer between the iodine permeation suppressing layer and the adhesive layer.
12. The polarizing plate with a retardation layer according to any one of claims 1 to 11, which has a total thickness of 60 μm or less.
13. An image display device comprising the polarizing plate with a retardation layer according to any one of claims 1 to 12.
14. The image display device according to claim 13, which is an organic electroluminescent display device or an inorganic electroluminescent display device.
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| JP2020160883A JP7114665B2 (en) | 2020-01-24 | 2020-09-25 | Polarizing plate with retardation layer and image display device using the same |
| PCT/JP2020/039432 WO2021149312A1 (en) | 2020-01-24 | 2020-10-20 | Retardation-layer-equipped polarizing plate and image display device using same |
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| WO2020111232A1 (en) * | 2018-11-29 | 2020-06-04 | 日東電工株式会社 | Polarizing film with adhesive layer, and image display device |
| JP2020126226A (en) * | 2019-02-04 | 2020-08-20 | 住友化学株式会社 | Polarizing plate and display device |
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