CN115804264A - 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
- Publication number
- CN115804264A CN115804264A CN202180045429.0A CN202180045429A CN115804264A CN 115804264 A CN115804264 A CN 115804264A CN 202180045429 A CN202180045429 A CN 202180045429A CN 115804264 A CN115804264 A CN 115804264A
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- Prior art keywords
- layer
- polarizing plate
- resin
- retardation
- protective layer
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Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- 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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding 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
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/55—Liquid crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
- B32B2329/04—Polyvinylalcohol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polarising Elements (AREA)
Abstract
The invention provides a polarizing plate with a retardation layer, which can inhibit cracks from generating during heating. The polarizing plate with a retardation layer of the present invention comprises a polarizing plate comprising a polarizer made of a polyvinyl alcohol resin film containing a dichroic material and a protective layer disposed on one side of the polarizer, and a retardation layer. The retardation layer is an alignment cured layer of a liquid crystal compound, and the protective layer has a thickness of 10 μm or less. In one embodiment, the polarizer satisfies the following formula (1) where x% is a monomer transmittance and y is a birefringence of the polyvinyl alcohol resin. In one embodiment, the polarizer satisfies the following formula (2) when the monomer transmittance is x% and the in-plane retardation of the polyvinyl alcohol resin film is znm. In one embodiment, the polarizer satisfies the following formula (3) where x% is a monomer transmittance and f is an orientation function of the polyvinyl alcohol resin. y < -0.011x +0.525 (1) z < -60x +2875 (2) f < -0.018x +1.11 (3).
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, a polarizing plate and a retardation plate are used in an image display device. In practice, a polarizing plate with a retardation layer, which is formed by integrating a polarizing plate and a retardation plate, is widely used (for example, patent document 1). Recently, as the demand for thinner image display devices has increased, the demand for thinner polarizing plates with retardation layers has also increased. Further, in recent years, demands for a curved image display device and/or a bendable or bendable image display device are increasing. Therefore, further thinning and further softening are also required for the polarizing plate and the polarizing plate with a retardation layer.
As a method for thinning the polarizing plate, there have been proposed a method of thinning the protective layer and laminating the protective layer only on one side of the polarizer. However, these methods are insufficient for protecting the polarizer and have room for improvement in durability. Further, there are problems as follows: by the heat treatment, cracks are likely to occur not only in the polarizer but also in the polarizing plate.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2001-343521
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above conventional problems, and a main object of the present invention is to provide a polarizing plate with a retardation layer, which can suppress the occurrence of cracks during heating.
Means for solving the problems
The polarizing plate with a retardation layer according to the embodiment of the present invention includes a polarizing plate including a polarizer made of a polyvinyl alcohol resin film containing a dichroic material and a protective layer disposed on one side of the polarizer, and a retardation layer. The retardation layer is an alignment cured layer of a liquid crystal compound, and the protective layer has a thickness of 10 μm or less. The polarizer satisfies the following formula (1) when the monomer transmittance is x% and the birefringence of the polyvinyl alcohol resin is y.
y<-0.011x+0.525 (1)
The polarizing plate with a retardation layer according to another embodiment of the present invention includes a polarizing plate including a polarizer made of a polyvinyl alcohol resin film containing a dichroic material and a protective layer disposed on one side of the polarizer, and the retardation layer. The retardation layer is an alignment cured layer of a liquid crystal compound, and the protective layer has a thickness of 10 μm or less. The polarizer satisfies the following formula (2) when the monomer transmittance is x% and the in-plane retardation of the polyvinyl alcohol resin film is znm.
z<-60x+2875 (2)
A polarizing plate with a retardation layer according to still another embodiment of the present invention includes a polarizing plate including a polarizer made of a polyvinyl alcohol resin film containing a dichroic material and a protective layer disposed on one side of the polarizer, and the retardation layer. The retardation layer is an alignment cured layer of a liquid crystal compound, and the protective layer has a thickness of 10 μm or less. The polarizer satisfies the following formula (3) when the monomer transmittance is x% and the orientation function of the polyvinyl alcohol resin is f.
f<-0.018x+1.11 (3)
In one embodiment, the total thickness of the polarizing plate with a retardation layer is 30 μm or less.
In one embodiment, the polarizer has a thickness of 10 μm or less.
In one embodiment, the polarizing material has a monomer transmittance of 40.0% or more and a degree of polarization of 99.0% or more.
In one embodiment, the protective layer is composed of at least 1 selected from the group consisting of a solid of a coating film of an organic solvent solution of a thermoplastic (meth) acrylic resin, a solid of a photocationic cured product of an epoxy resin, and a solid of a coating film of an organic solvent solution of an epoxy resin.
In one embodiment, the thermoplastic (meth) acrylic resin has at least 1 repeating unit selected from the group consisting of a lactone ring unit, a glutaric anhydride unit, a glutarimide unit, a maleic anhydride unit, and a maleimide unit.
In one embodiment, the protective layer is a photocationic cured product of an epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton.
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.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there is provided a polarizing plate with a retardation layer, comprising: a polarizer having a specific relationship between a monomer transmittance and a birefringence of polyvinyl alcohol (PVA) or an in-plane retardation of a PVA resin film; a protective layer having a thickness of 10 μm or less; and a phase difference layer of an alignment cured layer of a liquid crystal alignment compound. By forming such a polarizing plate with a retardation layer, it is possible to reduce the thickness of the polarizing plate with a retardation layer and to suppress the occurrence of cracks during heating. Further, the occurrence of cracks at the time of bending can be suppressed.
Drawings
Fig. 1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to 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 diagram showing an example of drying shrinkage treatment using a heating roller in the method for manufacturing a polarizing plate used for a polarizing plate with a retardation layer according to the present invention.
Detailed Description
Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
(definition 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 the in-plane refractive index is maximum (i.e., the slow axis direction), "ny" is a refractive index in a direction orthogonal to the slow axis in the plane (i.e., the fast axis direction), and "nz" is a refractive index in the thickness direction.
(2) In-plane retardation (Re)
"Re (. Lamda)" is an in-plane retardation measured at 23 ℃ with light having a wavelength of λ nm. For example, "Re (550)" is an in-plane retardation measured at 23 ℃ with light having a wavelength of 550 nm. For Re (λ), assuming that the thickness of the layer (thin film) is d (nm), the following formula is used: re (λ) = (nx-ny) × d.
(3) Retardation in thickness direction (Rth)
"Rth (. Lamda.)" is a phase difference in the thickness direction measured at 23 ℃ with light having a wavelength of. Lamda.nm. For example, "Rth (550)" is a phase difference in the thickness direction measured at 23 ℃ with light having a wavelength of 550 nm. With respect to Rth (λ), when the thickness of the layer (film) is d (nm), by the formula: rth (λ) = (nx-nz) × d.
(4) Coefficient of Nz
The Nz coefficient is determined by Nz = Rth/Re.
(5) Angle of rotation
When an angle is referred to in the present specification, the angle includes both clockwise and counterclockwise with respect to the reference direction. Thus, for example, "45" means ± 45 °.
A. Integral structure of polarizing plate with phase difference layer
Fig. 1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention. The polarizing plate 100 with a retardation layer according to the present embodiment includes a polarizing plate 10 and a retardation layer 20. The polarizing plate 10 includes: a polarizer 11, a 1 st protective layer 12 disposed on one side of the polarizer 11, and a 2 nd protective layer 13 disposed on the other side of the polarizer 11. Depending on the purpose, one of the 1 st protective layer 12 and the 2 nd protective layer 13 may be omitted. For example, when the retardation layer 20 can also function as a protective layer for the polarizer 11, the 2 nd protective layer 13 can be omitted. The retardation layer 20 is laminated on the polarizer 11 or the 2 nd protective layer 13 via an arbitrary suitable adhesive layer or adhesive layer (not shown). In the embodiment of the present invention, the polarizer 11 is formed of a polyvinyl alcohol resin film containing a dichroic material, and satisfies the following formula (1) when the monomer transmittance is x% and the birefringence of the polyvinyl alcohol resin is y. In one embodiment of the present invention, the polarizer 11 is made of a polyvinyl alcohol resin film containing a dichroic material, and satisfies the following formula (2) when the monomer transmittance is x% and the in-plane retardation of the polyvinyl alcohol resin film is znm. In one embodiment, the polarizer 10 satisfies the following formula (3) where the monomer transmittance is x% and the orientation function of the polyvinyl alcohol resin constituting the polarizer is f.
y<-0.011x+0.525 (1)
z<-60x+2875 (2)
f<-0.018x+1.11 (3)
Fig. 2 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention. As shown in fig. 2, in the polarizing plate with retardation layer 101 according to another embodiment, another retardation layer 50 and/or a conductive layer or an isotropic substrate with conductive layer 60 may be provided. The other retardation layer 50 and the conductive layer or the isotropic substrate with a conductive layer 60 are typically provided outside the retardation layer 20 (on the side opposite to the polarizing plate 10). Another phase difference layer is representative of a refractive index characteristic showing a relationship of nz > nx = ny. The other retardation layer 50 and the conductive layer or the isotropic substrate with a conductive layer 60 are typically provided in this order from the side of the retardation layer 20. The other retardation layer 50 and the conductive layer or the isotropic substrate with conductive layer 60 are typically any layers provided as needed, and either one 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, a polarizing plate with a retardation layer is applied to a so-called internal 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.
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. In the embodiment of the present invention, the 1 st retardation layer 20 is an alignment cured layer of a liquid crystal compound. The 1 st retardation layer 20 may be a single layer of the orientation cured layer as shown in fig. 1 and 2, or may have a laminated structure of a 1 st orientation cured layer 21 and a 2 nd orientation cured layer 22 as shown in fig. 3.
The above embodiments may be combined as appropriate, and a change which is obvious in the art may be applied to the constituent elements in the above embodiments. For example, the polarizing plate with retardation layer 102 of fig. 3 may be further provided with a 2 nd retardation layer 50 and/or a conductive layer or an isotropic substrate with conductive layer 60. For example, the configuration in which the isotropic substrate 60 with a conductive layer is provided outside the 2 nd retardation layer 50 may be replaced with an optically equivalent configuration (for example, a laminate of the 2 nd retardation layer and the conductive layer).
The polarizing plate with a retardation layer according to the embodiment of the present invention may further include another retardation layer. The optical properties (for example, 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 of the present invention may be in the form of a single sheet or a long sheet. The term "elongated shape" as used herein means an elongated shape having a length much longer than a width, and includes, for example, an elongated shape having a length 10 times or more, preferably 20 times or more, as long as a width. The long polarizing plate with the retardation layer may be rolled up.
In practice, an adhesive layer (not shown) is provided on the side of the retardation layer opposite to the polarizing plate, and the polarizing plate with the retardation layer can be attached to the image display unit. Further, it is preferable that a release film is temporarily adhered to the surface of the pressure-sensitive adhesive layer until the polarizing plate with the retardation layer is used. By temporarily adhering the release film, a roll can be formed while protecting the adhesive layer.
The total thickness of the polarizing plate with a retardation layer is preferably 30 μm or less, preferably 25 μm or less, and more preferably 20 μm or less. The total thickness may be 10 μm or more, for example. According to the embodiments of the present invention, such an extremely thin polarizing plate with a retardation layer can be realized. Further, the occurrence of cracks during heating can be suppressed. Such a polarizing plate with a retardation layer can have extremely excellent flexibility and bending durability. Such a polarizing plate with a retardation layer is particularly suitable for use in a curved image display device and/or a bendable or bendable image display device. The total thickness of the polarizing plate with a retardation layer is the total thickness of all layers constituting the polarizing plate with a retardation layer except for a pressure-sensitive adhesive layer for adhering the polarizing plate to an external adherend such as a panel or glass (that is, the total thickness of the polarizing plate with a retardation layer does not include a pressure-sensitive adhesive layer for adhering the polarizing plate with a retardation layer to an adjacent member such as an image display unit and a thickness of a release film capable of being temporarily adhered to the surface thereof).
The polarizing plate with a retardation layer according to the embodiment of the present invention has a basis weight of, for example, 6.5mg/cm 2 Below, preferably 2.0mg/cm 2 ～6.0mg/cm 2 More preferably 3.0mg/cm 2 ～5.5mg/cm 2 More preferably 3.5mg/cm 2 ～5.0mg/cm 2 . When the display panel is thin, the panel may be slightly deformed by the weight of the polarizing plate with a retardation layer, and display failure may occur. According to a formula of 6.5mg/cm 2 The polarizing plate with retardation layer of the following unit weight can prevent such deformation of the panel. In addition, the polarizing plate having the retardation layer per unit weight has good workability even when the polarizing plate is made thin, and exhibits excellent flexibility and bending durability.
Hereinafter, the components of the polarizing plate with a retardation layer will be described in more detail.
B. Polarizing plate
B-1. Polarizer
The polarizing film according to one embodiment of the present invention is composed of a PVA-based resin film containing a dichroic material, and satisfies the following formula (1) when the monomer transmittance is x% and the birefringence of the PVA-based resin is y. In addition, a polarizer according to another embodiment of the present invention is composed of a PVA-based resin film containing a dichroic material, and satisfies the following formula (2) when the monomer transmittance is x% and the in-plane retardation of the PVA-based resin film is znm. In one embodiment, the polarizer satisfies the following formula (3) where x% is a monomer transmittance and f is an orientation function of a polyvinyl alcohol resin constituting the polarizer.
y<-0.011x+0.525 (1)
z<-60x+2875 (2)
f<-0.018x+1.11 (3)
The birefringence of the PVA-based resin (hereinafter referred to as the birefringence of PVA or Δ n of PVA) and the in-plane retardation of the PVA-based resin film (hereinafter referred to as the "in-plane retardation of PVA") in the polarizer are both values related to the degree of orientation of the molecular chains of the PVA-based resin constituting the polarizer, and as the degree of orientation increases, the values may become larger. In the polarizer, the orientation of the molecular chains of the PVA-based resin in the absorption axis direction is looser than in the conventional polarizer, and therefore, the breakage in the absorption axis direction can be suppressed. As a result, a polarizing plate (consequently, a polarizing plate) having extremely excellent flexibility can be obtained. Such a polarizing plate (as a result, a polarizing plate) is preferably applied to a curved image display device, more preferably to a bendable image display device, and further preferably to a foldable image display device. In the prior art, it is sometimes difficult to obtain acceptable optical properties (typically, monomer transmittance and polarization degree) for a polarizer having a low degree of orientation, but a polarizer satisfying the above formula (1) and/or formula (2) can have both a lower degree of orientation of the PVA-based resin and acceptable optical properties than the prior art.
The polarizer according to the embodiment of the present invention preferably satisfies the following formula (1 a) and/or formula (2 a), and more preferably satisfies the following formula (1 b) and/or formula (2 b).
The polarizing element preferably satisfies the following formula (1 a) and/or formula (2 a), and more preferably satisfies the following formula (1 b) and/or formula (2 b).
-0.004x+0.18<y<-0.011x+0.525 (1a)
-0.003x+0.145<y<-0.011x+0.520 (1b)
-40x+1800<z<-60x+2875 (2a)
-30x+1450<z<-60x+2850 (2b)
In the present specification, the in-plane retardation of the PVA is 23 ℃ and the in-plane retardation of the PVA-based resin film at a wavelength of 1000 nm. By setting the near-infrared region as the measurement wavelength, the influence of iodine absorption in the polarizer can be eliminated, and the phase difference can be measured. The birefringence (in-plane birefringence) of the PVA is a value obtained by dividing the in-plane retardation of the PVA by the thickness of the polarizer.
The in-plane retardation of the PVA was evaluated as follows. First, phase difference values are measured at a plurality of wavelengths of 850nm or more, and the measured phase difference values are: r (λ) and wavelength: lambda is plotted and fitted to the Sellmeier equation using least squares. Wherein, A and B are fitting parameters and are coefficients determined by a least square method.
R(λ)＝A+B/(λ 2 -600 2 )
In this case, the phase difference value R (λ) can be separated into the in-plane phase difference (Rpva) of the PVA without wavelength dependence and the in-plane phase difference value (Ri) of iodine with strong wavelength dependence as follows.
Rpva＝A
Ri＝B/(λ 2 -600 2 )
From this separation formula, the in-plane retardation (i.e., rpva) of the PVA at the wavelength λ =1000nm can be calculated. The method for evaluating the in-plane retardation of the PVA is also described in japanese patent No. 5932760, and can be referred to as needed.
Further, the birefringence (Δ n) of the PVA can be calculated by dividing the retardation by the thickness.
Commercially available devices for measuring the in-plane retardation of PVA at the wavelength of 1000nm include KOBRA-WR/IR series and KOBRA-31X/IR series manufactured by Onchi measurement, inc.
The orientation function (f) of the polyvinyl alcohol resin constituting the polarizer used in the present invention preferably satisfies the following formula (3 a), and more preferably satisfies the following formula (3 b). If the orientation function is too small, acceptable monomer transmission and/or degree of polarization sometimes cannot be obtained.
-0.01x+0.50<f<-0.018x+1.11 (3a)
-0.01x+0.57<f<-0.018x+1.1 (3b)
The orientation function (f) is obtained by, for example, measurement using a fourier transform infrared spectrometer (FT-IR) and attenuated total reflection spectroscopy (ATR) using polarized light as measurement light. Specifically, germanium was used for microcrystals for bonding a polarizer, the incident angle of measurement light was set to 45 °, and incident polarized infrared light (measurement light) was set to polarized light (s-polarized light) vibrating in parallel with the surface bonding a sample of germanium crystals, and measurement was performed in a state where the stretching direction of the polarizer was arranged in parallel and perpendicular to the polarization direction of the measurement light, and 2941cm of the obtained absorbance spectrum was used -1 The intensity of (d) is calculated by the following equation. Here, the intensity I is 3330cm -1 Is a reference peak and is 2941cm -1 /3330cm -1 The value of (c). Note that the full orientation is indicated when f =1, and the random orientation is indicated when f = 0. Furthermore, we believe that 2941cm -1 The peak of (A) is represented by the main chain (-CH) of PVA in the polarizer 2 -) caused by vibrationThe absorption of (2).
f＝(3<cos 2 θ>-1)/2
＝(1-D)/[c(2D+1)]
＝-2×(1-D)/(2D+1)
Wherein the content of the first and second substances,
c＝(3cos 2 β-1)/2，2941cm -1 is β =90 °.
θ: angle of molecular chain relative to stretching direction
Beta: angle of transition dipole moment relative to molecular chain axis
D＝(I ⊥ )/(I // ) (in this case, the more the PVA molecules are oriented, the larger D is)
I ⊥ : measuring the absorption intensity of light in the case where the polarization direction of the light is perpendicular to the stretching direction of the polarizer
I // : measuring the absorption intensity of the polarized light when the polarized light direction is parallel to the stretching direction of the polarizer
The thickness of the polarizer is preferably 10 μm or less, and more preferably 8 μm or less. The lower limit of the thickness of the polarizer may be, for example, 1 μm. The thickness of the polarizer may be 2 μm to 10 μm in one embodiment, and may be 2 μm to 8 μm in another embodiment. By making the thickness of the polarizer very thin like this, the thermal shrinkage can be made very small. It is presumed that such a configuration also contributes to suppression of breakage in the absorption axis direction.
The polarizing element preferably exhibits dichroism of absorption at any wavelength of 380nm to 780 nm. The polarizing material preferably has a monomer transmittance of 40.0% or more, more preferably 41.0% or more. The upper limit of the monomer transmittance may be, for example, 49.0%. The polarizer has a monomer transmittance of 40.0% to 45.0% in one embodiment. The degree of polarization of the polarizer is preferably 99.0% or more, and more preferably 99.4% or more. The upper limit of the degree of polarization may be, for example, 99.999%. The degree of polarization of the polarizer is in one embodiment 99.0% to 99.99%. One feature of the polarizing member of the embodiment of the present invention is that: even if the PVA-based resin constituting the polarizer has a lower degree of orientation than conventional ones and has the in-plane retardation, birefringence, and/or orientation function as described above, such practically acceptable monomer transmittance and degree of polarization can be realized. This is presumably caused by the production method described later. The monomer transmittance is typically a Y value measured by an ultraviolet-visible spectrophotometer and corrected for visual sensitivity. The degree of polarization is typically determined by the following equation based on the parallel transmittance Tp and the orthogonal transmittance Tc obtained by measurement using an ultraviolet-visible spectrophotometer and by visual sensitivity correction.
Polarization degree (%) = { (Tp-Tc)/(Tp + Tc) } 1/2 ×100
The penetration strength of the polarizer is, for example, 30gf/μm or more, preferably 35gf/μm or more, more preferably 40gf/μm or more, still more preferably 45gf/μm or more, and particularly preferably 50gf/μm or more. The puncture strength may be, for example, 80gf/μm or less. By setting the puncture strength of the polarizer in such a range, the polarizer can be significantly suppressed from being cracked in the absorption axis direction. As a result, a polarizing plate having very excellent flexibility (as a result, a polarizing plate) can be obtained. The puncture strength is resistance to cracking of the polarizing material when the polarizing material is punctured with a predetermined strength. The puncture strength can be expressed, for example, by the following strength (breaking strength): the strength of breaking the polarizer when a predetermined needle is attached to a compression tester and the polarizer is punctured with the needle at a predetermined speed. The puncture strength is a puncture strength per unit thickness (1 μm) of the polarizer, as is clear from the unit.
The polarizing element is composed of a PVA-based resin film containing a dichroic material as described above. The PVA-based resin constituting the PVA-based resin film (substantially, polarizer) preferably contains a PVA-based resin modified with an acetoacetyl group. With such a configuration, a polarizer having a desired puncture strength can be obtained. The amount of the acetoacetyl group-modified PVA-based resin to be blended is preferably 5 to 20 wt%, more preferably 8 to 12 wt%, based on 100 wt% of the entire PVA-based resin. When the amount of the component is in such a range, the puncture strength can be set to a more appropriate range.
The polarizer can be typically produced using a laminate of two or more layers. Specific examples of the polarizer obtained by using the laminate include polarizers obtained by 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, as follows: 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 material from the PVA-based resin layer. In the present embodiment, a polyvinyl alcohol resin layer containing a halide and a polyvinyl alcohol resin is preferably formed on one side of the resin substrate. The stretching typically includes immersing the laminate in an aqueous boric acid solution and stretching. Further, the stretching preferably further includes subjecting the laminate to in-air stretching at a high temperature (e.g., 95 ℃ or higher) before the stretching in the aqueous boric acid solution. In the embodiment of the present invention, the total stretching magnification is preferably 3.0 to 4.5 times, which is significantly smaller than usual. Even at such a total draw ratio, a polarizer having acceptable optical characteristics can be obtained by a combination of addition of a halide and drying shrinkage treatment. Further, in the embodiment of the present invention, the stretching ratio of the in-air auxiliary stretching is preferably larger than the stretching ratio of the boric acid underwater stretching. By adopting such a configuration, a polarizer having acceptable optical characteristics can be obtained even if the total stretching magnification is small. The laminate is preferably subjected to a drying shrinkage treatment of shrinking by 2% or more in the width direction by heating while being conveyed in the longitudinal direction. In 1 embodiment, a method for producing a polarizing plate includes subjecting a laminate to in-air auxiliary stretching treatment, dyeing treatment, underwater stretching treatment, and drying shrinkage treatment in this order. By introducing the auxiliary stretching, even when the PVA-based resin is applied to the thermoplastic resin, the crystallinity of the PVA-based resin can be improved, and high optical characteristics can be realized. Further, by simultaneously improving the orientation of the PVA-based resin in advance, when the PVA-based resin is immersed in water in a subsequent dyeing step or stretching step, problems such as reduction in the orientation and dissolution of the PVA-based resin can be prevented, and high optical characteristics can be realized. Further, when the PVA-based resin layer is immersed in a liquid, disturbance of the orientation of the polyvinyl alcohol molecules and reduction of the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This makes it possible to improve the optical properties of the polarizer obtained through a treatment step of immersing the laminate in a liquid, such as dyeing or underwater stretching. Further, the optical properties can be improved by shrinking the laminate in the width direction by the drying shrinkage treatment. 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 off from the resin base material/polarizer laminate and an arbitrary appropriate protective layer may be laminated on the peeled surface according to the purpose. A detailed method for producing the polarizing film will be described later.
B-2. Method for manufacturing polarizing piece
The method for manufacturing a polarizing plate according to 1 embodiment of the present invention includes: forming a polyvinyl alcohol resin layer (PVA-based resin layer) containing a halide and a polyvinyl alcohol resin (PVA-based 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 in-water stretching treatment, and a drying shrinkage treatment in this order, wherein in the drying shrinkage treatment, the laminate is heated while being conveyed in the longitudinal direction, thereby shrinking the laminate by 1% to 10% in the width direction. The content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin. For the drying shrinkage treatment, the treatment is preferably carried out using a heated roller, and the temperature of the heated roller is preferably 60 to 120 ℃. The shrinkage in the width direction of the laminate due to the drying shrinkage treatment is preferably 1% to 10%. According to such a production method, the polarizing plate described in the above item B-1 can be obtained. In particular, a polarizer having excellent optical characteristics (typically, monomer transmittance and polarization degree) can be obtained by preparing a laminate having a PVA-based resin layer containing a halide, stretching the laminate in multiple stages including aerial auxiliary stretching and underwater stretching, and heating the stretched laminate with a heating roller.
B-2-1 preparation of laminate
As a method for producing a laminate of the thermoplastic resin substrate and the PVA-based resin layer, any appropriate method can be adopted. Preferably, a PVA-based resin layer is formed on the thermoplastic resin substrate by applying a coating solution containing a halide and a PVA-based resin to the surface of the thermoplastic resin substrate and drying the coating solution. As described above, the content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin.
As a method for applying the coating liquid, any appropriate method can be adopted. Examples thereof include roll coating, spin coating, wire bar coating, dip coating, die coating, curtain coating, spray coating, and knife coating (comma coating). The coating/drying temperature of the coating liquid is preferably 50 ℃ or higher.
The thickness of the PVA resin layer is preferably 2 to 30 μm, more preferably 2 to 20 μm. By making the thickness of the PVA-based resin layer before stretching extremely thin and reducing the total stretching magnification as described later, a polarizer having acceptable monomer transmittance and polarization degree even if the orientation function is extremely small can be obtained.
The thermoplastic resin substrate may be subjected to a surface treatment (e.g., corona treatment) before the PVA-based resin layer is formed, or an easy-adhesion layer may be formed on the thermoplastic resin substrate. By performing such a treatment, the adhesion between the thermoplastic resin substrate and the PVA-based resin layer can be improved.
B-2-1-1. Thermoplastic resin base Material
As the thermoplastic resin substrate, any suitable thermoplastic resin film can be used. The thermoplastic resin base material is described in detail in, for example, japanese patent laid-open publication No. 2012-73580 and japanese patent No. 6470455. The entire disclosure of this publication is incorporated herein by reference.
B-2-1-2 coating liquid
The coating liquid contains a halide and a PVA-based resin as described above. The coating liquid is typically a solution of the halide and the PVA-based resin solvent in a solvent. Examples of the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These may be used alone or in combination of two or more. Among these, water is preferred. The concentration of the PVA-based resin in the solution is preferably 3 to 20 parts by weight based on 100 parts by weight of the solvent. When the resin concentration is such as this, a uniform coating film can be formed which adheres to the thermoplastic resin substrate. The content of the halide in the coating liquid is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin.
Additives may be compounded in the coating liquid. Examples of the additives include plasticizers and surfactants. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin. Examples of the surfactant include nonionic surfactants. These can be used for the purpose of further improving the uniformity, dyeability and stretchability of the PVA-based resin layer obtained.
As the PVA-based resin, any suitable resin can be used. For example, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are mentioned. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer. The saponification degree of the PVA resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, and more preferably 99.0 mol% to 99.93 mol%. The degree of saponification can be determined in accordance with JIS K6726-1994. By using the PVA-based resin having such a saponification degree, a polarizing element having excellent durability can be obtained. If the degree of saponification is too high, gelation may occur. As described above, the PVA-based resin preferably contains an acetoacetyl group-modified PVA-based resin.
The average polymerization degree of the PVA-based resin can be appropriately selected according to the purpose. The average polymerization degree is usually 1000 to 10000, preferably 1200 to 4500, and more preferably 1500 to 4300. The average degree of polymerization can be determined in accordance with JIS K6726-1994.
As the halide, any suitable halide can be used. For example, iodide and sodium chloride may be mentioned. Examples of the iodide include potassium iodide, sodium iodide, and lithium iodide. Among these, potassium iodide is preferable.
The amount of the halide in the coating liquid is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin, and more preferably 10 to 15 parts by weight based on 100 parts by weight of the PVA-based resin. If the amount of the halide is more than 20 parts by weight based on 100 parts by weight of the PVA-based resin, the halide may bleed out, and the finally obtained polarizer may become cloudy.
In general, the orientation of polyvinyl alcohol molecules in the PVA-based resin is increased by stretching the PVA-based resin layer, but when the stretched PVA-based resin layer is immersed in a liquid containing water, the orientation of polyvinyl alcohol molecules may be disturbed and the orientation may be reduced. In particular, when a laminate of a thermoplastic resin and a PVA-based resin layer is stretched in boric acid water at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin when the laminate is stretched in boric acid water, the orientation degree tends to decrease significantly. For example, in the case where the PVA film itself is usually stretched in boric acid water at 60 ℃, and the laminate of a-PET (thermoplastic resin substrate) and a PVA-based resin layer is stretched at a high temperature of about 70 ℃, the orientation of the PVA at the initial stage of stretching may be lowered at a stage before the PVA is raised by underwater stretching. On the other hand, by producing a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin substrate and stretching the laminate at a high temperature in air (auxiliary stretching) before stretching the laminate in boric acid water, crystallization of the PVA-based resin in the PVA-based resin layer of the laminate after the auxiliary stretching can be promoted. As a result, in the case where the PVA-based resin layer is immersed in the liquid, disturbance of the orientation of the polyvinyl alcohol molecules and deterioration of the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This makes it possible to improve the optical properties of the polarizer obtained through a treatment step of immersing the laminate in a liquid, such as dyeing or underwater stretching.
B-2-2. Auxiliary stretching treatment in air
In particular, in order to obtain high optical properties, a 2-stage stretching method combining dry stretching (auxiliary stretching) and boric acid underwater stretching is selected. By introducing the auxiliary stretching as in the 2-stage stretching, the stretching can be performed while suppressing crystallization of the thermoplastic resin substrate. Further, when a PVA-based resin is coated on a thermoplastic resin substrate, in order to suppress the influence of the glass transition temperature of the thermoplastic resin substrate, it is necessary to lower the coating temperature than in the case of coating the PVA-based resin on a metal drum in general, and as a result, there is a problem that crystallization of the PVA-based resin is relatively low and sufficient optical characteristics cannot be obtained. On the other hand, even when the PVA-based resin is applied to the thermoplastic resin by introducing the auxiliary stretching, the crystallinity of the PVA-based resin can be improved, and high optical characteristics can be realized. Further, by simultaneously improving the orientation of the PVA-based resin in advance, it is possible to prevent problems such as reduction in orientation and dissolution of the PVA-based resin when immersed in water in the subsequent dyeing step and stretching step, and to realize high optical characteristics.
The stretching method of the in-air auxiliary stretching may be fixed-end stretching (for example, a method of stretching using a tenter) or free-end stretching (for example, a method of uniaxially stretching a laminate by passing the laminate between rolls having different peripheral speeds). In order to obtain high optical properties, free end stretching can be used actively. In 1 embodiment, the in-flight stretching treatment includes a heated roller stretching step of stretching the laminate while conveying the laminate in the longitudinal direction thereof by a circumferential speed difference between heated rollers. The in-air stretching process typically includes a zone stretching process and a heated roll stretching process. The order of the area stretching step and the heating roller stretching step is not limited, and the area stretching step may be performed first or the heating roller stretching step may be performed first. The zone stretching process may be omitted. In 1 embodiment, the zone stretching step and the heated roller stretching step are performed in this order. In another embodiment, stretching is performed by holding the film end in a tenter stretching machine and expanding the distance between the tenters in the moving direction (expansion of the distance between the tenters is a stretching magnification). In this case, the distance of the tenter in the width direction (direction perpendicular to the moving direction) can be set to be arbitrarily close. Preferably can be connected in seriesThe near-free-end stretching mode sets the stretching ratio in the moving direction. In the case of free end stretching, the shrinkage in the width direction = (1/stretching ratio) 1/2 To calculate.
The in-air auxiliary stretching may be performed in one stage or may be performed in multiple stages. When the stretching is performed in multiple stages, the stretching ratio is the product of the stretching ratios in the respective stages. The stretching direction of the in-air auxiliary stretching is preferably substantially the same as the stretching direction of the underwater stretching.
The stretching ratio in the air-assisted stretching is preferably 1.0 to 4.0 times, more preferably 1.5 to 3.5 times, and still more preferably 2.0 to 3.0 times. When the stretching magnification of the in-air auxiliary stretching is within such a range, the total stretching magnification can be set to a desired range in combination with the underwater stretching, and a desired orientation function can be realized. As a result, a polarizer in which breaking in the absorption axis direction is suppressed can be obtained. Further, as described above, the stretching ratio of the in-air auxiliary stretching is preferably larger than the stretching ratio of the boric acid underwater stretching. By making such a constitution, even if the total magnification of stretching is small, a polarizing member having acceptable optical characteristics can be obtained. More specifically, the ratio of the stretching ratio of the air-assisted stretching to the stretching ratio of the underwater stretching (underwater stretching/air-assisted stretching) is preferably 0.4 to 0.9, and more preferably 0.5 to 0.8.
The stretching temperature of the in-air auxiliary stretching may be set to any appropriate value depending on the material for forming the thermoplastic resin base material, the stretching method, and the like. The stretching temperature is preferably not lower than the glass transition temperature (Tg) of the thermoplastic resin substrate, more preferably not lower than the glass transition temperature (Tg) +10 ℃, and particularly preferably not lower than Tg +15 ℃. On the other hand, the upper limit of the stretching temperature is preferably 170 ℃. By stretching at such a temperature, it is possible to suppress rapid progress of crystallization of the PVA-based resin and to suppress defects caused by the crystallization (for example, to prevent orientation of the PVA-based resin layer caused by stretching).
B-2-3 insolubilization treatment, dyeing treatment and crosslinking treatment
If necessary, after the in-air auxiliary stretching treatment, the insolubilization treatment is performed before the stretching treatment in water and the dyeing treatment. The insolubilization treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. The dyeing treatment is typically performed by dyeing the PVA-based resin layer with a dichroic substance (typically, iodine). If necessary, a crosslinking treatment is performed after the dyeing treatment and before the stretching treatment in water. The crosslinking treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. Details of the insolubilization treatment, dyeing treatment and crosslinking treatment are described in, for example, japanese patent laid-open No. 2012-73580 (described above).
B-2-4 stretching treatment in water
The underwater stretching treatment is performed by immersing the laminate in a stretching bath. The stretching in water can be performed at a temperature lower than the glass transition temperature (typically, about 80 ℃) of the thermoplastic resin substrate or the PVA-based resin layer, and the PVA-based resin layer can be stretched while suppressing crystallization thereof. As a result, a polarizer having excellent optical characteristics can be manufactured.
Any suitable method may be used for stretching the laminate. Specifically, the stretching may be performed at a fixed end or at a free end (for example, a method of passing the laminate between rollers having different peripheral speeds to perform uniaxial stretching). Free end stretching is preferably chosen. The stretching of the laminate may be performed in one stage or may be performed in multiple stages. When the stretching is performed in multiple stages, the total stretching magnification is the product of the stretching magnifications in the respective stages.
The underwater stretching is preferably performed by immersing the laminate in an aqueous boric acid solution (boric acid underwater stretching). By using the aqueous boric acid solution as the stretching bath, the PVA-based resin layer can be given rigidity to withstand the tension applied during stretching and water resistance to be insoluble in water. Specifically, boric acid generates tetrahydroxyborate anions in an aqueous solution and can be crosslinked with the PVA-based resin by hydrogen bonds. As a result, rigidity and water resistance can be imparted to the PVA-based resin layer, and the PVA-based resin layer can be stretched well, whereby a polarizer having excellent optical characteristics can be produced.
The aqueous boric acid solution is preferably obtained by dissolving boric acid and/or a borate in water as a solvent. The boric acid concentration is preferably 1 to 10 parts by weight, more preferably 2.5 to 6 parts by weight, and particularly preferably 3 to 5 parts by weight, based on 100 parts by weight of water. By setting the boric acid concentration to 1 part by weight or more, the dissolution of the PVA-based resin layer can be effectively suppressed, and a polarizing plate with higher characteristics can be produced. In addition to boric acid or a borate, an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, or the like in a solvent may be used.
The above-mentioned stretching bath (aqueous boric acid solution) is preferably compounded with an iodide. By adding the iodide, elution of iodine adsorbed to the PVA-based resin layer can be suppressed. Specific examples of the iodide are as described above. The concentration of the iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of water.
The drawing temperature (liquid temperature of the drawing bath) is preferably 40 to 85 ℃ and more preferably 60 to 75 ℃. At such a temperature, the PVA-based resin layer can be stretched at a high magnification while dissolution thereof is suppressed. Specifically, as described above, the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60 ℃ or higher in relation to the formation of the PVA-based resin layer. In this case, if the stretching temperature is lower than 40 ℃, there is a fear that the thermoplastic resin substrate cannot be stretched well even when plasticization of the thermoplastic resin substrate by water is considered. On the other hand, if the temperature of the stretching bath is high, the solubility of the PVA-based resin layer may be high, and thus excellent optical characteristics may not be obtained. The immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
The stretching ratio by underwater stretching is preferably 1.0 to 3.0 times, more preferably 1.0 to 2.0 times, and further preferably 1.0 to 1.5 times. If the stretching magnification in underwater stretching is in such a range, the total stretching magnification can be set to a desired range, and a desired orientation function can be realized. As a result, a polarizer in which breaking along the absorption axis direction is suppressed can be obtained. The total draw ratio (the total draw ratio when the in-air auxiliary drawing and the underwater drawing are combined) is, for example, 3.0 to 4.5 times, preferably 3.0 to 4.0 times, and more preferably 3.0 to 3.5 times the original length of the laminate, as described above. By properly combining addition of a halide to the coating liquid, adjustment of the stretching ratios of the in-air auxiliary stretching and the underwater stretching, and the drying shrinkage treatment, a polarizer having acceptable optical characteristics can be obtained even at such a total stretching ratio.
B-2-5 drying shrinkage treatment
The drying shrinkage treatment may be performed by heating the entire region to heat the region, or may be performed by heating the transport roller (using a so-called hot roller) (hot roller drying method). Both are preferably used. By drying using a heating roller, the laminate can be effectively inhibited from curling by heating, and a polarizer having excellent appearance can be produced. Specifically, by drying the laminate in a state where the laminate is along the heating roller, the crystallization of the thermoplastic resin substrate can be effectively promoted to increase the crystallinity, and the crystallinity of the thermoplastic resin substrate can be favorably increased even at a relatively low drying temperature. As a result, the thermoplastic resin substrate has increased rigidity, and is able to withstand shrinkage of the PVA-based resin layer due to drying, and curl can be suppressed. Further, since the laminate can be dried while being kept flat by using the heating roller, not only curling but also wrinkles can be suppressed. In this case, the laminate is shrunk in the width direction by a drying shrinkage treatment, whereby the optical properties can be improved. This is because the orientation of PVA and PVA/iodine complex can be effectively improved. The shrinkage in the width direction of the laminate by the drying shrinkage treatment is preferably 1% to 10%, more preferably 2% to 8%, and particularly preferably 4% to 6%.
Fig. 4 is a schematic diagram showing an example of the drying shrinkage process. In the drying shrinkage process, the laminate 200 is dried while being conveyed by the conveying rollers R1 to R6 and the guide rollers G1 to G4 heated to a predetermined temperature. In the illustrated example, the conveying rollers R1 to R6 are arranged so as to alternately and continuously heat the surface of the PVA resin layer and the surface of the thermoplastic resin substrate, but the conveying rollers R1 to R6 may be arranged so as to continuously heat only one surface (for example, the thermoplastic resin substrate surface) of the laminate 200.
The drying condition can be controlled by adjusting the heating temperature of the conveying roller (temperature of the heating roller), the number of heating rollers, the contact time with the heating roller, and the like. The temperature of the heated roller is preferably 60 to 120 ℃, more preferably 65 to 100 ℃, and particularly preferably 70 to 80 ℃. The crystallinity of the thermoplastic resin can be favorably increased to favorably suppress curling, and an optical laminate having extremely excellent durability can be produced. The temperature of the heating roller may be measured by a contact thermometer. In the example of the figure, 6 conveying rollers are provided, but there is no particular limitation as long as there are a plurality of conveying rollers. The number of the conveying rollers is usually 2 to 40, preferably 4 to 30. The contact time (total contact time) between the laminate and the heating roller is preferably 1 to 300 seconds, more preferably 1 to 20 seconds, and still more preferably 1 to 10 seconds.
The heating roller may be installed in a heating furnace (for example, an oven) or may be installed in a general production line (room temperature environment). Preferably, the heating furnace is provided with an air blowing means. By using the drying by the hot roller and the hot air drying in combination, a rapid temperature change between the hot rollers can be suppressed, and the shrinkage in the width direction can be easily controlled. The temperature of the hot air drying is preferably 30 to 100 ℃. The hot air drying time is preferably 1 to 300 seconds. The wind speed of the hot wind is preferably about 10m/s to 30 m/s. The wind speed is the wind speed in the heating furnace, and can be measured by a miniature blade type digital anemometer.
B-2-6 other treatment
It is preferable to perform the washing treatment after the stretching treatment in water and before the drying shrinkage treatment. The cleaning treatment is typically performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution.
B-3 protective layer
In the embodiment of the present invention, the thickness of the protective layer is 10 μm or less. The thickness of the protective layer is 10 μm or less, which contributes to thinning of the polarizing plate. The polarizing plate with a retardation layer can prevent cracks from being generated during heating even if the thickness of the protective layer is 10 μm or less. The thickness of the protective layer is preferably 7 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The thickness of the protective layer is, for example, 1 μm or more.
The protective layer may be formed of any suitable material. Examples thereof include: cellulose resins such as Triacetylcellulose (TAC), and transparent resins such as polyester, polyvinyl alcohol, polycarbonate, polyamide, polyimide, polyether sulfone, polysulfone, polystyrene, polynorbornene, polyolefin, (meth) acrylic, and acetate; a thermosetting resin or an ultraviolet-curable resin such as (meth) acrylic acid-based, urethane-based, (meth) acrylic urethane-based, epoxy-based, or silicone-based resins; a glassy polymer such as a siloxane polymer.
The protective layer may be a thin film, a solid of a coating film, or a cured product (e.g., a photocationic cured product). In one embodiment, the protective layer is composed of at least 1 selected from the group consisting of a solid substance of a coating film of an organic solvent solution of a thermoplastic (meth) acrylic resin (hereinafter, the (meth) acrylic resin may be simply referred to as an acrylic resin), a photo cation cured product of an epoxy resin, and a solid substance of a coating film of an organic solvent solution of an epoxy resin. The following description will be specifically made.
B-3-1. Solid product of coating film of organic solvent solution of thermoplastic acrylic resin
In one embodiment, the protective layer is formed of a solid product of a coating film of an organic solvent solution of a thermoplastic acrylic resin.
B-3-1-1 acrylic resin
The glass transition temperature (Tg) of the acrylic resin is preferably 100 ℃ or higher. As a result, the Tg of the protective layer was 100 ℃ or higher. When the Tg of the acrylic resin is 100 ℃ or higher, a polarizing plate including a protective layer obtained from such a resin can be a polarizing plate having excellent durability. The Tg of the acrylic resin is preferably 110 ℃ or higher, more preferably 115 ℃ or higher, still more preferably 120 ℃ or higher, and particularly preferably 125 ℃ or higher. On the other hand, the Tg of the acrylic resin is preferably 300 ℃ or lower, preferably 250 ℃ or lower, more preferably 200 ℃ or lower, and particularly preferably 160 ℃ or lower. When the Tg of the acrylic resin is in such a range, moldability is excellent.
As the acrylic resin, any suitable acrylic resin may be used as long as it has Tg as described above. The acrylic resin typically contains an alkyl (meth) acrylate as a main component as a monomer unit (repeating unit). In the present specification, "(meth) acrylic" means acrylic and/or methacrylic. Examples of the alkyl (meth) acrylate constituting the main skeleton of the acrylic resin include alkyl (meth) acrylates in which a linear or branched alkyl group has 1 to 18 carbon atoms. These may be used alone or in combination. Further, any suitable comonomer may be introduced into the acrylic resin by copolymerization. The repeating unit derived from the alkyl (meth) acrylate is typically represented by the following general formula (1):
in the general formula (1), R 4 Represents a hydrogen atom or a methyl group, R 5 Represents a hydrogen atom or an optionally substituted aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms. Examples of the substituent include halogen and hydroxyl. Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5, 6-pentahydroxyhexyl (meth) acrylate, 2,3,4, 5-tetrahydroxypentyl (meth) acrylate, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylateAnd 2- (hydroxyethyl) acrylic acid methyl ester. In the general formula (1), R 5 Preferably a hydrogen atom or a methyl group. Thus, a particularly preferred alkyl (meth) acrylate is methyl acrylate or methyl methacrylate.
The acrylic resin may contain only a single alkyl (meth) acrylate unit, or may contain R in the above general formula (1) 4 And R 5 Different plurality of alkyl (meth) acrylate units.
The content ratio of the alkyl (meth) acrylate unit in the acrylic resin is preferably 50 to 98 mol%, more preferably 55 to 98 mol%, still more preferably 60 to 98 mol%, particularly preferably 65 to 98 mol%, and most preferably 70 to 97 mol%. If the content ratio is less than 50 mol%, the effects (e.g., high heat resistance and high transparency) derived from the alkyl (meth) acrylate unit may not be sufficiently exhibited. If the content ratio is more than 98 mol%, the resin may be brittle and easily broken, and high mechanical strength may not be sufficiently exhibited, resulting in poor productivity.
The acrylic resin preferably has a repeating unit containing a ring structure. Examples of the repeating unit having a ring structure include 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 containing a ring structure may contain only 1 kind of repeating unit in the acrylic resin, or may contain 2 or more kinds of repeating units therein.
The lactone ring unit is preferably represented by the following general formula (2):
in the general formula (2), R 1 、R 2 And R 3 Each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may 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) 1 、R 2 And R 3 A plurality of different lactone ring units. Acrylic resins having a lactone ring unit are described in, for example, japanese patent application laid-open No. 2008-181078, the description 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 an alkyl group having 1 to 8 carbon atoms, 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 preferred 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 A different plurality of 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. Regarding the glutaric anhydride unit, in addition to the units represented by R in the above general formula (3) 13 The above description of glutarimide units applies in addition to the substituted nitrogen atom being an oxygen atom.
Since the structure of the maleic anhydride unit and the maleimide (N-substituted maleimide) unit is defined by names, detailed description thereof is 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%. If the content ratio is too small, the Tg may be less than 100 ℃ and the heat resistance, solvent resistance and surface hardness of the resulting protective layer may be insufficient. If the content is too large, moldability and transparency may be insufficient.
The acrylic resin may contain a repeating unit other than the alkyl (meth) acrylate unit and the repeating unit containing a ring structure. Examples of such a repeating unit include a repeating unit derived from a vinyl monomer copolymerizable with the monomers constituting the above-mentioned unit (other vinyl monomer unit). Examples of the other vinyl monomer include acrylic acid, methacrylic acid, crotonic acid, 2- (hydroxymethyl) acrylic acid, 2- (hydroxyethyl) acrylic acid, acrylonitrile, methacrylonitrile, ethacrylonitrile (ethacrylonitrile), allyl glycidyl ether, maleic anhydride, itaconic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methallylamine, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, N-phenylmaleimide, phenylaminoethyl methacrylate, styrene, α -methylstyrene, p-glycidyl styrene, p-aminostyrene, and 2-styryl-oxazoline. These may be used alone or in combination. The kind, amount, combination, content and the like of the other vinyl monomer units can be appropriately set according to the purpose.
The weight average molecular weight of the acrylic resin is preferably 1000 to 2000000, more preferably 5000 to 1000000, further preferably 10000 to 500000, particularly preferably 50000 to 500000, and most preferably 60000 to 150000. The weight average molecular weight can be determined by polystyrene conversion using, for example, gel permeation chromatography (GPC system, manufactured by tokyo co. Tetrahydrofuran is used as the solvent.
The acrylic resin may be obtained by appropriately combining the above monomer units and polymerizing the monomer units by any appropriate polymerization method.
In the embodiment of the present invention, an acrylic resin and another resin may be used in combination. That is, the monomer component constituting the acrylic resin and the monomer component constituting the other resin may be copolymerized, and the copolymer may be subjected to molding of a protective layer described later; a mixture of an acrylic resin and another resin may be used for forming the protective layer. Examples of the other resin include thermoplastic resins such as styrene resins, polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene ether, polyacetal, polyimide, and polyetherimide. The kind and amount of the resin to be used in combination may be appropriately set according to the purpose, the desired properties of the obtained film, and the like. For example, a styrene resin (preferably, an acrylonitrile-styrene copolymer) can be used in combination as a retardation controller.
When an acrylic resin and another resin are used in combination, the content of the acrylic resin in the mixture of the acrylic resin and the other resin is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, still more preferably 70 to 100% by weight, and particularly preferably 80 to 100% by weight. When the content is less than 50% by weight, the high heat resistance and high transparency inherent in the acrylic resin may not be sufficiently reflected.
B-3-2 photo cation condensate of epoxy resin
In one embodiment, the protective layer is formed of a photocationic cured product of an epoxy resin. By using such a protective layer, a polarizing plate having both excellent durability and excellent flexibility and a polarizing plate with a retardation layer can be provided. As described above, since the protective layer is a photocationic cured product, the protective layer-forming composition contains a photocationic polymerization initiator. The photo cation polymerization initiator is a photosensitizer having a function as a photo acid generator, and typically includes an ionic onium salt formed of a cation portion and an anion portion. In the onium salt, the cation portion absorbs light, and the anion portion serves as a generation source of an acid. The ring-opening polymerization of the epoxy group is carried out by an acid generated from the photo cation polymerization initiator. The protective layer obtained as a photo cation cured product has a high glass transition temperature and can reduce the amount of iodine adsorbed. Therefore, a polarizing plate having both excellent durability and excellent flexibility can be provided.
B-3-2-1 epoxy resin
As the epoxy resin, any suitable epoxy resin may be used. In the present embodiment, an epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton can be preferably used. Examples of the aromatic skeleton include a benzene ring, a naphthalene ring, and a fluorene ring. The epoxy resin may be used in combination of 2 or more than 1 kind. An epoxy resin having a biphenyl skeleton as an aromatic skeleton is preferably used. By using an epoxy resin having a biphenyl skeleton, a polarizing plate having both excellent durability and excellent flexibility can be provided. Hereinafter, an epoxy resin having a biphenyl skeleton will be described in detail as a representative example.
In one embodiment, the epoxy resin having a biphenyl skeleton is an epoxy resin including the following structure. The epoxy resin having a biphenyl skeleton may be used alone of 1 kind, or may be used in combination of 2 or more kinds.
(in the formula, R 14 ～R 21 Each independently represents a hydrogen atom, a linear or branched substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, or a halogen element).
R 14 ～R 21 Each independently represents a hydrogen atom, a linear or branched substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, or a halogen element. Examples of the linear or branched substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexylCyclohexyl, n-heptyl, cycloheptyl, methylcyclohexyl, n-octyl, cyclooctyl, n-nonyl, 3, 5-trimethylcyclohexyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, cyclododecyl, phenyl, benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, phenethyl, 2-phenylisopropyl and the like. Preferred examples of the linear or branched substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Preferred examples of the halogen element include fluorine and bromine.
In 1 embodiment, the epoxy resin having a biphenyl skeleton is an epoxy resin represented by the following formula.
(wherein R is 14 ～R 21 As described above, n represents an integer of 0 to 6).
In 1 embodiment, the epoxy resin having a biphenyl skeleton is an epoxy resin having only a biphenyl skeleton. By using an epoxy resin having only a biphenyl skeleton, the durability of the resultant protective layer can be further improved.
In 1 embodiment, the epoxy resin having a biphenyl skeleton may include a chemical structure other than the biphenyl skeleton. Examples of the chemical structure other than the biphenyl skeleton include a bisphenol skeleton, an alicyclic structure, an aromatic ring structure, and the like. In this embodiment, the proportion (molar ratio) of the chemical structure other than the biphenyl skeleton is preferably smaller than that of the biphenyl skeleton.
As the epoxy resin having a biphenyl skeleton, a commercially available one can be used. Examples of the commercially available product include products manufactured by Mitsubishi chemical corporation, trade name: jER YX4000, jER YX4000H, jER YL6121, jER YL664, jER YL6677, jER YL6810, and jER YL 7399.
The epoxy resin having a biphenyl skeleton preferably has a glass transition temperature (Tg) of 90 ℃ or higher. As a result, the Tg of the protective layer becomes 90 ℃ or higher. When the epoxy resin having a biphenyl skeleton has a Tg of 90 ℃ or higher, a polarizing plate including the obtained protective layer is likely to have excellent durability. The Tg of the epoxy resin having a biphenyl skeleton is preferably 100 ℃ or higher, more preferably 110 ℃ or higher, still more preferably 120 ℃ or higher, and particularly preferably 125 ℃ or higher. On the other hand, the Tg of the epoxy resin having a biphenyl skeleton is preferably 300 ℃ or less, more preferably 250 ℃ or less, still more preferably 200 ℃ or less, and particularly preferably 160 ℃ or less. When the Tg of the epoxy resin having a biphenyl skeleton falls within such a range, moldability is excellent.
The epoxy equivalent of the epoxy resin having a biphenyl skeleton is preferably 100 g/equivalent or more, more preferably 150 g/equivalent or more, and further preferably 200 g/equivalent or more. The epoxy equivalent of the epoxy resin having a biphenyl skeleton is preferably 3000 g/equivalent or less, more preferably 2500 g/equivalent or less, and further preferably 2000 g/equivalent or less. When the epoxy equivalent of the epoxy resin having a biphenyl skeleton is in the above range, a more stable protective layer (a protective layer in which residual monomers are small and which is sufficiently cured) can be obtained. In the present specification, the term "epoxy equivalent" refers to "the mass of an epoxy resin containing 1 equivalent of epoxy group", and can be measured according to JIS K7236.
In the embodiment of the present invention, an epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton may be used in combination with another resin. That is, a mixture of an epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton and another resin may be subjected to the molding of the protective layer. Examples of the other resin include a styrene-based resin, a thermoplastic resin such as polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene ether, polyacetal, polyimide, or polyether imide, and a curable resin such as an acrylic resin or an oxetane resin. Acrylic resins and oxetane resins are preferably used. The kind and amount of the resin to be used in combination may be appropriately set according to the purpose, the desired properties of the obtained film, and the like. For example, a styrene resin may be used in combination as a phase difference control agent.
As the acrylic resin, any suitable acrylic resin can be used. Examples of the (meth) acrylic compound include a (meth) acrylic compound having one (meth) acryloyl group in the molecule (hereinafter, also referred to as a "monofunctional (meth) acrylic compound"), and a (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule (hereinafter, also referred to as a "polyfunctional (meth) acrylic compound"). These (meth) acrylic compounds may be used alone or in combination of 2 or more. These acrylic resins are described in, for example, japanese patent laid-open publication No. 2019-168500. The entire disclosure of this publication is incorporated herein by reference.
As the oxetane resin, any suitable compound having 1 or more oxetanyl groups in the molecule is used. Examples thereof include oxetane compounds having 1 oxetanyl group in the molecule, such as 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, 3-ethyl-3- (oxiranylmethoxy) oxetane, (3-ethyloxetan-3-yl) methyl (meth) acrylate, and the like; oxetane compounds having 2 or more oxetanyl groups in the molecule, such as 3-ethyl-3 { [ (3-ethyloxetan-3-yl) methoxy ] methyl } oxetane, 1, 4-bis [ (3-ethyl-3-oxetanyl) methoxymethyl ] benzene, 4' -bis [ (3-ethyl-3-oxetanyl) methoxymethyl ] biphenyl, and the like; and so on. These oxetane resins may be used alone in 1 kind, or 2 or more kinds may be used in combination.
As the oxetane resin, 3-ethyl-3-hydroxymethyloxetane, 1, 4-bis [ (3-ethyl-3-oxetanyl) methoxymethyl ] benzene, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (oxiranylmethoxy) oxetane, (3-ethyloxetan-3-yl) methyl (meth) acrylate, 3-ethyl-3 { [ (3-ethyloxetan-3-yl) methoxy ] methyl } oxetane and the like are preferably used. These oxetane resins are easily available and excellent in dilutability (low viscosity) and compatibility.
In 1 embodiment, an oxetane resin having a molecular weight of 500 or less and being liquid at room temperature (25 ℃) is preferably used from the viewpoint of compatibility and adhesiveness. In 1 embodiment, an oxetane compound containing 2 or more oxetanyl groups in the molecule, an oxetane compound containing 1 oxetanyl group and 1 (meth) acryloyl group or 1 epoxy group in the molecule, and 3-ethyl-3 { [ (3-ethyloxetan-3-yl) methoxy ] methyl } oxetane, 3-ethyl-3- (oxiranylmethoxy) oxetane, and (3-ethyloxetan-3-yl) methyl (meth) acrylate are preferably used. By using these oxetane resins, curability and durability of the protective layer can be improved.
As the oxetane resin, a commercially available product can be used. Specifically, ARON OXETANE OXT-101, ARON OXETANE OXT-121, ARON OXETANE OXT-212, and ARON OXETANE OXT-221 (all manufactured by TOYOBO SYNTHETIC CO., LTD.) can be used. Preferably, ARON OXETANE OXT-101 and ARON OXETANE OXT-221 can be used.
When an epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton is used in combination with another resin, the content of the epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton in a mixture of the epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton and another resin is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, much more preferably 70 to 100% by weight, particularly preferably 80 to 100% by weight. When the content is less than 50% by weight, the heat resistance of the protective layer and sufficient adhesion to the polarizer may not be obtained.
When the epoxy resin having a biphenyl skeleton and the oxetane resin are used in combination, the content of the oxetane resin is preferably 1 to 50 parts by weight, more preferably 5 to 45 parts by weight, and further preferably 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin having a biphenyl skeleton and the oxetane resin. When the amount is within the above range, curability is improved, and adhesion between the protective layer and the polarizer is also improved.
B-3-2-2 photo cation polymerization initiator
The photo cation polymerization initiator is a photosensitizer having a function as a photo acid generator, and typically includes an ionic onium salt formed of a cation portion and an anion portion. In the onium salt, the cation portion absorbs light, and the anion portion serves as an acid generation source. The ring-opening polymerization of the epoxy group is carried out by an acid generated from the photo cation polymerization initiator. As the photo cation polymerization initiator, any suitable compound that can cure an epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton by irradiation with light such as ultraviolet rays can be used. The photo cation polymerization initiator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the photo cation polymerization initiator include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, p- (phenylsulfur) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylsulfur) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonium) phenyl ] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonium) phenyl ] sulfide bishexafluoroantimonate, (2, 4-cyclopentadien-1-yl) [ (1-methylethyl) benzene ] -Fe-hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and the like. It is preferable to use a triphenylsulfonium salt type photo-cation polymerization initiator of hexafluoroantimonate type and a diphenyliodonium salt type photo-cation polymerization initiator of hexafluoroantimonate type.
As the photo cation polymerization initiator, commercially available products can be used. Commercially available products include SP-170 (manufactured by ADEKA corporation) of triphenylsulfonium salt type hexafluoroantimonate, CPI-101A (manufactured by SAN-APRO corporation), WPAG-1056 (manufactured by Wako pure chemical industries, ltd.), and WPI-116 (manufactured by Wako pure chemical industries, ltd.) of diphenyliodonium salt type hexafluoroantimonate.
The content of the photo cation polymerization initiator is preferably 0.1 to 3 parts by weight, more preferably 0.25 to 2 parts by weight, relative to 100 parts by weight of the epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton. When the content of the photo cation polymerization initiator is less than 0.1 part by weight, the curing may not be sufficiently performed even by irradiation with light (ultraviolet rays).
B-3-3 solid substance of coating film of epoxy resin in organic solvent solution
In one embodiment, the protective layer is formed of a solid of a coating film of an organic solvent solution of an epoxy resin.
B-3-3-1. Epoxy resin
In the present embodiment, the epoxy resin preferably has a glass transition temperature (Tg) of 90 ℃ or higher. As a result, the Tg of the protective layer becomes 90 ℃ or higher. If the Tg of the epoxy resin is 90 ℃ or higher, a polarizing plate including a protective layer obtained from such a resin tends to be a polarizing plate having excellent durability. The Tg of the epoxy resin is preferably 100 ℃ or higher, more preferably 110 ℃ or higher, still more preferably 120 ℃ or higher, and particularly preferably 125 ℃ or higher. On the other hand, the Tg of the epoxy resin is preferably 300 ℃ or lower, more preferably 250 ℃ or lower, still more preferably 200 ℃ or lower, and particularly preferably 160 ℃ or lower. When the Tg of the epoxy resin is within such a range, moldability is excellent.
As the epoxy resin, any suitable epoxy resin may be used as long as it has Tg as described above. The epoxy resin typically refers to a resin having an epoxy group in a molecular structure. As the epoxy resin, an epoxy resin having an aromatic ring in the molecular structure is preferably used. By using an epoxy resin having an aromatic ring, an epoxy resin having a higher Tg can be obtained. Examples of the aromatic ring in the epoxy resin having an aromatic ring in the molecular structure include a benzene ring, a naphthalene ring, and a fluorene ring. The epoxy resin may be used in 1 kind alone, or 2 or more kinds may be used in combination. When 2 or more epoxy resins are used, an epoxy resin containing an aromatic ring and an epoxy resin containing no aromatic ring may be used in combination.
Specific examples of the epoxy resin having an aromatic ring in the molecular structure include epoxy resins having 2 epoxy groups such as bisphenol a diglycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, resorcinol diglycidyl ether type epoxy resin, hydroquinone diglycidyl ether type epoxy resin, terephthalic acid diglycidyl ester type epoxy resin, bisphenoxyethanolfluorene diglycidyl ether type epoxy resin, bisphenol fluorene diglycidyl ether type epoxy resin, and bisphenol fluorene diglycidyl ether type epoxy resin; epoxy resins having 3 epoxy groups such as novolak-type epoxy resins, N, O-triglycidyl-p-or-m-aminophenol-type epoxy resins, N, O-triglycidyl-4-amino-m-or-5-amino-O-cresol-type epoxy resins, and 1,1- (triglycidyloxyphenyl) methane-type epoxy resins; epoxy resins having 4 epoxy groups such as glycidylamine type epoxy resins (for example, diaminodiphenylmethane type, diaminodiphenylsulfone type, and metaxylylenediamine type). Furthermore, glycidyl ester type epoxy resins such as hexahydrophthalic anhydride type epoxy resin, tetrahydrophthalic anhydride type epoxy resin, dimer acid type epoxy resin, and p-hydroxybenzoic acid type epoxy resin can be used.
The weight average molecular weight of the epoxy resin is preferably 1000 to 2000000, more preferably 5000 to 1000000, further preferably 10000 to 500000, particularly preferably 50000 to 500000, and most preferably 60000 to 150000. The weight average molecular weight can be determined by polystyrene conversion using, for example, gel permeation chromatography (GPC system, manufactured by tokyo co. Tetrahydrofuran is used as the solvent.
The epoxy equivalent of the epoxy resin is preferably 1000 g/equivalent or more, more preferably 3000 g/equivalent or more, and further preferably 5000 g/equivalent or more. The epoxy equivalent of the epoxy resin is preferably 30000 g/equivalent or less, more preferably 25000 g/equivalent or less, and further preferably 20000 g/equivalent or less. By setting the epoxy equivalent to the above range, a more stable protective layer can be obtained. In the present specification, "epoxy equivalent" means "the mass of an epoxy resin containing 1 equivalent of epoxy group", and can be measured according to JIS K7236.
In the embodiment of the present invention, the epoxy resin and the other resin may be used in combination. That is, a mixture of an epoxy resin and another resin may be used for molding the protective layer. Examples of the other resin include thermoplastic resins such as styrene resins, polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene ether, polyacetal, polyimide, and polyetherimide. The kind and amount of the resin to be used in combination may be appropriately set according to the purpose, the desired properties of the obtained film, and the like. For example, a styrene resin may be used in combination as a phase difference control agent.
When the epoxy resin and the other resin are used in combination, the content of the epoxy resin in the mixture of the epoxy resin and the other resin is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, still more preferably 70 to 100% by weight, and particularly preferably 80 to 100% by weight. When the content is less than 50% by weight, the heat resistance of the protective layer and sufficient adhesion to the polarizer may not be obtained.
B-3-4. Composition and characteristics of protective layer
In 1 embodiment, the protective layer is composed of at least 1 selected from the group consisting of a solid substance of a coating film of an organic solvent solution of a thermoplastic acrylic resin, a photo cation cured substance of an epoxy resin, and a solid substance of a coating film of an organic solvent solution of an epoxy resin, as described above. In the case of such a protective layer, the thickness can be reduced significantly compared to an extrusion-molded film. The thickness of the protective layer is 10 μm or less as described above. Further, although it is theoretically unclear, such a protective layer has an advantage that it is less likely to shrink during film formation than a cured product of another thermosetting resin or active energy ray-curable resin (for example, an ultraviolet-curable resin), and does not contain a residual monomer or the like, and therefore, it is possible to suppress deterioration of the film itself and to suppress adverse effects on the polarizing plate (polarizer) due to the residual monomer or the like. Further, compared with a solid product of an aqueous coating film such as an aqueous solution or an aqueous dispersion, there is an advantage that moisture absorption and moisture permeability are small, and thus humidification durability is excellent. As a result, a polarizing plate having excellent durability, which can maintain optical characteristics even in a heated and humidified environment, can be realized.
The Tg of the protective layer is as described for the acrylic resin and the epoxy resin, respectively.
The protective layer is preferably substantially optically isotropic. In the present specification, "substantially optically isotropic" means that the in-plane retardation Re (550) is 0nm to 10nm and the retardation Rth (550) in the thickness direction is-20 nm to +10nm. The in-plane retardation Re (550) is more preferably 0nm to 5nm, still more preferably 0nm to 3nm, particularly preferably 0nm to 2nm. The retardation Rth (550) in the thickness direction is more preferably from-5 nm to +5nm, still more preferably from-3 nm to +3nm, and particularly preferably from-2 nm to +2nm. When Re (550) and Rth (550) of the protective layer are in such ranges, it is possible to prevent adverse effects on display characteristics when the polarizing plate including the protective layer is applied to an image display device. Re (550) was an in-plane retardation of the film measured at 23 ℃ under light having a wavelength of 550 nm. Re (550) is represented by formula: re (550) = (nx-ny) × d. Rth (550) is a retardation in the thickness direction of the film measured by light having a wavelength of 550nm at 23 ℃. Rth (550) is represented by the formula: rth (550) = (nx-nz) × d. Where nx is a refractive index in a direction in which an in-plane refractive index is maximum (i.e., a slow axis direction), ny is a refractive index in a direction orthogonal to the slow axis in the plane (i.e., a fast axis direction), nz is a refractive index in a thickness direction, and d is a thickness (nm) of the thin film.
The higher the light transmittance at 380nm of the protective layer at a thickness of 3 μm, the more preferable. Specifically, the light transmittance is preferably 85% or more, more preferably 88% or more, and further preferably 90% or more. When the light transmittance is in such a range, desired transparency can be secured. The light transmittance can be measured by a method according to ASTM-D-1003, for example.
The lower the haze of the protective layer, the more preferred. Specifically, the haze is preferably 5% or less, more preferably 3% or less, further preferably 1.5% or less, and particularly preferably 1% or less. When the haze is 5% or less, a good transparency can be imparted to the film. Further, even in the case of a polarizing plate on the viewing side used for an image display device, the display contents can be viewed well.
The YI of the protective layer at a thickness of 3 μm is preferably 1.27 or less, more preferably 1.25 or less, further preferably 1.23 or less, and particularly preferably 1.20 or less. When YI exceeds 1.3, the optical transparency may be insufficient. YI can be obtained from the tristimulus values (X, Y, Z) of the color obtained by measurement using a high-speed integrating sphere type spectral transmittance measuring instrument (trade name DOT-3C: manufactured by Colorkun technologies research Co., ltd.) by the following formula.
YI＝[(1.28X-1.06Z)/Y]×100
The b value (scale according to hue of Hunter color system) of the protective layer at a thickness of 3 μm is preferably less than 1.5, more preferably 1.0 or less. When the b value is 1.5 or more, an undesirable color tone may appear. The b value can be obtained, for example, as follows: a sample of the film constituting the protective layer was cut to a 3cm square, and the hue was measured by a high-speed integrating sphere type spectral transmittance measuring instrument (trade name: DOT-3C, manufactured by Colorkun technical research Co., ltd.), and the hue was evaluated by the Hunter color system.
The protective layer (for example, a solid of a coating film or a photo cation cured product) may contain any appropriate additive according to the purpose. Specific examples of the additive include an ultraviolet absorber; a leveling agent; antioxidants such as hindered phenol type, phosphorus type, and sulfur type; 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 so on. The additive may be added during polymerization of the acrylic resin or may be added to the solution during film formation. The kind, amount, combination, addition amount, and the like of the additive can be appropriately set according to the purpose.
An easy-adhesion layer may be formed on the polarizer side of the protective layer. The easy-adhesion layer contains, for example, an aqueous polyurethane and an oxazoline-based crosslinking agent. By forming such an easy-adhesion layer, the adhesion between the protective layer and the polarizer can be improved. Further, a hard coat layer may be formed on the protective layer. In the case of forming the hard coat layer, the hard coat layer may be formed so that the total of the thickness of the protective layer (for example, a solid of the coating film) and the thickness of the hard coat layer is 10 μm or less. The hard coat layer may be formed when the protective layer is used as a protective layer of the visual recognition side polarizing plate. When both the easy-adhesion layer and the hard coat layer are formed, it is representative that they may be formed on different sides of the protective layer, respectively.
C. 1 st phase difference layer
As described above, the 1 st retardation layer 20 is an alignment cured layer of a liquid crystal compound. By using the liquid crystal compound, the difference between nx and ny of the obtained retardation layer can be made very large as compared with a non-liquid crystal material, and therefore, the thickness of the retardation layer that can be used for obtaining a desired in-plane retardation is made much smaller. As a result, the polarizing plate with a retardation layer can be further thinned and lightened. In the present specification, the "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, a rod-like liquid crystal compound is typically aligned in the slow axis direction of the 1 st retardation layer (planar 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, if the liquid crystal monomers are polymerized or crosslinked 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, and they are non-liquid crystal. 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 becomes a retardation layer which is not affected by temperature change and is excellent in stability.
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 still more 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 (WO 00/37585), EP358208 (US 5211877), EP66137 (US 4388453), WO93/22397, EP0261712, DE19504224, DE4408171, GB2280445 and the like can be used. Specific examples of such polymerizable mesogen compounds include a trade name LC242 from BASF, a trade name E7 from Merck, and a trade name LC-Sillicon-CC3767 from Wacker-Chem. The liquid crystal monomer is preferably, for example, a nematic liquid crystal monomer.
The alignment cured layer of the liquid crystal compound 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 oriented cured layer formed on the substrate may be transferred to the surface of polarizing plate 10. In another embodiment, the substrate may be the 2 nd protective layer 13. In this case, since the transfer step can be omitted and the alignment cured layer (1 st retardation layer) is continuously laminated from the start of formation by roll-to-roll, the productivity is further improved.
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. 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 a method for forming an alignment cured layer are described in jp 2006-163343 a. The description of this publication is incorporated herein by reference.
As another example of the alignment cured layer, a form in which a discotic liquid crystal compound is aligned in any one of a homeotropic alignment, a hybrid alignment, and an oblique alignment may be mentioned. The discotic liquid crystal compound is typically a discotic liquid crystal compound in which the discotic plane is substantially vertically aligned with respect to the film plane of the 1 st retardation layer. The term "the discotic liquid-crystalline compound is substantially perpendicular" means that the average value of the angle formed by the film plane and the disc plane of the discotic liquid-crystalline compound is preferably 70 ° to 90 °, more preferably 80 ° to 90 °, and still more preferably 85 ° to 90 °. The discotic liquid crystal compound generally refers to a liquid crystal compound having a discotic molecular structure in which a cyclic parent nucleus such as benzene, 1,3, 5-triazine, calixarene, etc. is disposed at the center of the molecule and a linear alkyl group, alkoxy group, substituted benzoyloxy group, etc. are substituted radially as side chains. Typical examples of discotic liquid crystals include: deslade et al, mol. Crystal.liq. Crystal.Vol.71, page 111 (1981), benzene derivatives, triphenylene derivatives, truxene derivatives, phthalocyanine derivatives; b. a cyclohexane derivative described in kohne et al, angelw. Chem. 96, page 70 (1984); and macrocycles of the nitrogen crown or phenylacetylene series described in J.M.Lehn et al, J.chem.Soc.chem.Commun. 1794 (1985), J.Zhang et al, J.Am.chem.Soc.116, 2655 (1994). More specific examples of discotic liquid crystal compounds include those described in, for example, japanese patent application laid-open Nos. 2006-133652, 2007-108732, and 2010-244038. The disclosures of the above documents and publications are incorporated herein by reference.
In one embodiment, the 1 st retardation layer 20 is a single layer of an alignment cured layer of a liquid crystal compound, as shown in fig. 1 and 2. When the 1 st retardation layer 20 is composed of a single layer of an alignment cured layer of a liquid crystal compound, its thickness 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 extremely thinner than that of the resin film.
The 1 st retardation layer is representative of 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 of the alignment cured 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 160nm. 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 impairing 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, a very excellent antireflection property 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 °. When the angle θ is within such a range, the 1 st retardation layer is made into a λ/4 plate as described above, whereby a polarizing plate with a retardation layer having very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics) can be obtained.
In another embodiment, as shown in fig. 3, the 1 st phase difference layer 20 may have a laminated structure of a 1 st orientation-cured layer 21 and a 2 nd orientation-cured layer 22. At this time, either one of the 1 st oriented cured layer 21 and the 2 nd oriented 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 orientation cured layer 21 and the 2 nd orientation cured layer 22 can be adjusted so that a desired in-plane retardation of λ/4 plate or λ/2 plate can be obtained. For example, when the 1 st orientation cured layer 21 functions as a λ/2 plate and the 2 nd orientation cured layer 22 functions as a λ/4 plate, the thickness of the 1 st orientation cured layer 21 is, for example, 2.0 μm to 3.0 μm, and the thickness of the 2 nd orientation cured layer 22 is, for example, 1.0 μm to 2.0 μm. In this case, the in-plane retardation Re (550) of the first oriented cured layer 1 is preferably 200nm to 300nm, more preferably 230nm to 290nm, and still more preferably 250nm to 280nm. The in-plane retardation Re (550) of the 2 nd orientation-cured layer is as described above with respect to the orientation-cured layer of a single layer. The angle formed by the slow axis of the 1 st orientation cured layer and the absorption axis of the polarizer is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and further preferably about 15 °. The angle formed by the slow axis of the 2 nd orientation 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. As for the liquid crystal compounds constituting the 1 st and 2 nd alignment cured layers, the methods for forming the 1 st and 2 nd alignment cured layers, the optical characteristics, and the like, as described above with respect to the single-layer alignment cured layer.
D. Phase difference layer 2
The 2 nd phase difference layer may be a so-called Positive C-plate (Positive C-plate) whose refractive index characteristic shows a relationship of nz > nx = ny, as described above. By using the positive C plate as the 2 nd retardation layer, the oblique reflection can be prevented well, and the wide viewing angle of the antireflection function can be realized. 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 10nm.
The 2 nd phase difference 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 application 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.
E. 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 thickness of the conductive layer is preferably 10nm or more.
The conductive layer may be transferred from the substrate to the 1 st retardation layer (or the 2 nd retardation layer if the 2 nd retardation layer is present) and then the conductive layer itself may be used as a constituent layer of the polarizing plate with a retardation layer, or may be laminated on the 1 st retardation layer (or the 2 nd retardation layer if the 2 nd retardation layer is present) in the form of a laminate of the conductive layer and the substrate (substrate with a conductive layer). The substrate is preferably 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 thickness of the isotropic base material is, for example, 20 μm or more.
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.
F. Image display device
The polarizing plate with a retardation layer described in the above items a to E can be applied to an image display device. Therefore, the present invention includes 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). An image display device according to an embodiment of the present invention includes the polarizing plate with a retardation layer described in the above items a to E 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, or inorganic EL unit) (such that the polarizer is on the visual recognition side). In 1 embodiment, the image display device has a curved shape (substantially curved display screen), and/or can be flexed or bent. In such an image display device, the polarizing plate with a retardation layer according to the present invention is remarkably effective.
[ 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. Unless otherwise specified, "parts" and "%" in examples and comparative examples are based on weight.
[ example 1]
1. Fabrication of polarizing elements
An amorphous ethylene isophthalate copolymer polyethylene terephthalate film (thickness: 100 μm) having a long shape, a water absorption of 0.75% and a Tg of about 75 ℃ was used as a thermoplastic resin base material. One side of the resin substrate was subjected to corona treatment (treatment condition: 55 W.min/m) 2 )。
In the following, with 9:1 an aqueous PVA solution (coating solution) was prepared by adding 13 parts by weight of potassium iodide to 100 parts by weight of a PVA resin obtained by mixing polyvinyl alcohol (degree of polymerization 4200, degree of saponification of 99.2 mol%) and acetoacetyl group-modified PVA (product name "GOHSEFIMER Z410" manufactured by Nippon synthetic chemical industries, ltd.).
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 13.5 μm, thereby producing a laminate.
The obtained laminate was uniaxially stretched to 2.4 times at the free end in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ℃ (in-air auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilization bath (an 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, the polarizing plate was immersed in a dyeing bath (aqueous iodine solution prepared by mixing iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ℃ for 60 seconds while adjusting the concentration so that the monomer transmittance (Ts) of the final polarizing plate became 40.5% (dyeing treatment).
Subsequently, the substrate was immersed in a crosslinking bath (an aqueous boric acid solution prepared by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid to 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (crosslinking treatment).
Then, the laminate was uniaxially stretched in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds so that the total stretching ratio became 3.0 times (underwater stretching treatment: stretching ratio in underwater stretching treatment was 1.25 times) while being immersed in an aqueous boric acid solution (boric acid concentration: 4.0 wt%, potassium iodide: 5.0 wt%) having a liquid temperature of 62 ℃.
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 ℃.
Thereafter, the sheet was dried in an oven maintained at 90 ℃ while maintaining the contact surface temperature of the sheet at 75 ℃ for about 2 seconds with a SUS-made heating roll (drying shrinkage treatment). The shrinkage in the width direction of the laminate by the drying shrinkage treatment was 2%.
Thus, a polarizing element having a thickness of 7.4 μm was formed on the resin substrate.
2. Manufacture of polarizing plate
An aqueous polyurethane resin (trade name, manufactured by first Industrial pharmaceutical Co., ltd.): SUPER FLEX 210-R) was dissolved in a mixed solvent of pure water and isopropyl alcohol, and the obtained solution was applied to the surface of the polarizing plate formed on the resin base material obtained above. Then, the resultant was dried at 60 ℃ to remove the solvent, thereby forming an easy-adhesion layer having a thickness of 0.15. Mu.m. 20 parts of an acrylic resin having methyl methacrylate units (trade name: B728, manufactured by NAKAI CHEMICAL Co.) were dissolved in 80 parts of methyl ethyl ketone to obtain an acrylic resin solution (20%). The acrylic resin solution was applied to the easy-adhesion layer using a wire bar, and the coating film was dried at 60 ℃ for 5 minutes to form an acrylic resin layer constituting a solid product of the coating film. The acrylic resin layer had a thickness of 2 μm and a Tg of 116 ℃. Subsequently, 70 parts by weight of dimethylol tricyclodecane diacrylate (trade name: LIGHT TACRYLATE DCP-A, manufactured by CO.R.), 20 parts by weight of isobornyl acrylate (trade name: LIGHT TACRYLATE IB-XA, manufactured by CO.R.), 10 parts by weight of 1, 9-nonanediol diacrylate (trade name: LIGHT TACRYLATE 1.9NA-A, manufactured by CO.R.) and 3 parts by weight ofbase:Sub>A photopolymerization initiator (trade name: IRGACURE 907, manufactured by BASF) were mixed inbase:Sub>A solvent to obtainbase:Sub>A coating solution. The obtained coating liquid was applied onto the protective layer so that the thickness after curing became 3 μm. Then, the solvent was dried, and the cumulative light amount was 300mJ/cm using a high-pressure mercury lamp 2 The hard coat layer was formed by irradiating ultraviolet rays in a nitrogen atmosphere. The thickness of the hard coat layer was 3 μm. Then, in order to stably perform the subsequent bonding operation with the retardation layer, the pressure-sensitive adhesive layer of the polyethylene terephthalate (PET) film with the pressure-sensitive adhesive layer is bonded to the protective layer for reinforcement. Then, the resin substrate was peeled off to obtain a polarizing plate having a configuration of a PET film with a pressure-sensitive adhesive layer, a protective layer (hard coat layer/acrylic resin layer (solid product of coating film))/easy-to-adhere layer/polarizer.
3. Preparing the 1 st oriented cured layer and the 2 nd oriented cured layer constituting the retardation 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 brushed with a brush cloth to conduct 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 in bonding to the polarizer. The liquid crystal coating liquid was applied to the alignment-treated surface by a bar coater, and heat-dried at 90 ℃ for 2 minutes, thereby aligning the liquid crystal compound. Irradiating the thus formed liquid crystal layer with 100mJ/cm using a metal halide lamp 2 The liquid crystal layer is cured by the light of (3), 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 270nm. Further, the liquid crystal alignment cured layer A has nx>ny = nz refractive index profile.
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 be 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 140nm. Further, the liquid crystal alignment cured layer B has a refractive index distribution of nx > ny = nz.
4. Manufacturing polarizing plate with phase difference 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 orientation cured layer a became 15 ° and the angle formed by the absorption axis of the polarizer and the slow axis of the orientation cured layer B became 75 °. The respective transfer (bonding) was performed by an ultraviolet curing adhesive (thickness 1.0 μm). Subsequently, the adhesive layer-attached PET film was peeled off. Thus, a polarizing plate with a retardation layer having a structure of protective layer (hard coat layer/acrylic resin layer (solid matter of coating film))/easy-to-adhere layer/polarizer/adhesive layer/retardation layer (1 st oriented cured layer/adhesive layer/2 nd oriented cured layer) was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 19 μm.
[ examples 2 to 4]
A polarizer having a thickness of 7.4 μm was formed on a resin substrate in the same manner as in example 1, except that a dye bath having a different iodine concentration (weight ratio of iodine to potassium iodide = 1).
A polarizing plate with a retardation layer having a structure of a protective layer (hard coat layer/acrylic resin layer (solid material of coating film))/easy-to-adhere layer/polarizing plate/adhesive layer/retardation layer (1 st oriented cured layer/adhesive layer/2 nd oriented cured layer) was obtained in the same manner as in example 1, except that the obtained laminate having a structure of a polarizing plate/resin substrate was used. The total thickness of the obtained polarizing plate with a retardation layer was 19 μm.
[ examples 5 to 8]
A polarizing plate having a thickness of 6.7 μm was formed on a resin substrate in the same manner as in example 1, except that the stretching ratio in the underwater stretching treatment was 1.46 times, the total stretching ratio was 3.5 times, and dyeing baths having different iodine concentrations (weight ratio of iodine to potassium iodide = 1.
A polarizing plate with a retardation layer having a structure of protective layer (hard coat layer/acrylic resin layer (solid material of coating film))/easy adhesion layer/polarizing element/adhesion layer/retardation layer (1 st oriented cured layer/adhesion layer/2 nd oriented cured layer) was obtained in the same manner as in example 1, except that the obtained laminate having a structure of polarizing element/resin substrate was used. The total thickness of the obtained polarizing plate with a retardation layer was 18 μm.
[ example 9]
A polarizing plate with a retardation layer was obtained in the same manner as in example 7, except that an acrylic resin (lactone ring unit: 30 mol%) which is polymethyl methacrylate having a lactone ring unit was used in place of the acrylic resin having a methyl methacrylate unit (trade name: B728, manufactured by NAPHYONITA. Co., ltd.). The total thickness of the obtained polarizing plate with a retardation layer was 18 μm.
[ example 10]
A polarizing plate with a retardation layer was obtained in the same manner as in example 9, except that an acrylic resin (4 mol% of glutarimide ring units) which is polymethyl methacrylate having glutarimide ring units was used instead of the acrylic resin having methyl methacrylate units (trade name: B728, manufactured by Nanba Ltd.). The total thickness of the obtained polarizing plate with a retardation layer was 18 μm.
[ example 11]
In example 9, a solid protective layer constituting a coating film was formed using an epoxy resin solution (20%) prepared by dissolving 20 parts of an epoxy resin (product name: jER (registered trademark) YX6954BH30, weight average molecular weight: 36000, and epoxy equivalent: 13000, manufactured by mitsubishi chemical corporation) in 80 parts of methyl ethyl ketone, instead of the acrylic resin solution. Specifically, the epoxy resin solution was applied to the easy-adhesion layer using a wire bar, and the coating film was dried at 60 ℃ for 3 minutes to form a protective layer. The thickness of the protective layer was 3 μm and Tg was 130 ℃. A polarizing plate 7 with a retardation layer was obtained in the same manner as in example 9, except that the protective layer was formed and the easy-adhesion layer and the hard coat layer were not formed on the polarizer. The total thickness of the obtained polarizing plate with a retardation layer was 16 μm.
[ example 12]
A polarizing plate with a retardation layer was obtained in the same manner as in example 7, except that a protective layer was formed, and no easy-adhesion layer and no hard coat layer were formed on the polarizer as described below. The total thickness of the obtained polarizing plate with a retardation layer was 16 μm.
An epoxy resin solution was obtained by dissolving 15 parts of an epoxy resin having a biphenyl skeleton (product name: jER (registered trademark) YX4000, manufactured by mitsubishi chemical corporation) in 83.8 parts of methyl ethyl ketone. To the obtained epoxy resin solution, 1.2 parts of a photo cation polymerization initiator (product name: CPI (registered trademark) -100P, manufactured by SANAPRO corporation) was added to obtain a protective layer forming composition. The obtained protective layer-forming composition was applied to the easy-adhesion layer using a wire bar, and the coating film was dried at 60 ℃ for 3 minutes. Then, makeThe cumulative light amount of the mercury lamp was 600mJ/cm 2 The protective layer is formed by irradiating ultraviolet rays. The thickness of the protective layer was 3 μm.
[ example 13]
A polarizing plate with a retardation layer was obtained in the same manner as in example 12, except that a bisphenol type epoxy resin (product name: jER (registered trademark) 828, manufactured by mitsubishi chemical corporation) was used instead of the epoxy resin having a biphenyl skeleton. The total thickness of the obtained polarizing plate with a retardation layer was 16 μm.
[ example 14]
A polarizing plate with a retardation layer was obtained in the same manner as in example 12, except that a hydrogenated bisphenol epoxy resin (product name: jeR (registered trademark) YX8000, manufactured by Mitsubishi chemical) was used instead of the epoxy resin having a biphenyl skeleton. The total thickness of the obtained polarizing plate with a retardation layer was 16 μm.
[ example 15]
An epoxy resin solution was obtained by dissolving 15 parts of a hydrogenated bisphenol epoxy resin (product name: jER (registered trademark) YX8000, manufactured by mitsubishi chemical corporation) and 10 parts of an OXETANE resin (product name: ARONE OXETANE (registered trademark) OXT-221, manufactured by east asian synthesis corporation) in 73 parts of methyl ethyl ketone. 2 parts of a photo cation polymerization initiator (product name: CPI (registered trademark) -100P, manufactured by SANAPRO Co., ltd.) was added to the obtained epoxy resin solution to obtain a protective layer forming composition. A polarizing plate with a retardation layer was obtained in the same manner as in example 12, except that the obtained protective layer-forming composition was used. The total thickness of the obtained polarizing plate with a retardation layer was 16 μm.
[ example 16]
A polarizing plate with a retardation layer was obtained in the same manner as in example 15, except that the thickness of the protective layer was set to 8 μm.
[ example 17]
A polarizing plate with a retardation layer was obtained in the same manner as in example 15, except that the thickness of the protective layer was changed to 10 μm.
[ example 18]
Except that an ultraviolet curable epoxy resin (DAICEL Co., ltd.) was usedA resist (cured product) was formed in the same manner as in example 12, except that the product was named "CELLOXIDE 2021P"). Specifically, a composition containing 95 wt% of the epoxy resin and 5 wt% of a photopolymerization initiator (CPI-100P, manufactured by SANAPRO) was applied to the easy-adhesion layer, and the total light amount was 500mJ/cm using a high-pressure mercury lamp in an air atmosphere 2 The cured layer (protective layer) was formed by irradiating ultraviolet rays. A polarizing plate with a retardation layer was produced in the same manner as in example 7, except that the protective layer was used. The thickness of the polarizer was 16 μm.
[ examples 19 to 22]
A polarizing plate having a thickness of 6.2 μm was formed on a resin substrate in the same manner as in example 1, except that the stretching magnification in water was set to 1.67 times (as a result, the total stretching magnification was 4.0 times) and that a dye bath having different iodine concentrations (weight ratio of iodine to potassium iodide = 1.
A polarizing plate with a retardation layer having a structure of a protective layer (hard coat layer/acrylic resin layer (solid material of coating film))/easy-to-adhere layer/polarizing plate/adhesive layer/retardation layer (1 st oriented cured layer/adhesive layer/2 nd oriented cured layer) was obtained in the same manner as in example 1, except that the obtained laminate having a structure of a polarizing plate/resin substrate was used. The total thickness of the obtained polarizing plate with a retardation layer was 18 μm.
[ examples 23 to 26]
A polarizing plate having a thickness of 6.0 μm was formed on a resin substrate in the same manner as in example 1, except that the stretching ratio in the underwater stretching was 1.88 times, the total stretching ratio was 4.5 times, and dyeing baths having different iodine concentrations were used (the weight ratio of iodine to potassium iodide = 1.
A polarizing plate with a retardation layer having a structure of protective layer (hard coat layer/acrylic resin layer (solid material of coating film))/easy adhesion layer/polarizing element/adhesion layer/retardation layer (1 st oriented cured layer/adhesion layer/2 nd oriented cured layer) was obtained in the same manner as in example 1, except that the obtained laminate having a structure of polarizing element/resin substrate was used. The total thickness of the obtained polarizing plate with a retardation layer was 17.0. Mu.m.
Comparative examples 1 to 4
A polarizing material having a thickness of 5.5 μm was formed on a resin substrate in the same manner as in example 1, except that the stretching ratio in the underwater stretching was 2.29 times, the total stretching ratio was 5.5 times, and dyeing baths having different iodine concentrations (weight ratio of iodine to potassium iodide = 1.
A polarizing plate with a retardation layer having a structure of a protective layer (hard coat layer/acrylic resin layer (solid material of coating film))/easy-to-adhere layer/polarizing plate/adhesive layer/retardation layer (1 st oriented cured layer/adhesive layer/2 nd oriented cured layer) was obtained in the same manner as in example 1, except that the obtained laminate having a structure of a polarizing plate/resin substrate was used. The total thickness of the obtained polarizing plate with a retardation layer was 16 μm.
Comparative example 5
A polarizing plate having a thickness of 5.5 μm was obtained in the same manner as in example 1, except that the stretching ratio in the underwater stretching treatment was 2.29 times, the total stretching ratio was 5.5 times, and the liquid temperature of the stretching bath was 70 ℃. A polarizing plate with a retardation layer was obtained in the same manner as in example 1, except that an acrylic resin film having a thickness of 40 μm was laminated on the surface of the obtained polarizer via an ultraviolet-curable adhesive as a protective layer. The total thickness of the obtained polarizing plate with a retardation layer was 53 μm.
Comparative example 6
A polarizing plate with a retardation layer was obtained in the same manner as in comparative example 2, except that an acrylic film having a thickness of 20 μm was used as the protective layer. The total thickness of the obtained polarizing plate with a retardation layer was 33 μm.
Comparative example 7
A polarizing plate with a retardation layer was obtained in the same manner as in comparative example 2, except that the protective layer was formed in the same manner as in example 11. The total thickness of the obtained polarizing plate with a retardation layer was 15 μm.
Comparative example 8
A polarizing plate with a retardation layer was obtained in the same manner as in comparative example 2, except that the protective layer was formed in the same manner as in example 12. The total thickness of the obtained polarizing plate with a retardation layer was 15 μm.
Comparative example 9
A polarizing plate with a retardation layer was obtained in the same manner as in comparative example 2, except that the protective layer was formed in the same manner as in example 15. The total thickness of the obtained polarizing plate with a retardation layer was 15 μm.
[ evaluation ]
The polarizing plates with retardation layers obtained in examples and comparative examples were used to perform the following evaluations. The results are shown in Table 1.
(1) Thickness of
The thickness of the polarizer was measured using an interferometric film thickness gauge (manufactured by tsukamur electronics, product name "MCPD-3000"). The calculated wavelength range used in the thickness calculation was 400nm to 500nm, and the refractive index was 1.53. The thickness of the protective layer was measured by appropriately selecting the calculated wavelength range and the refractive index using an interference film thickness meter (manufactured by tsukamur electronics, product name "MCPD-3000"). The thickness of the easy adhesion layer was determined by Scanning Electron Microscope (SEM) observation. The thickness of more than 10 μm was measured using a digital micrometer (product name "KC-351C" manufactured by Anritsu Co., ltd.).
(2) In-plane retardation (Re) of PVA
The polarizers (polarizers themselves) obtained by peeling off the resin base material from the polarizer/thermoplastic resin base material laminate obtained in examples and comparative examples were evaluated for the in-plane retardation (Rpva) of PVA at a wavelength of 1000nm (a value obtained by subtracting the in-plane retardation (Ri) of iodine from the total in-plane retardation at a wavelength of 1000nm according to the principle described) using a retardation measuring apparatus (product name "KOBRA-31X100/IR" manufactured by prince measuring machines). The absorption edge wavelength is 600nm.
(3) Birefringence (Δ n) of PVA
The birefringence (Δ n) of the PVA was calculated by dividing the in-plane retardation of the PVA measured in the above (2) by the thickness of the polarizer.
(4) Function of orientation
The polarizers used in the examples and comparative examples were subjected to attenuated total reflection spectroscopy (A) on the polarizer surface using a Fourier transform infrared spectrometer (FT-IR) (product name: frontier, manufactured by Perkin Elmer Co., ltd.) and polarized infrared rays as measurement lightTR: attentuated total reflection). Germanium was used for the microcrystals for closely adhering the polarizers, and the incident angle of the measurement light was set to 45 °. The orientation function was calculated according to the following procedure. The incident polarized infrared ray (measurement light) is polarized light (s-polarized light) vibrating parallel to the surface to which the sample of germanium crystals is bonded, and each absorbance spectrum is measured in a state where the polarizing direction of the measurement light is perpendicular (#) and parallel (///) to the stretching direction of the polarizer. Calculated from the obtained absorbance spectrum to be (3330 cm) -1 Strength) as reference (2941 cm) -1 Strength) I. I.C. A ⊥ Obtained for an absorbance spectrum obtained when the stretching direction of the polarizer was arranged perpendicularly ([ quadrature ]) to the polarizing direction of the measurement light (2941 cm) -1 Strength)/(3330 cm -1 Strength). In addition, I // Obtained from an absorbance spectrum obtained when the polarizing material was disposed so that the stretching direction of the polarizing material was parallel (/ /) to the polarizing direction of the measurement light (2941 cm) -1 Strength)/(3330 cm -1 Strength). Here, (2941 cm) -1 Intensity) is 2770cm to be the bottom of the absorbance spectrum -1 And 2990cm -1 2941cm at baseline -1 (3330 cm) of (A) -1 Strength) of 2990cm -1 And 3650cm -1 3330cm at baseline -1 Absorbance of (b). Using the obtained I ⊥ And I // The orientation function f is calculated according to equation 1. The full orientation was indicated when f =1, and the random orientation was indicated when f = 0. Furthermore, 2941cm -1 The peak of (A) is called the main chain (-CH) of PVA in the polarizer 2 -) absorption by vibration. Furthermore, 3330cm -1 The peak of (b) is absorption due to vibration of the hydroxyl group of the PVA.
(formula 1) f = (3)<cos 2 θ>-1)/2
＝(1-D)/[c(2D+1)]
Wherein the content of the first and second substances,
c＝(3cos 2 beta-1)/2, 2941cm was used as described above -1 When the temperature of the water is higher than the set temperature,
θ: angle of molecular chain relative to stretching direction
Beta: angle of transition dipole moment relative to molecular chain axis
D＝(I ⊥ )/(I // )
I ⊥ : measuring the absorption intensity of light in the case where the polarization direction of the light is perpendicular to the stretching direction of the polarizer
I // : measuring the absorption intensity when the polarization direction of light is parallel to the stretching direction of the polarizer
(5) Rate of occurrence of cracks
The polarizing plates with retardation layers obtained in examples and comparative examples were cut into dimensions of 10mm × 10 mm. The cut polarizing plate with a retardation layer was bonded to a glass plate (thickness: 1.1 mm) via an acrylic adhesive layer having a thickness of 20 μm. After the sample bonded to the glass plate was placed in an oven at 100 degrees for 120 hours, the presence or absence of cracks in the absorption axis direction (MD direction) of the polarizer was visually checked. This evaluation was performed using 3 polarizing plates with retardation layers, and the number of polarizing plates with retardation layers in which cracks occurred was evaluated.
(6) Resistance to bending
The polarizing plates with retardation layers obtained in examples and comparative examples were cut into 50mm × 100mm dimensions. At this time, the polarizer is cut out so that the absorption axis direction of the polarizer becomes the longitudinal direction. The cut polarizing plate with a retardation layer was subjected to a bending test at room temperature using a bending tester (product name: DLDM111LH, manufactured by Yuasa-system Co.). Specifically, the polarizing plate with a retardation layer was set to have a deflection diameter at 60rpm so that the retardation layer side of the polarizing plate became inner and the protective layer or the hard coat layer formed on the protective layer became outer
(R is 0.5 mm), and the polarizing plate with a retardation layer was folded 5 ten thousand times in the absorption axis direction. Then, the presence or absence of cracks in the polarizing plate with a retardation layer after the test was visually confirmed, and the one with no cracks was regarded as good, and the one with cracks was regarded as not good. The folding direction is the transmission axis direction of the polarizer.
(7) Transmittance and degree of polarization of monomer
The polarizers used in the examples and comparative examples were respectively designated as the single transmittance Ts, the parallel transmittance Tp, and the vertical transmittance Tc measured by an ultraviolet-visible spectrophotometer (product name "V-7100" by japan spectrophotometers) as Ts, tp, and Tc of the polarizers. These Ts, tp and Tc are Y values measured in a 2-degree field of view (C light source) according to JIS Z8701 and corrected for visibility.
From the Tp and Tc thus obtained, the polarization degree P was determined by the following equation.
Polarization degree P (%) = { (Tp-Tc)/(Tp + Tc) } 1/2 ×100
(8) Puncture strength
The polarizing material was peeled off from the polarizing material/thermoplastic resin substrate laminate used in examples and comparative examples, and the laminate was placed on a compression tester (KATO TECH co., ltd., product name "NDG5" needle penetration force measurement specification) equipped with a needle, and subjected to puncture at a puncture speed of 0.33 cm/sec in an environment of room temperature (23 ℃ ± 3 ℃), and the strength at which the polarizing material was broken was defined as the breaking strength (puncture strength). Evaluation value the breaking strength of 10 test pieces was measured and the average value thereof was used. It should be noted that the needle tip diameter is used
0.5R needle. For the polarizer to be measured, a jig having a circular opening with a diameter of about 11mm was clamped and fixed from both sides of the polarizer, and then a test was performed on the central puncture needle of the opening.
[ Table 1]
As is clear from table 1, the polarizing plates with retardation layers of examples 1 to 26 were inhibited from cracking even when subjected to heat treatment. Further, the durability at bending is also excellent.
Industrial applicability
The polarizing plate with a retardation layer of the present invention is suitable for use in an image display device.
Description of the reference numerals
10: polarizing plate
11: polarizing piece
12: 1 st protective layer
13: the 2 nd protective layer
20: retardation layer
100: polarizing plate with phase difference layer
101: polarizing plate with phase difference layer
102: polarizing plate with phase difference layer
Claims (10)
1. A polarizing plate with a retardation layer, which comprises a polarizing element and a protective layer, wherein the polarizing element comprises a polyvinyl alcohol resin film containing a dichroic material, and the protective layer is disposed on one side of the polarizing element;
the phase difference layer is an orientation curing layer of a liquid crystal compound;
the thickness of the protective layer is less than 10 μm;
the polarizer satisfies the following formula (1) when the monomer transmittance is x% and the birefringence of the polyvinyl alcohol resin is y:
y<-0.011x+0.525 (1)。
2. a polarizing plate with a retardation layer, which comprises a polarizing element and a protective layer, wherein the polarizing element comprises a polyvinyl alcohol resin film containing a dichroic material, and the protective layer is disposed on one side of the polarizing element;
the phase difference layer is an orientation curing layer of a liquid crystal compound;
the thickness of the protective layer is less than 10 μm;
the polarizer satisfies the following formula (2) when the monomer transmittance is x% and the in-plane retardation of the polyvinyl alcohol resin film is znm:
z<-60x+2875 (2)。
3. a polarizing plate with a retardation layer, which comprises a polarizing element and a protective layer, wherein the polarizing element is composed of a polyvinyl alcohol resin film containing a dichroic material, and the protective layer is disposed on one side of the polarizing element;
the phase difference layer is an orientation curing layer of a liquid crystal compound;
the thickness of the protective layer is less than 10 μm;
the polarizer satisfies the following formula (3) when the monomer transmittance is x% and the orientation function of the polyvinyl alcohol resin is f:
f<-0.018x+1.11 (3)。
4. the polarizing plate with a retardation layer according to any one of claims 1 to 3, having a total thickness of 30 μm or less.
5. The polarizing plate with a retardation layer according to any one of claims 1 to 4, wherein the thickness of the polarizing element is 10 μm or less.
6. The polarizing plate with a retardation layer according to any one of claims 1 to 5, wherein the polarizing element has a single-body transmittance of 40.0% or more and a polarization degree of 99.0% or more.
7. The polarizing plate with a retardation layer according to any one of claims 1 to 6, wherein the protective layer is composed of at least 1 selected from the group consisting of a solid substance of a coating film of an organic solvent solution of a thermoplastic (meth) acrylic resin, a photo cation cured substance of an epoxy resin, and a solid substance of a coating film of an organic solvent solution of an epoxy resin.
8. The polarizing plate with a retardation layer according to claim 7, wherein the thermoplastic (meth) acrylic resin has at least 1 repeating unit selected from the group consisting of a lactone ring unit, a glutaric anhydride unit, a glutarimide unit, a maleic anhydride unit, and a maleimide unit.
9. The polarizing plate with a retardation layer according to claim 7, wherein the protective layer is a photo cation cured product of an epoxy resin having at least 1 selected from the group consisting of an aromatic skeleton and a hydrogenated aromatic skeleton.
10. An image display device comprising the polarizing plate with a retardation layer according to any one of claims 1 to 9.
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| JP2020-110628 | 2020-06-26 | ||
| JP2020110628 | 2020-06-26 | ||
| JP2020-133459 | 2020-08-06 | ||
| JP2020133459 | 2020-08-06 | ||
| PCT/JP2021/022774 WO2021261344A1 (en) | 2020-06-26 | 2021-06-16 | Retardation-layer-equipped polarizing plate and image display device using same |
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| JP (1) | JPWO2021261344A1 (en) |
| KR (1) | KR20230028728A (en) |
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| JP2001343521A (en) | 2000-05-31 | 2001-12-14 | Sumitomo Chem Co Ltd | Polarizing plate and method for manufacturing the same |
| JP5036191B2 (en) * | 2005-03-16 | 2012-09-26 | 日本合成化学工業株式会社 | Polyvinyl alcohol film and method for producing the same |
| JP6202062B2 (en) * | 2014-09-30 | 2017-09-27 | 住友化学株式会社 | Method for measuring strength of polarizing film and polarizing plate |
| KR102645969B1 (en) * | 2014-12-12 | 2024-03-08 | 스미또모 가가꾸 가부시키가이샤 | Method for producing polarizing film, and polarizing film |
| JP2017003954A (en) * | 2015-06-12 | 2017-01-05 | 住友化学株式会社 | Polarizing film and polarizing plate including the same |
| JP6833687B2 (en) * | 2015-07-16 | 2021-02-24 | 東海精密工業株式会社 | Manufacturing method of polarized molded article |
| JP2017187731A (en) * | 2016-03-30 | 2017-10-12 | 住友化学株式会社 | Manufacturing methods for stretched film and polarizing film |
| JP6684630B2 (en) * | 2016-03-31 | 2020-04-22 | 住友化学株式会社 | Polarizing plate and method of manufacturing polarizing plate |
| JP2017062517A (en) * | 2017-01-12 | 2017-03-30 | 日東電工株式会社 | Polarizing film with retardation layer, and image display device |
| CN110431454B (en) * | 2017-03-28 | 2021-07-16 | 日本瑞翁株式会社 | Phase difference plate, multilayer phase difference plate, polarizing plate, image display device, and polymerizable compound |
| JP6784839B2 (en) * | 2017-06-22 | 2020-11-11 | 日東電工株式会社 | Laminated body and manufacturing method of laminated body |
| KR102442993B1 (en) * | 2018-02-14 | 2022-09-13 | 후지필름 가부시키가이샤 | Circular polarizer with image display device and photosensitive adhesive |
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