CN113423572A - Polarizing plate, method for producing same, and image display device using same - Google Patents
Polarizing plate, method for producing same, and image display device using same Download PDFInfo
- Publication number
- CN113423572A CN113423572A CN202080013941.2A CN202080013941A CN113423572A CN 113423572 A CN113423572 A CN 113423572A CN 202080013941 A CN202080013941 A CN 202080013941A CN 113423572 A CN113423572 A CN 113423572A
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- China
- Prior art keywords
- layer
- polarizing plate
- polarizer
- stretching
- liquid crystal
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- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- 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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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- 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
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
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- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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Abstract
Provided is a polarizing plate which has excellent bendability and in which changes in optical characteristics due to bending are suppressed. The polarizing plate of the present invention comprises: the optical element includes a polarizer, a protective layer disposed on one side of the polarizer, and an optical function layer disposed on the other side of the polarizer. The polarizing plate has a puncture strength of 10gf/μm or more. In one embodiment, the optically functional layer functions as a protective layer different from the protective layer. In another embodiment, the optical functional layer is a retardation layer having a circular polarization function or an elliptical polarization function.
Description
Technical Field
The present invention relates to a polarizing plate, a method for producing the same, 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 phase difference 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). In recent years, as the demand for a curved image display device and/or a foldable or foldable image display device has increased, a polarizing plate (as a result, a polarizing plate with a retardation layer) is also required to have excellent bendability as mechanical characteristics and to be free from a change in optical characteristics due to bending. However, a polarizing plate satisfying such characteristics (as a result, a polarizing plate with a retardation layer) still leaves room for practical studies.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3325560
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above conventional problems, and a main object thereof is to provide a polarizing plate having excellent bendability and in which a change in optical characteristics due to bending is suppressed.
Means for solving the problems
The polarizing plate of the present invention comprises: the polarizer comprises a polarizer, a protective layer arranged on one side of the polarizer, and an optical functional layer arranged on the other side of the polarizer, wherein the penetration strength of the polarizer is more than 10 gf/mum.
In one embodiment, the optically functional layer has a thickness of 20 μm or less.
In one embodiment, the optically functional layer functions as a protective layer different from the protective layer.
In another embodiment, the optically functional layer is a retardation layer having a circular polarization function or an elliptical polarization function. In this case, the retardation layer is a single layer of an alignment cured layer of a liquid crystal compound, the Re (550) of the retardation layer is 100nm to 190nm, and the angle formed by the slow axis of the retardation layer and the absorption axis of the polarizer is 40 ° to 50 °. As another example, the retardation layer has a laminated structure of a 1 st alignment cured layer of a liquid crystal compound and a 2 nd alignment cured layer of a liquid crystal compound; the Re (550) of the oriented cured layer of the 1 st liquid crystal compound is 200 to 300nm, and the angle formed by the slow axis and the absorption axis of the polarizer is 10 to 20 degrees; the Re (550) of the alignment cured layer of the 2 nd liquid crystal compound is 100 to 190nm, and the angle formed by the slow axis and the absorption axis of the polarizer is 70 to 80 degrees.
In one embodiment, the polarizer has a thickness of 10 μm or less.
In one embodiment, the protective layer has a thickness of 50 μm or less.
In one embodiment, the total thickness of the polarizing plate is 60 μm or less.
In one embodiment, the polarizer is formed of a polyvinyl alcohol resin film containing iodine. In one embodiment, the polarizer includes an acetoacetyl-modified polyvinyl alcohol resin.
According to another aspect of the present invention, there is provided a method of manufacturing the polarizing plate. The manufacturing method comprises the following steps: forming a polyvinyl alcohol resin layer on one side of a long thermoplastic resin base material to form a laminate; and stretching and dyeing the laminate to form a polarizing plate from the polyvinyl alcohol resin layer, wherein the polarizing plate has a puncture strength of 10gf/μm or more.
In one embodiment, the above manufacturing method includes: a polyvinyl alcohol resin layer containing a polyvinyl alcohol resin and containing an iodide or sodium chloride is formed on one side of the thermoplastic resin substrate.
In one embodiment, the above manufacturing method includes: the laminate is subjected to an in-air auxiliary stretching treatment, a dyeing treatment, an in-water stretching treatment, and a drying shrinkage treatment in which the laminate is shrunk by 2% or more in the width direction by heating while being conveyed in the longitudinal direction, in this order.
In one embodiment, the difference between the width residual ratio and the free shrinkage width residual ratio in the above-mentioned in-air auxiliary stretching is 2% or more.
In one embodiment, the stretching ratio in the aerial auxiliary stretching is 2.3 times or more.
According to another aspect of the present invention, there is provided an image display device. The image display device is provided with the polarizing plate.
In one embodiment, the image display device is an organic electroluminescence display device or an inorganic electroluminescence display device. In one embodiment, the image display device can be folded or folded.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polarizing plate having excellent bendability and in which a change in optical characteristics due to bending is suppressed can be obtained by setting the puncture strength of a polarizing material to a predetermined value or more.
Drawings
Fig. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention.
Fig. 2 is a schematic view showing an example of drying shrinkage treatment using a heating roller in the method for manufacturing a polarizing plate of the present invention.
Detailed Description
The following description will explain embodiments of the present invention, but the present invention is not limited to these embodiments.
(definitions of terms and symbols)
The terms and symbols in the present specification are defined as follows.
(1) Refractive index (nx, ny, nz)
"nx" is a refractive index in a direction in which an in-plane refractive index is 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. lamda.nm. For example, "Re (550)" is an in-plane retardation measured at 23 ℃ with light having a wavelength of 550 nm. When the thickness of the layer (thin film) is d (nm), Re (λ) is represented by the formula: re (λ) ═ (nx-ny) × d.
(3) Retardation in thickness direction (Rth)
"Rth (λ)" is a phase difference in the thickness direction measured at 23 ℃ with light having a wavelength of λ nm. For example, "Rth (550)" is a phase difference in the thickness direction measured at 23 ℃ with light having a wavelength of 550 nm. When the thickness of the layer (film) is d (nm), Rth (λ) is expressed by the following formula: rth (λ) ═ n x-nz × d.
(4) Coefficient of Nz
The Nz coefficient is obtained by Nz ═ Rth/Re.
(5) Angle of rotation
When an angle is referred to in this specification, the angle includes angles in both clockwise and counterclockwise directions with respect to a reference direction. Thus, for example, "45" means ± 45 °.
A. Integral constitution of polarizing plate
Fig. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. The polarizing plate 100 of the present embodiment includes: a polarizer 10, a protective layer 30 disposed on one side of the polarizer 10, and an optically functional layer 20 disposed on the other side of the polarizer. In the embodiment of the present invention, the polarizing material has a puncture strength of 10gf/μm or more. By setting the puncture strength of the polarizer to such a range, a polarizing plate having excellent bendability can be realized. The puncture strength indicates the fracture resistance of the polarizing element when the polarizing element is punctured with a predetermined strength. The piercing strength can be expressed, for example, as a strength at which a predetermined needle is attached to a compression tester and the polarizing material is broken when the needle is pierced through the polarizing material at a predetermined speed. As can be seen from the unit, the puncture strength is the puncture strength per unit thickness (1 μm) of the polarizer.
The thickness of the optically functional layer 20 is preferably 20 μm or less. With such a configuration, an extremely thin polarizing plate can be realized. In one embodiment, the optically functional layer functions as a protective layer other than protective layer 30. Such a protective layer can also function as a retardation layer having a predetermined retardation and optical characteristics. In another embodiment, the optical functional layer is a retardation layer having a circular polarization function or an elliptical polarization function. Such a retardation layer can also function as a protective layer for a polarizer. When the optical function layer is a retardation layer, in one embodiment, the retardation layer is an alignment cured layer of a liquid crystal compound. The phase difference layer may be a single layer of the orientation cured layer, or may have a laminated structure of the 1 st orientation cured layer and the 2 nd orientation cured layer. Hereinafter, a polarizing plate having a retardation layer as an optical functional layer may be referred to as a polarizing plate with a retardation layer.
Each layer or optical film constituting the polarizing plate is typically bonded via an adhesive layer. Examples of the adhesive layer include an adhesive layer and an adhesive layer. In the embodiment of the present invention, an adhesive layer can be suitably used. With such a configuration, the polarizing plate can be further thinned. As the adhesive constituting the adhesive layer, an active energy ray-curable adhesive (for example, an ultraviolet-curable adhesive) is typically mentioned.
Other retardation layers may be provided in the polarizing plate with a retardation layer. The other retardation layer is typically provided on the outer side of the retardation layer 20 (the side opposite to the polarizer 10). Other retardation layers are typically represented by a relationship showing a refractive index characteristic nz > nx ═ ny. As such another retardation layer, it is preferable to provide the retardation layer as a single layer of the alignment cured layer. For convenience, the retardation layer 20 may be referred to as a 1 st retardation layer, and the other retardation layers may be referred to as 2 nd retardation layers. The polarizing plate with a retardation layer 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 may have a conductive layer or an isotropic substrate with a conductive layer. The conductive layer or the isotropic substrate with the conductive layer is typically disposed outside the optically functional layer 20 (opposite to the polarizer 10). When the polarizing plate is a polarizing plate with a retardation layer having a retardation layer and another retardation layer, the other retardation layer and the conductive layer or the isotropic base material with a conductive layer are typically provided in this order from the side of the retardation layer (optical functional layer) 20. When a conductive layer or an isotropic substrate with a conductive layer is provided, a polarizing plate or a polarizing plate with a retardation layer can be applied to a so-called inner touch panel type input display device in which a touch sensor is incorporated between an image display unit (for example, an organic EL unit) and the polarizing plate.
The polarizing plate of the present invention may be in the form of a sheet or a long strip. In the present specification, the "elongated shape" refers to an elongated shape having a length sufficiently long with respect to the width, and includes, for example, an elongated shape having a length 10 times or more, preferably 20 times or more with respect to the width. The long polarizing plate may be wound in a roll shape.
In practical applications, an adhesive layer (not shown) is provided on the side of the optically functional layer opposite to the polarizer so that the polarizing plate 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 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 is preferably 100 μm or less, more preferably 80 μm or less, further preferably 70 μm or less, and particularly preferably 60 μm or less. The lower limit of the total thickness may be, for example, 25 μm. According to the embodiments of the present invention, such an extremely thin polarizing plate can be realized. Such a polarizing plate can have extremely excellent bendability due to a synergistic effect with the effect based on the puncture strength of the polarizer. Such a polarizing plate can be suitably applied to a curved image display device, a bendable or foldable image display device, and can be particularly suitably applied to a bendable or foldable image display device. The total thickness of the polarizing plate is the sum of the thicknesses of all layers constituting the polarizing plate except for the adhesive layer.
Hereinafter, the constituent elements of the polarizing plate will be described in more detail.
B. Polarizing piece
The polarizing plate 10 has a puncture strength of 10gf/μm or more, for example, 13gf/μm or more, preferably 20gf/μm or more, more preferably 30gf/μm or more, and still more preferably 40gf/μm or more, as described above. The upper limit of the puncture strength may be, for example, 80gf/μm. By setting the puncture strength of the polarizer to such a range, a polarizing plate having excellent bendability can be realized.
The polarizer is typically made of a polyvinyl alcohol (PVA) resin film containing a dichroic material (typically iodine). Preferably, the PVA-based resin constituting the PVA-based resin film (substantially, polarizer) contains an acetoacetyl group-modified PVA-based resin. With such a configuration, a polarizer having a desired piercing strength can be obtained. The amount of the acetoacetyl group-modified PVA resin is preferably 5 to 20 wt%, more preferably 8 to 12 wt%, based on 100 wt% of the total PVA resin. If the amount of the compound is in such a range, the puncture strength can be set to a more suitable range.
The boric acid content of the polarizing material is preferably 10% by weight or more, more preferably 13% by weight to 25% by weight.
When the boric acid content of the polarizer is in such a range, the ease of curl adjustment at the time of lamination can be favorably maintained by a synergistic effect with the iodine content described later, and curl at the time of heating can be favorably suppressed and appearance durability at the time of heating can be favorably improved. The boric acid content can be calculated as the amount of boric acid contained in the polarizer per unit weight, for example, by a neutralization method using the following formula.
The iodine content of the polarizer is preferably 2.0 wt% or more, and more preferably 2.0 wt% to 10 wt%. If the iodine content of the polarizer is in such a range, the curl adjustment can be favorably maintained by the synergistic effect with the boric acid content, and the appearance durability can be favorably improved while suppressing the curl during heating. In the present specification, "iodine content" refers to the amount of all iodine contained in the polarizer (PVA-based resin film). More specifically, in the polarizer, iodine is represented by iodide ion (I)-) Iodine molecule (I)2) Polyiodide (I)3 -、I5 -) When the form exists, the iodine content in the present specification means an amount of iodine including all of these forms. The iodine content can be calculated, for example, by a standard curve method of fluorescent X-ray analysis. Note that, in the polarizing plate, polyiodide exists in a state of forming a PVA-iodine complex. By forming such a complex, absorption dichroism can be exhibited in a wavelength range of visible light. Specifically, a complex of PVA and triiodide ion (PVA. I)3 -) A complex of PVA and a pentaiodide ion (PVA. I) having an absorption peak at about 470nm5 -) Has an absorption peak around 600 nm. As a result, the polyiodide can absorb light in a wide range of visible light depending on its form. On the other hand, iodide ion (I)-) Has an absorption peak near 230nm, and does not substantially participate in the absorption of visible light. Therefore, the polyiodide existing in a state of a complex with PVA is mainly related to the absorption performance of the polarizer.
The thickness of the polarizer is preferably 1 μm to 10 μm, more preferably 1 μm to 8 μm, and still more preferably 2 μm to 5 μm. The thickness of the polarizer was 5 μm to 8 μm in 1 embodiment.
The polarizing element preferably exhibits dichroism of absorption at any wavelength of 380nm to 780 nm. The polarizer preferably has a single transmittance Ts of 40.0% to 48.0%, more preferably 41.0% to 46.0%. The degree of polarization P of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and still more preferably 99.9% or more. The monomer transmittance is typically a Y value measured by an ultraviolet-visible spectrophotometer and corrected for photosensitivity. The polarization degree is typically determined by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc obtained by measuring and correcting the visibility using an ultraviolet-visible spectrophotometer.
Polarization degree (%) { (Tp-Tc)/(Tp + Tc) }1/2×100
The polarizer can be typically produced using a laminate of two or more layers. As a specific example of the polarizer obtained using the laminate, there is a polarizer obtained using a laminate of a resin base material and a PVA-based resin layer formed by coating the resin base material. A polarizer obtained using a laminate of a resin base material and a PVA-based resin layer formed by coating the resin base material 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 was stretched and dyed to prepare a polarizing element 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 to perform stretching. Further, the stretching may further include, if necessary: prior to stretching in an aqueous boric acid solution, the laminate is subjected to in-air stretching at a high temperature (e.g., 95 ℃ or higher). Further, in the present embodiment, the laminate is preferably subjected to a drying shrinkage treatment in which the laminate is shrunk by 2% or more in the width direction by heating while being conveyed in the longitudinal direction. Typically, the production method of the present embodiment includes subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in this order. By introducing the auxiliary stretching, the crystallinity of the PVA can be improved even when the PVA is coated on the thermoplastic resin, and high optical characteristics can be realized. Further, by improving the orientation of the PVA in advance, it is possible to prevent problems such as degradation of the orientation and dissolution of the PVA when immersed in water in the subsequent dyeing step and stretching step, and to realize high optical characteristics. 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 can improve the optical properties of the polarizing film obtained through a treatment step of immersing the laminate in a liquid, such as dyeing treatment or underwater stretching treatment. Further, the optical characteristics 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 according to the purpose may be laminated on the peeled surface. Details of the method for manufacturing the polarizer will be described in item G below.
C. Optically functional layer
C-1. optical function layer as protective layer
When the optical function layer 20 functions as a protective layer different from the protective layer 30, the protective layer is preferably a thin protective layer having a thickness of 20 μm or less, as described above. The thickness of the protective layer is more preferably 18 μm or less, still more preferably 15 μm or less, and particularly preferably 10 μm or less. The lower limit of the thickness of the protective layer may be, for example, 1 μm.
The protective layer (optical function layer) may be formed of a resin thin film or may be formed of a cured product of a coating film. Examples of the resin constituting the resin film include a cycloolefin resin and an acrylic resin. The cured product of the coating film may be, for example, a cured product of a coating film of an organic solvent solution of a predetermined acrylic resin. When the protective layer is formed of a cured product of the coating film, the thickness can be made extremely smaller than that of the resin thin film.
The protective layer (optical functional layer) is typically disposed on the image display unit side when the polarizing plate is applied to an image display device. In one embodiment, the protective layer is preferably optically isotropic. In the present specification, "optically isotropic" means that the in-plane retardation Re (550) is 0nm to 10nm and the retardation Rth (550) in the thickness direction is-10 nm to +10 nm. In another embodiment, the protective layer may be a phase difference layer having any suitable phase difference value. In this case, the in-plane retardation Re (550) of the protective layer (retardation layer) is, for example, 110nm to 150 nm.
C-2. optical function layer as phase difference layer with circular polarization function or elliptical polarization function
When the optical functional layer 20 is a retardation layer having a circular polarization function or an elliptical polarization function, the retardation layer may be a stretched film of a resin film or an oriented cured layer of a liquid crystal compound. Preferably an oriented 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 extremely large as compared with a non-liquid crystal material, and therefore the thickness of the retardation layer for obtaining a desired in-plane retardation can be made extremely small as compared with a stretched film. As a result, the polarizing plate with a retardation layer can be further thinned. As a result, a polarizing plate with a retardation layer having extremely excellent bendability can be realized by a synergistic effect with the effect of the puncture strength of the polarizing material. Hereinafter, the alignment cured layer of the liquid crystal compound will be described in detail. The retardation layer formed of a stretched film of a resin film is described in, for example, japanese patent laid-open nos. 2017-54093 and 2018-60014. The descriptions of these publications are incorporated herein by reference.
The "alignment cured layer" in the present specification means a layer in which a liquid crystal compound is aligned in a predetermined direction in a 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 the present embodiment, typically, the rod-like liquid crystal compound is aligned in a state of being aligned in the slow axis direction of the 1 st retardation layer (homogeneous alignment).
Examples of the liquid crystal compound include a liquid crystal compound in which a liquid crystal phase is 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 developing the 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 each alone or in combination.
When the liquid crystal compound is a liquid crystal monomer, the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the alignment state of the liquid crystal monomer can be fixed by polymerizing or crosslinking (i.e., curing) the liquid crystal monomer. After the liquid crystal monomers are aligned, for example, when the liquid crystal monomers are polymerized or crosslinked with each other, the alignment state can be fixed thereby. Here, the polymer is formed by polymerization, and the 3-dimensional network structure is formed by crosslinking, but they are non-liquid crystalline. Therefore, the 1 st retardation layer formed does not undergo a phase transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change, which is typical of liquid crystalline compounds, for example. As a result, the 1 st retardation layer is a retardation layer which is not affected by temperature change and has extremely excellent stability.
The temperature range in which the liquid crystal monomer exhibits liquid crystallinity differs depending on the type thereof. Specifically, the temperature range is preferably 40 to 120 ℃, more preferably 50 to 100 ℃, and most preferably 60 to 90 ℃.
As the liquid crystal monomer, any suitable liquid crystal monomer can be used. For example, polymerizable mesogenic compounds described in Japanese patent application laid-open No. 2002-533742(WO00/37585), EP358208(US5211877), EP66137(US4388453), WO93/22397, EP0261712, DE19504224, DE4408171, GB2280445 and the like can be used. Specific examples of such polymerizable mesogenic compounds include trade name LC242 from BASF, trade name E7 from Merck, and trade name LC-Sillicon-CC3767 from Wacker-Chem. The liquid crystal monomer is preferably a nematic liquid crystal monomer, for example.
The alignment cured layer of the liquid crystal compound may be formed by: the method for producing a liquid crystal display device includes applying an alignment treatment to a surface of a predetermined substrate, applying a coating liquid containing a liquid crystal compound to the surface, aligning 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 alignment cured layer formed on the substrate may be transferred to the surface of the polarizer 10.
As the alignment treatment, any appropriate alignment treatment may be adopted. Specifically, mechanical alignment treatment, physical alignment treatment, and chemical alignment treatment can be mentioned. Specific examples of the mechanical orientation treatment include brushing and stretching. Specific examples of the physical alignment treatment include magnetic field alignment treatment and electric field alignment treatment. Specific examples of the chemical alignment treatment include oblique vapor deposition and photo alignment treatment. The treatment conditions for the various alignment treatments may be any suitable conditions according to the purpose.
The alignment of the liquid crystal compound is performed by performing a treatment at a temperature at which the liquid crystal phase is exhibited according to 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 according to the alignment treatment direction of the substrate surface.
In one embodiment, the alignment state is fixed 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 japanese patent application laid-open No. 2006-163343. The description of this publication is incorporated herein by reference.
As another example of the alignment cured layer, a form in which the discotic liquid crystal compound is aligned in any state of vertical alignment, hybrid alignment, and tilt alignment can be cited. The discotic liquid crystal compound is typically a discotic liquid crystal compound in which the discotic plane is aligned substantially perpendicular to the film plane of the 1 st retardation layer. The discotic liquid crystalline compound being substantially perpendicular means: the average value of the angle formed by the film surface and the disk surface 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 molecular structure in which a cyclic parent nucleus such as benzene, 1,3, 5-triazine, calixarene, or the like is arranged at the center of the molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, or the like is substituted as a side chain thereof in a radial shape. Typical examples of the discotic liquid crystal include a study report of c.destrande et al, a study report of mol.cryst.liq.cryst.71, a benzene derivative described on page 111 (1981), a triphenylene derivative, a truxene derivative, a phthalocyanine derivative, a study report of b.kohne et al, a study report of angelw.chem.96, a cyclohexane derivative described on page 70 (1984), a study report of j.m.lehn et al, a study report of j.chem.soc.chem.commun, a study report of 1794 (1985), a study report of j.zhang et al, a study report of j.am.chem.soc.116, an azacrown ether-based macrocycle described on page 2655 (1994), and a phenylacetylene-based macrocycle. Further specific examples of the discotic liquid crystal compound include compounds described in 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 retardation layer (optical function layer) 20 is a single layer of an alignment cured layer of a liquid crystal compound. When the retardation layer (hereinafter, also referred to as the 1 st retardation layer as described above) is composed of a single layer of an alignment cured layer of a liquid crystal compound, the thickness thereof is preferably 0.5 to 7 μm, more preferably 1 to 5 μm. By using the liquid crystal compound, an in-plane retardation equivalent to that of the resin film can be realized with a thickness extremely smaller than that of the resin film.
The 1 st retardation layer is typically a layer exhibiting a refractive index characteristic 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 can function as a λ/4 plate. In this case, the in-plane retardation Re (550) of the 1 st retardation layer is preferably 100nm to 190nm, more preferably 110nm to 170nm, and still more preferably 130nm to 160 nm. Here, "ny ═ nz" includes not only the case where ny and nz are completely equal but also the case where ny and nz are substantially equal. Therefore, ny > nz or ny < nz may be used in some cases 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. By satisfying such a relationship, when the obtained polarizing plate with a retardation layer is used in an image display device, a very excellent reflection hue can be realized.
The 1 st retardation layer may exhibit anomalous dispersion wavelength characteristics in which the phase difference value becomes larger according to the wavelength of the measurement light, may exhibit normal wavelength dispersion characteristics in which the phase difference value becomes smaller according to the wavelength of the measurement light, and may exhibit flat wavelength dispersion characteristics in which the phase difference value hardly changes according to the wavelength of the measurement light. In one embodiment, the 1 st phase difference layer exhibits anomalous dispersion wavelength characteristics. In this case, Re (450)/Re (550) of the retardation layer is preferably 0.8 or more and less than 1, and more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection characteristics can be achieved.
The angle θ formed by the slow axis of the 1 st retardation layer 20 and the absorption axis of the polarizer 10 is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and still more preferably about 45 °. If the angle θ is in such a range, a polarizing plate with a retardation layer having very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics) can be obtained by using λ/4 plate as the 1 st retardation layer as described above.
In another embodiment, the 1 st phase difference layer 20 may have a laminated structure of the 1 st orientation cured layer and the 2 nd orientation cured layer. In this case, either one of the 1 st oriented cured layer and the 2 nd oriented cured layer 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 and the 2 nd orientation cured layer can be adjusted in such a manner that a desired in-plane phase difference of λ/4 plate or λ/2 plate is obtained. For example, when the 1 st orientation cured layer functions as a λ/2 plate and the 2 nd orientation cured layer functions as a λ/4 plate, the thickness of the 1 st orientation cured layer is, for example, 2.0 μm to 3.0 μm, and the thickness of the 2 nd orientation cured layer 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 280 nm. 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 further preferably about 75 °. With such a configuration, a characteristic close to an ideal anomalous dispersion characteristic can be obtained, and as a result, a very excellent antireflection characteristic 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 for the single-layer alignment cured layer.
D. Phase difference layer 2
As described above, the 2 nd retardation layer may be a so-called Positive C-plate (Positive C-plate) having refractive index characteristics showing a relationship of nz > nx ═ ny. By using the positive C plate as the 2 nd retardation layer, the oblique reflection can be prevented well, and the antireflection function can be made wide in viewing angle. The 2 nd retardation layer is preferably provided in the case where the 1 st retardation layer is a single layer of the orientation cured layer. The retardation Rth (550) in the thickness direction of the 2 nd retardation layer is preferably from-50 nm to-300 nm, more preferably from-70 nm to-250 nm, still more preferably from-90 nm to-200 nm, and particularly preferably from-100 nm to-180 nm. Here, "nx ═ ny" includes not only a case where nx and ny are strictly equal but also a case where nx and ny are substantially equal. That is, the in-plane retardation Re (550) of the 2 nd retardation layer may be less than 10 nm.
The 2 nd retardation layer having a refractive index characteristic of nz > nx ═ ny may be formed of any suitable material. The 2 nd retardation layer is preferably formed of a film containing a liquid crystal material fixed in homeotropic alignment. The liquid crystal material (liquid crystal compound) capable of homeotropic alignment 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 compound and the method for forming the retardation layer described in paragraphs [0020] to [0028] of Japanese patent laid-open No. 2002-333642. In this case, the thickness of the 2 nd retardation layer is preferably 0.5 to 10 μm, more preferably 0.5 to 8 μm, and still more preferably 0.5 to 5 μm.
E. Protective layer
The protective layer 30 may be formed of any suitable thin film that can be used as a protective layer of a polarizer. Specific examples of the material to be the main component of the film include cellulose resins such as Triacetylcellulose (TAC), polyester resins, polyvinyl alcohol resins, polycarbonate resins, polyamide resins, polyimide resins, polyether sulfone resins, polysulfone resins, polystyrene resins, polynorbornene resins, polyolefin resins, (meth) acrylic resins, acetate resins, and the like transparent resins. Further, there may be mentioned thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, silicone and the like, ultraviolet-curable resins and the like. Other examples include glassy polymers such as siloxane polymers. Further, the polymer film described in Japanese patent application laid-open No. 2001-343529 (WO01/37007) may be used. As a material of the film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in a side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in a side chain can be used, and for example, a resin composition having an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer can be mentioned. The polymer film may be, for example, an extrusion molded product of the resin composition.
As described later, the polarizing plate or the polarizing plate with a retardation layer of the present invention is typically disposed on the viewing side of the image display device, and the protective layer 30 is typically disposed on the viewing side thereof. Therefore, the protective layer 30 may be subjected to surface treatment such as hard coating treatment, antireflection treatment, adhesion prevention treatment, and antiglare treatment as needed. Further, the protective layer 30 may be subjected to a process for improving the visibility when the vision is recognized through the polarized sunglasses (typically, imparting a (elliptical) polarization function and imparting a super high retardation) as necessary. By performing such processing, even when the display screen is visually recognized through a polarizing lens such as a polarizing sunglass, excellent visual recognition can be achieved. Therefore, the polarizing plate or the polarizing plate with a retardation layer can be suitably applied to an image display device that can be used outdoors.
The thickness of the protective layer is preferably 50 μm or less, and more preferably 5 to 40 μm. When the surface treatment is performed, the thickness of the outer protective layer is a thickness including the thickness of the surface treatment layer.
F. Conductive layer or isotropic substrate with conductive layer
The conductive layer can be formed by forming a metal oxide film on any suitable substrate by any suitable film forming method (for example, vacuum deposition, sputtering, CVD, ion plating, spraying, or the like). Examples of the metal oxide include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. Among them, indium tin composite oxide (ITO) is preferable.
When the conductive layer contains a metal oxide, the thickness of the conductive layer is preferably 50nm or less, and more preferably 35nm or less. The lower limit of the thickness of the conductive layer is preferably 10 nm.
The conductive layer may be transferred from the substrate to the optical functional layer (or to the 2 nd retardation layer when the 2 nd retardation layer is present) so that the conductive layer itself is a constituent layer of the polarizing plate with a retardation layer, or may be laminated on the optical functional layer (or to the 2 nd retardation layer when the 2 nd retardation layer is present) in the form of a laminate with the substrate (substrate with a conductive layer). Preferably, the substrate is optically isotropic, and thus the conductive layer can be used as an isotropic substrate with a conductive layer for a polarizing plate.
As the optically isotropic substrate (isotropic substrate), any appropriate isotropic substrate can be used. Examples of the material constituting the isotropic base include a material having a resin not having a conjugated system such as a norbornene-based resin or an olefin-based resin as a main skeleton, and a material having a cyclic structure such as a lactone ring or a glutarimide ring in a main chain of an acrylic resin. When such a material is used, the retardation accompanying the molecular chain orientation can be suppressed to a small level when forming an isotropic base material. The thickness of the isotropic base material is preferably 50 μm or less, more preferably 35 μm or less. The lower limit of the thickness of the isotropic base material is, for example, 20 μm.
The conductive layer of 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 can function as touch sensor electrodes for sensing contact with the touch panel. As the patterning method, any appropriate method may be adopted. Specific examples of the patterning method include a wet etching method and a screen printing method.
G. Method for manufacturing polarizing piece
The polarizer can be produced, for example, by a method including the steps of: 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 produce a laminate; and subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in this order, wherein the laminate is shrunk by 2% or more in the width direction by heating while being conveyed in the longitudinal direction. 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. The drying shrinkage treatment is preferably carried out using a heated roller, and the temperature of the heated roller is preferably 60 to 120 ℃. The shrinkage rate in the width direction of the laminate by the drying shrinkage treatment is preferably 2% or more. According to such a manufacturing method, the polarizing plate described in the above item B can be obtained. In particular, by producing a laminate including a halide-containing PVA-based resin layer, stretching the laminate in multiple stages including air-assisted stretching and underwater stretching, and heating the stretched laminate with a heating roller, a polarizer having excellent optical characteristics (typically, monomer transmittance and polarization degree) and suppressed variation in optical characteristics can be obtained. Specifically, by using a heating roller in the drying and shrinking treatment step, the laminate can be uniformly shrunk over the entire laminate while being conveyed. This can not only improve the optical characteristics of the obtained polarizer, but also stably produce a polarizer excellent in optical characteristics, and can suppress variations in the optical characteristics (particularly, the single transmittance) of the polarizer.
G-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. It is preferable that: the 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 3 to 40 μm, and more preferably 3 to 20 μm.
Before the PVA-based resin layer is formed, the thermoplastic resin substrate may be subjected to a surface treatment (for example, corona treatment), or an easy-adhesion layer may be formed on the thermoplastic resin substrate. By performing such treatment, the adhesion between the thermoplastic resin substrate and the PVA-based resin layer can be improved.
G-1-1. thermoplastic resin base Material
As the thermoplastic resin substrate, any suitable thermoplastic resin film can be used. The details of the thermoplastic resin substrate are described in, for example, Japanese patent laid-open No. 2012-73580. The entire disclosure of this publication is incorporated herein by reference.
G-1-2 coating liquid
As described above, the coating liquid contains a halide and a PVA-based resin. The coating liquid is typically a solution obtained by dissolving the halide and the PVA-based resin in a solvent. Examples of the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various 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 preferable. 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. With such a resin concentration, a uniform coating film can be formed which adheres to the thermoplastic resin substrate. The content of the halide in the coating liquid is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin.
Additives may be compounded into the coating liquid. Examples of the additive include a plasticizer and a surfactant. 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. Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymers. 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-based 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-. By using the PVA-based resin having such a saponification degree, a polarizing plate having excellent durability can be obtained. If the saponification degree 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 polymerization degree can be determined in accordance with JIS K6726-.
As the halide, any suitable halide can be used. For example, iodide and sodium chloride are listed. 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. When the amount of the halide exceeds 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 PVA resin layer is stretched, and therefore, the orientation of polyvinyl alcohol molecules in the PVA resin is high, but when the stretched PVA resin layer is immersed in a liquid containing water, the orientation of polyvinyl alcohol molecules may be disturbed, and the orientation may be lowered. In particular, when a laminate of a thermoplastic resin and a PVA-based resin layer is stretched in an aqueous boric acid solution, the orientation degree tends to be remarkably decreased when the laminate is stretched in an aqueous boric acid solution at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin. For example, while the PVA film itself is usually stretched in an aqueous boric acid solution at 60 ℃, the laminate of a-PET (thermoplastic resin substrate) and a PVA-based resin layer is stretched at a high temperature of about 70 ℃, and in this case, the orientation of the PVA at the initial stage of stretching may be reduced in a stage before it is improved by underwater stretching. On the other hand, by preparing 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 an aqueous boric acid solution, crystallization of the PVA-based resin in the PVA-based resin layer of the laminate after the auxiliary stretching can be promoted. As a result, when the PVA-based resin layer is immersed in a liquid, the alignment disorder and the decrease in alignment of the polyvinyl alcohol molecules can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This can improve the optical properties of the polarizer obtained through a treatment step of immersing the laminate in a liquid, such as dyeing treatment and underwater stretching treatment.
G-2 auxiliary stretching treatment in air
In particular, in order to obtain high optical characteristics, a 2-stage stretching method in which dry stretching (auxiliary stretching) and stretching in an aqueous boric acid solution are combined may be selected. By introducing the auxiliary stretching as in the 2-stage stretching, the thermoplastic resin base material can be stretched while suppressing crystallization, the problem of the reduction in stretchability due to excessive crystallization of the thermoplastic resin base material in the subsequent stretching in an aqueous boric acid solution can be solved, and the laminate can be stretched to a higher magnification. 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, the coating temperature needs to be lowered as compared with the case where a PVA-based resin is coated on a normal metal drum, and as a result, there is a possibility that crystallization of the PVA-based resin becomes relatively low and sufficient optical characteristics cannot be obtained. In contrast, 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 improving the orientation of the PVA-based resin in advance, it is possible to prevent problems such as a decrease in orientation and dissolution of the PVA-based resin when the PVA-based resin is immersed in water in a 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 one embodiment, the stretching method of the in-air assisted stretching may be, for example, biaxial stretching using a tenter stretcher. By appropriately setting the stretching conditions of biaxial stretching, a predetermined biaxial property can be imparted to the obtained polarizer. As a result, a polarizer having a desired piercing strength can be realized.
The stretching ratio in the longitudinal direction in the air-assisted stretching is preferably 2.3 times or more, and more preferably 2.4 times to 3.5 times. In the embodiment of the present invention, the width residual ratio (width after shrinkage:%) is controlled by using the biaxial stretching as described above. Specifically, the difference between the width residual ratio during the air-assisted stretching (i.e., after the air-assisted stretching) and the free shrink width residual ratio is preferably 2% or more, more preferably 3% or more, and still more preferably 5% or more. The maximum value of this difference is, for example, 15%. Here, the free shrink width residual ratio is a width residual ratio when free end stretching is performed in the longitudinal direction at the same stretching ratio. Specifically, the residual free shrink width ratio when the stretch ratio is x times can be (1/x)1/2) X 100. For example, when the stretch ratio is 2.4 times, the free shrink width residual ratio is (1/(2.4)1/2) X 100 ═ 64.5%. This is because it is considered that in the free shrinkage, when the stretching is performed in the longitudinal direction, shrinkage occurs at the same rate in the width direction and the thickness direction. The maximum stretching ratio (longitudinal direction) when the in-air auxiliary stretching and the underwater stretching are combined is preferably 5.0 times or more, more preferably 5.5 times or more, and still more preferably 6.0 times or more, with respect to the original length of the laminate. In the present specification, the "maximum stretching ratio" means a stretching ratio immediately before the laminate breaks, and means a stretching ratio at which the laminate is separately observed to break, and is a value lower than this value by 0.2.
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 less than the glass transition temperature (Tg) of the thermoplastic resin substrate, more preferably not less than the glass transition temperature (Tg) +10 ℃ of the thermoplastic resin substrate, and particularly preferably not less than Tg +15 ℃. On the other hand, the upper limit of the stretching temperature is preferably 170 ℃. By stretching at such a temperature, rapid progress of crystallization of the PVA-based resin can be suppressed, and defects (for example, defects) caused by the crystallization can be suppressedHampering the orientation of the PVA-based resin layer by stretching). The crystallization index of the PVA based resin after the in-air auxiliary stretching is preferably 1.3 to 1.8, more preferably 1.4 to 1.7. The crystallization index of the PVA-based resin can be measured by ATR method using a fourier transform infrared spectrometer. Specifically, measurement was carried out using polarized light as measurement light, and 1141cm of the obtained spectrum was used-1And 1440cm-1The crystallization index of (d) was calculated according to the following equation.
Crystallization index ═ IC/IR)
Wherein the content of the first and second substances,
IC: 1141cm when measurement light is made incident and measurement is performed-1The strength of (a) is high,
IR: 1440cm when measurement light was incident and measured-1The strength of (2).
G-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 and 73580 (mentioned above).
G-4 stretching treatment in water
The underwater stretching treatment is performed by immersing the laminate in a stretching bath. By the underwater stretching treatment, the thermoplastic resin substrate and the PVA resin layer can be stretched at a temperature lower than the glass transition temperature (typically, about 80 ℃), and the PVA resin layer can be stretched to a high magnification 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 by fixed-end stretching or free-end stretching (for example, a method of uniaxially stretching the laminate by passing the laminate between rollers having different peripheral speeds). Free end stretching is preferably chosen. The stretching of the laminate may be performed in one stage, or may be performed in a plurality of stages. When the stretching is performed in a plurality of stages, the stretching ratio (maximum stretching ratio) of the laminate described later is the product of the stretching ratios in the respective stages.
The underwater stretching is preferably performed by immersing the laminate in an aqueous boric acid solution (stretching in an aqueous boric acid solution). By using an aqueous boric acid solution as a stretching bath, rigidity capable of withstanding the tension applied during stretching and water resistance not dissolving in water can be imparted to the PVA-based resin layer. Specifically, boric acid can be crosslinked with the PVA-based resin by generating a tetrahydroxyborate anion in an aqueous solution and by means of a hydrogen bond. 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 properties 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. When the boric acid concentration is 1 part by weight or more, the dissolution of the PVA-based resin layer can be effectively suppressed, and a polarizing plate having 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 iodide is preferably compounded into the above-mentioned stretching bath (aqueous boric acid solution). By adding an 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 to 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, as the temperature of the stretching bath is higher, the solubility of the PVA-based resin layer is higher, and there is a fear that excellent optical characteristics cannot be obtained. The immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
The stretching ratio by underwater stretching is preferably 1.5 times or more, more preferably 3.0 times or more. The total stretch ratio of the laminate is preferably 5.0 times or more, and more preferably 5.5 times or more, the original length of the laminate. By realizing such a high stretch ratio, a polarizer having extremely excellent optical characteristics can be manufactured. Such a high stretch ratio can be achieved by using an underwater stretching method (stretching in an aqueous boric acid solution).
G-5 drying shrinkage treatment
The drying shrinkage treatment may be performed by heating the entire zone to heat the zone, 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 the laminate using a heating roller, the laminate can be efficiently 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 efficiently promoted to increase the crystallinity, and the crystallinity of the thermoplastic resin substrate can be favorably increased even at a low drying temperature. As a result, the thermoplastic resin substrate has increased rigidity and is resistant to shrinkage of the PVA-based resin layer due to drying, and curling is suppressed. Further, since the laminate can be dried while maintaining a flat state by using the heating roller, not only curling but also wrinkles can be suppressed. At this time, the laminate is shrunk in the width direction by the drying shrinkage treatment, and 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%. By using the heating roller, the laminate can be continuously shrunk in the width direction while being conveyed, and high productivity can be achieved.
Fig. 2 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 disposed 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 disposed so as to continuously heat only one surface (for example, the surface of the thermoplastic resin substrate) of the laminate 200.
The drying conditions can be controlled by adjusting the heating temperature of the conveying roller (temperature of the heating roller), the number of heating rollers, the time of contact with the heating roller, and the like. The temperature of the heating roller is preferably 60 to 120 ℃, more preferably 65 to 100 ℃, and particularly preferably 70 to 80 ℃. The crystallinity of the thermoplastic resin can be favorably increased, curling can be favorably suppressed, and an optical laminate having extremely excellent durability can be produced. The temperature of the heating roller can be measured by a contact thermometer. In the example shown in the figure, 6 conveying rollers are provided, but there is no particular limitation as long as there are a plurality of conveying rollers. The 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 drying by the heating roller and hot air drying in combination, a rapid temperature change between the heating rollers can be suppressed, and the shrinkage in the width direction can be easily controlled. The temperature of the hot air drying is preferably 30 to 100 ℃. The hot air drying time is preferably 1 to 300 seconds. The wind speed of the hot 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 digital wind speed meter of a miniature blade type.
G-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.
H. Image display device
The polarizing plate according to items A to G above can be applied to an image display device. Accordingly, the present invention includes an image display device using such a polarizing plate. 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 according to items a to G on a visual recognition side thereof. The polarizing plates are laminated such that the optically functional layers are on the image display unit (for example, liquid crystal unit, organic EL unit, and inorganic EL unit) (such that the polarizer is on the visual recognition side). In one embodiment, the image display device has a curved shape (substantially a curved display screen) and/or is capable of being bent or folded. In such an image display device, the polarizing plate of 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.
(1) Thickness of
In the state of the polarizing plate/thermoplastic resin substrate laminate used in examples and comparative examples, measurement was performed using an interference film thickness meter (product name "MCPD-3000" manufactured by tsukamur electronic corporation). The wavelength range for calculating the thickness was 400nm to 500nm, and the refractive index was 1.53. In comparative examples 3 and 4, the polarizer itself was measured using a numerical table (product name "DG 205", manufactured by peakock kazaki corporation).
(2) Transmittance and degree of polarization of monomer
The polarizers were peeled from the laminates of polarizers and thermoplastic resin substrates used in examples and comparative examples, and the monomer transmittance Ts, parallel transmittance Tp, and orthogonal transmittance Tc of the polarizers were measured using an ultraviolet-visible spectrophotometer (V-7100, manufactured by japan spectrophotometers) as Ts, Tp, and Tc, respectively. These Ts, Tp and Tc are Y values obtained by measuring and correcting the visual sensitivity using a 2-degree visual field (C light source) according to JIS Z8701.
From the Tp and Tc thus obtained, the degree of polarization P is determined by the following equation.
Polarization degree P (%) { (Tp-Tc)/(Tp + Tc) }1/2×100
(3) Boric acid content
The polarizing material was peeled off from the polarizing material/thermoplastic resin substrate laminate used in examples and comparative examples to collect a predetermined amount of the polarizing material, and then dried at 120 ℃ for 2 hours to evaporate water, and the weight was measured. Next, the polarizer was dissolved in a suitable amount of hot water, and the boric acid weight in the polarizer was determined by neutralization. The boric acid content (% by weight) was calculated from the ratio of the obtained boric acid weight to the weight of the polarizing material before dissolution in hot water.
(4) Puncture strength
The polarizing material was peeled 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 "NDG 5", specification for needle penetration force measurement) equipped with a needle, and subjected to piercing at a piercing 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 piercing strength. The puncture strength of 10 test pieces was measured, and the average value thereof was used as the evaluation value. It is noted that the needle uses a tip diameter
0.5R needle. The measured polarizer was fixed from both sides thereof using a jig having a circular opening with a diameter of 11mmThe puncture test was performed at the center of the opening.
(5) Bending test
The polarizing plates with retardation layers obtained in examples and comparative examples were cut to a size of 120mm (direction orthogonal to the absorption axis direction of the polarizer) × 30mm (absorption axis direction) to obtain measurement samples. For the measurement sample, a continuous bending test was performed using a continuous bending test apparatus (Yuasa System co., ltd, product name "DLDMLH-FS") in a no-load U-stretch mode. The bending speed was 60rpm, the bending amplitude was 20mm, the bending radius was 0.5mm, and the number of bending times was 50000. The bending is performed by sliding the grip portion while gripping the end portion in the longitudinal direction of the measurement sample so that the retardation layer of the measurement sample is located inside. Evaluation was performed according to the following criteria.
O: no cracking occurred in 50000 bends
X: in a bending ratio of less than 50000 times, any one of the components is broken
When the measurement sample is cracked, the crack is along the absorption axis direction (the width direction of the measurement sample).
[ example 1]
1. Fabrication of polarizing elements
As the thermoplastic resin substrate, an amorphous copolymerized polyethylene terephthalate isophthalate film (thickness: 100 μm) having a water absorption of 0.75% and a Tg of about 75 ℃ in a long form was used. One surface of the resin substrate is subjected to corona treatment.
In the following, with 9: 1 an aqueous PVA solution (coating solution) was prepared by mixing 100 parts by weight of a PVA resin comprising polyvinyl alcohol (having a polymerization degree of 4200 and a saponification degree of 99.2 mol%) and acetoacetyl-modified PVA (trade name "GOHSEFIMER Z410" available from Nippon synthetic chemical industries, Ltd.) and adding 13 parts by weight of potassium iodide.
The aqueous PVA solution was applied to the corona-treated surface of the resin substrate and dried at 60 ℃ to form a PVA-based resin layer having a thickness of 13 μm, thereby producing a laminate.
The obtained laminate was stretched (substantially biaxially stretched) to 2.4 times in the longitudinal direction (longitudinal direction) while controlling the transverse shrinkage by a tenter stretcher adjusted to 140 ℃. The width residual ratio in the in-air stretching treatment was 75.0%, and the difference between the width residual ratio and the free shrink width residual ratio (width residual ratio — free shrink width residual ratio) was 10.5%.
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 resultant was immersed in a dyeing bath (aqueous iodine solution prepared by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ℃ for 60 seconds while adjusting the concentration so that the monomer transmittance (Ts) of the finally obtained polarizer became a predetermined value (dyeing treatment).
Subsequently, the substrate was immersed in a crosslinking bath (an aqueous boric acid solution prepared by adding 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, while immersing the laminate in a bath having a liquid temperature of 70 ℃ (a boric acid aqueous solution prepared by adding 5 parts by weight of potassium iodide to 100 parts by weight of water and adjusting the boric acid concentration so that the boric acid content of the polarizer becomes a predetermined value), uniaxial stretching (2.3 times) was performed between rolls having different peripheral speeds so that the total stretching ratio in the longitudinal direction (longitudinal direction) was 5.5 times (underwater stretching treatment).
Then, the laminate was immersed in a cleaning bath (aqueous solution containing 4 parts by weight of potassium iodide per 100 parts by weight of water) at a liquid temperature of 20 ℃.
Then, the sheet was dried in an oven maintained at 90 ℃ while being in contact with an SUS-made heating roll maintained at 75 ℃ for about 2 seconds (drying shrinkage treatment). The shrinkage in the width direction of the laminate by the drying shrinkage treatment was 5.2%.
In this manner, a polarizing plate having a thickness of 5 μm was formed on the resin substrate. The polarizing plate had a puncture strength of 26.4gf/μm. The polarizing material had a single transmittance of 42.0% and a degree of polarization of 99.996%.
2. Manufacture of polarizing plate
An acrylic film (surface refractive index 1.50, 40 μm) as a protective layer was bonded to the surface (the surface opposite to the resin substrate) of the polarizer obtained above via an ultraviolet-curable adhesive. Specifically, the curable adhesive was applied so that the total thickness was 1.0 μm, and the adhesive was bonded using a roll mill. Then, the adhesive is cured by irradiating UV light from the protective layer side. Then, after cutting both ends, the resin base material was peeled off to obtain a long polarizing plate having a protective layer/polarizer.
3. Production of alignment cured layer of liquid Crystal Compound (liquid Crystal alignment cured layer) constituting 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 brushing cloth to conduct orientation treatment. The orientation treatment direction was set to be 45 ° with respect to the absorption axis direction of the polarizer when viewed from the visual recognition side when the polarizing plate was bonded. The liquid crystal coating liquid was applied to the alignment-treated surface by a bar coater, and heated and dried at 90 ℃ for 2 minutes, thereby aligning the liquid crystal compound. For the liquid crystal layer thus formed, irradiation with a metal halide lamp was performed at 100mJ/cm2The liquid crystal layer is cured by the light to form a liquid crystal alignment cured layer a on the PET film. The thickness of the liquid crystal alignment cured layer A was 1.0. mu.m, and the in-plane retardation Re (550) was 140 nm. Further, the liquid crystal alignment cured layer A has nx>ny is nz.
4. Manufacture of polarizing plate with phase difference layer
The cured liquid crystal alignment layer a obtained in the above 3 was transferred onto the polarizer surface of the polarizing plate obtained in the above 2. The transfer (bonding) was performed by using the ultraviolet curing adhesive (thickness 1.0 μm) used in the above 2. In this way, a polarizing plate with a retardation layer having a structure of protective layer/adhesive layer/polarizer/adhesive layer/retardation layer (liquid crystal alignment cured layer) was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 48 μm. The obtained polarizing plate with a retardation layer was subjected to the evaluation in (4) above. The results are shown in Table 1.
[ example 2]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the retardation layer had a 2-layer structure of a liquid crystal alignment cured layer. Specifically, as described below. A liquid crystal alignment cured layer B1 was formed on the PET film in the same manner as in example 1, except that the coating thickness was changed and the alignment treatment direction was set to a direction of 15 ° with respect to the direction of the absorption axis of the polarizer when viewed from the viewing side. The thickness of the liquid crystal alignment cured layer B1 was 2.0. mu.m, and the in-plane retardation Re (550) was 270 nm. Further, a liquid crystal alignment cured layer B2 was formed on the PET film in the same manner as in example 1, except that the alignment treatment direction was set to a direction of 75 ° with respect to the direction of the absorption axis of the polarizer when viewed from the viewing side. The thickness of the liquid crystal alignment cured layer B2 was 1.0. mu.m, and the in-plane retardation Re (550) was 140 nm. Next, the liquid crystal alignment cured layers B1 and B2 obtained above were sequentially transferred onto the same polarizer surface as in example 1. Each transfer (bonding) was performed with the use of the ultraviolet-curable adhesive (thickness: 1.0 μm) used in example 1. In this way, a polarizing plate with a retardation layer having a structure of protective layer/adhesive layer/polarizer/adhesive layer/retardation layer (1 st liquid crystal alignment cured layer/adhesive layer/2 nd liquid crystal alignment cured layer) was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 51 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 3]
A polarizing plate was produced in the same manner as in example 1, except that a cycloolefin resin (COP) film (thickness 13 μm) was used as another protective layer instead of the retardation layer as the optical functional layer. The total thickness of the polarizing plate was 60 μm. The obtained polarizing plate was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 4]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, 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 28 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 5]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the protective layer was changed from an acrylic film to a COP film (thickness: 13 μm). The total thickness of the obtained polarizing plate with a retardation layer was 21 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 6]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the conditions of the dyeing treatment were changed so that the monomer transmittance of the polarizing plate was 43.0%. The polarizing degree of the polarizing member was 99.990%, and the puncture strength was 28.7gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 48 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 7]
A polarizing plate with a retardation layer was produced in the same manner as in example 6, except that the thickness of the PVA-based resin layer was set to 20 μm (as a result, the thickness of the polarizer was set to 8 μm), and the conditions of the dyeing treatment were changed so that the monomer transmittance of the polarizer was 43.1%. The polarizing member had a degree of polarization of 99.991% and a puncture strength of 26.6gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 51 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 8]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the conditions of the dyeing treatment were changed so that the monomer transmittance of the polarizing plate was 44.5%. The polarizing member had a degree of polarization of 99.750% and a puncture strength of 27.6gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 48 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 9]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the stretching conditions were changed so that the difference between the width residual ratio in the air-assisted stretching and the free shrink width residual ratio was 3.1%, and the conditions of the dyeing treatment were changed so that the single body transmittance of the polarizer was 41.9%. The polarizing member had a thickness of 5.5 μm, a degree of polarization of 99.997%, and a puncture strength of 13.6gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 48.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 10]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the stretching conditions were changed so that the difference between the width residual ratio in the air-assisted stretching and the free shrink width residual ratio was 3.1%, and the conditions of the dyeing treatment were changed so that the single body transmittance of the polarizer was 41.2%. The polarizing member had a thickness of 5.5 μm, a degree of polarization of 99.997%, and a puncture strength of 11.6gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 48.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 11]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the stretching conditions were changed so that the difference between the width residual ratio in the air-assisted stretching and the free shrink width residual ratio was 3.5%, and the conditions of the dyeing treatment were changed so that the monomer transmittance of the polarizer was 43.0%. The polarizing member had a thickness of 5.5 μm, a degree of polarization of 99.994%, and a puncture strength of 20.5gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 48.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ example 12]
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the stretching ratio of the aerial auxiliary stretching was 3.0 times, the stretching ratio in water was 1.8 times, the stretching conditions were changed such that the difference between the width residual ratio in the aerial auxiliary stretching and the free shrinkage width residual ratio was 10.3%, and the conditions of the dyeing treatment were changed such that the monomer transmittance of the polarizing material was 43.0%. The polarizing degree of the polarizing member was 99.990%, and the puncture strength was 28.3gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 48 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
Comparative example 1
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the PVA-based resin layer was formed without using the acetoacetyl group-modified PVA, the stretching conditions were changed such that the difference between the width residual rate in the air-assisted stretching and the free shrinkage width residual rate was 0.5%, and the conditions of the dyeing treatment were changed such that the monomer transmittance of the polarizer was 41.9%. The polarizing member had a degree of polarization of 99.997% and a puncture strength of 8.4gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 48 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
Comparative example 2
The polarizer was fabricated as follows.
As the thermoplastic resin substrate, an amorphous copolymerized polyethylene terephthalate isophthalate film (thickness: 100 μm) having a water absorption of 0.75% and a Tg of about 75 ℃ in a long form was used. One surface of the resin substrate is subjected to corona treatment.
To 100 parts by weight of polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) was added 13 parts by weight of potassium iodide to prepare an aqueous PVA solution (coating solution).
The aqueous PVA solution was applied to the corona-treated surface of the resin substrate and dried at 60 ℃ to form a PVA-based resin layer having a thickness of 13 μm, thereby producing a laminate.
The obtained laminate was subjected to 5.0-fold stretching by roll-to-roll stretching at 150 ℃ (in-air stretching treatment). The width residual ratio in the in-air stretching treatment was 43.9%, and the difference between the width residual ratio and the free shrink width residual ratio (width residual ratio-free shrink width residual ratio) was-0.8%.
Next, the laminate was immersed for 60 seconds (dyeing treatment) in a dyeing bath (a solution in which the concentration of iodine and potassium iodide in an aqueous solution at a liquid temperature of 30 ℃ (in a weight ratio of iodine to potassium iodide is 1: 7) and the amount of water was adjusted so that the monomer transmittance (Ts) of the polarizer became a predetermined value).
Subsequently, the substrate was immersed in a crosslinking bath (an aqueous solution of boric acid containing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid per 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (first crosslinking treatment).
Then, the laminate was immersed in a crosslinking bath (an aqueous boric acid solution prepared by adding 5 parts by weight of potassium iodide to 100 parts by weight of water and adjusting the boric acid concentration so that the boric acid content of the polarizer became a predetermined value) at a liquid temperature of 60 ℃. The underwater stretching as in example 1 was not performed. (crosslinking treatment 2).
Then, the laminate was immersed in a cleaning bath (aqueous solution containing 4 parts by weight of potassium iodide per 100 parts by weight of water) at a liquid temperature of 20 ℃.
Then, the sheet was dried in an oven maintained at 90 ℃ while being in contact with an SUS-made heating roll maintained at 75 ℃ for about 2 seconds (drying shrinkage treatment). The shrinkage in the width direction of the laminate by the drying shrinkage treatment was 4.0%.
In this manner, a polarizing plate having a thickness of 5 μm was formed on the resin substrate. The polarizing material had a monomer transmittance of 42.0%, a polarization degree of 99.920%, and a puncture strength of 6.5gf/μm.
A polarizing plate with a retardation layer was produced in the same manner as in example 1, except that the polarizing plate was used. The total thickness of the obtained polarizing plate with a retardation layer was 48 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
Comparative example 3
1. Fabrication of polarizing elements
A polyvinyl alcohol resin film (PE 6000, manufactured by clony) having an average polymerization degree of 2400, a saponification degree of 99.9 mol%, and a thickness of 60 μm was stretched in the conveying direction 2.4 times while being swollen by being immersed for 30 seconds between rolls at a peripheral speed ratio in a swelling bath (water bath) at 20 ℃. The dipping time at this time was about 60 seconds. Next, the dyed polyvinyl alcohol film was stretched 4.2 times in the transport direction based on the original polyvinyl alcohol film while being immersed in a crosslinking bath (aqueous solution having a boric acid concentration of 3.0 wt% and a potassium iodide concentration of 3.0 wt%) at 40 ℃. The obtained polyvinyl alcohol film was immersed in a 64 ℃ stretching bath (an aqueous solution of boric acid prepared by adding 5 parts by weight of potassium iodide to 100 parts by weight of water and adjusting the boric acid concentration so that the boric acid content of the polarizer became a predetermined value) for 50 seconds, stretched 6.0 times in the transport direction based on the original polyvinyl alcohol film (stretching step), and then immersed in a 20 ℃ cleaning bath (an aqueous solution of potassium iodide at a concentration of 3.0% by weight) for 5 seconds (cleaning step). The washed polyvinyl alcohol film was dried at 30 ℃ for 2 minutes to prepare a polarizer (thickness: 25 μm). The boric acid content and puncture strength of the polarizer in this state were measured.
2. Manufacture of polarizing plate
As the adhesive, an aqueous solution containing a polyvinyl alcohol resin having an acetoacetyl group (average polymerization degree of 1200, saponification degree of 98.5 mol%, acetoacetylation degree of 5 mol%) and methylolmelamine at a weight ratio of 3:1 was used. Using this adhesive, an acrylic film (thickness 40 μm) similar to that of example 1 was bonded to one surface of the polarizer obtained above by a roll laminator, and then dried by heating in an oven (temperature 60 ℃ c. for 5 minutes), thereby producing a polarizing plate having a structure of a protective layer (thickness 40 μm)/an adhesive layer/polarizer.
3. Manufacture of polarizing plate with phase difference layer
The liquid crystal alignment cured layer a was transferred onto the surface of the polarizer of the polarizing plate obtained in the above 2. in the same manner as in example 1, and a polarizing plate with a retardation layer having a structure of protective layer/adhesive layer/polarizing plate/adhesive layer/retardation layer (liquid crystal alignment cured layer) was produced. The polarizing material had a monomer transmittance of 42.4%, a polarization degree of 99.997%, and a puncture strength of 6.7gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 68 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
Comparative example 4
A polarizing plate with a retardation layer having a structure of protective layer/adhesive layer/polarizer/adhesive layer/retardation layer (liquid crystal alignment cured layer) was produced in the same manner as in comparative example 3, except that PE3000 (manufactured by clony, average polymerization degree 2400, saponification degree 99.9 mol%, thickness 30 μm) was used instead of PE6000 as the polyvinyl alcohol resin film. The polarizing material had a thickness of 12 μm, a monomer transmittance of 42.5%, a degree of polarization of 99.997%, and a puncture strength of 6.9gf/μm. The total thickness of the obtained polarizing plate with a retardation layer was 55 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ Table 1]
[ evaluation ]
When the examples and comparative examples are compared, it is clear that: according to the embodiments of the present invention, a polarizing plate (polarizing plate with a retardation layer) having excellent bendability can be obtained. Further, in the examples, it was confirmed that the change in optical characteristics due to bending was within a practically allowable range.
Industrial applicability
The polarizing plate of the present invention can be suitably used for image display devices such as liquid crystal display devices, organic EL display devices, and inorganic EL display devices.
Description of the reference numerals
10 polarizer
20 phase difference layer
30 protective layer
100 polarizing plate
Claims (19)
1. A polarizing plate, comprising: a polarizer, a protective layer disposed on one side of the polarizer, and an optically functional layer disposed on the other side of the polarizer,
the penetration strength of the polarizer is 10gf/μm or more.
2. The polarizing plate according to claim 1, wherein the optically functional layer has a thickness of 20 μm or less.
3. The polarizing plate according to claim 1 or 2, wherein the optically functional layer functions as a protective layer other than the protective layer.
4. The polarizing plate according to any one of claims 1 to 3, wherein the optically functional layer is a retardation layer having a circular polarization function or an elliptical polarization function.
5. The polarizing plate according to claim 4, wherein the phase difference layer is a single layer of an alignment cured layer of a liquid crystal compound,
the Re (550) of the phase difference layer is 100 nm-190 nm,
the slow axis of the phase difference layer and the absorption axis of the polarizer form an angle of 40-50 degrees.
6. The polarizing plate according to claim 4, wherein the phase difference layer has a laminated structure of an alignment cured layer of a 1 st liquid crystal compound and an alignment cured layer of a 2 nd liquid crystal compound,
the Re (550) of the alignment cured layer of the 1 st liquid crystal compound is 200 to 300nm, the angle formed by the slow axis and the absorption axis of the polarizer is 10 to 20 DEG,
the Re (550) of the alignment cured layer of the 2 nd liquid crystal compound is 100 to 190nm, and the angle formed by the slow axis and the absorption axis of the polarizer is 70 to 80 degrees.
7. The polarizing plate according to any one of claims 1 to 6, wherein the polarizing element has a thickness of 10 μm or less.
8. The polarizing plate according to any one of claims 1 to 7, wherein the protective layer has a thickness of 50 μm or less.
9. The polarizing plate according to any one of claims 1 to 8, having a total thickness of 60 μm or less.
10. The polarizing plate according to any one of claims 1 to 9, wherein the polarizing element is composed of a polyvinyl alcohol resin film containing iodine.
11. The polarizing plate of claim 10, wherein the polarizer comprises an acetoacetyl-modified polyvinyl alcohol resin.
12. The method for manufacturing a polarizing plate according to any one of claims 1 to 11, comprising:
forming a polyvinyl alcohol resin layer on one side of a long thermoplastic resin base material to form a laminate; and the number of the first and second groups,
stretching and dyeing the laminate to form a polarizing plate from the polyvinyl alcohol resin layer,
the penetration strength of the polarizer is 10gf/μm or more.
13. The production method according to claim 12, wherein a polyvinyl alcohol resin layer containing a polyvinyl alcohol resin and containing an iodide or sodium chloride is formed on one side of the thermoplastic resin substrate.
14. The method of manufacturing of claim 13, comprising: the laminate is subjected to an in-air auxiliary stretching treatment, a dyeing treatment, an in-water stretching treatment, and a drying shrinkage treatment in this order, wherein the laminate is heated while being conveyed in the longitudinal direction, and thereby shrunk by 2% or more in the width direction.
15. The production method according to claim 14, wherein a difference between a width residual ratio and a free shrink width residual ratio in the in-air auxiliary stretching is 2% or more.
16. The production method according to claim 14 or 15, wherein a stretch ratio in the aerial auxiliary stretching is 2.3 times or more.
17. An image display device comprising the polarizing plate according to any one of claims 1 to 11.
18. The image display device according to claim 17, which is an organic electroluminescent display device or an inorganic electroluminescent display device.
19. An image display device according to claim 17 or 18, which is capable of being folded or collapsed.
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| JP2019022537 | 2019-02-12 | ||
| JP2019-022537 | 2019-02-12 | ||
| PCT/JP2020/004805 WO2020166505A1 (en) | 2019-02-12 | 2020-02-07 | Polarizing plate, manufacturing method thereof, and image display device using said polarizing plate |
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| CN113423572A true CN113423572A (en) | 2021-09-21 |
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| KR (1) | KR20210127928A (en) |
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| WO (1) | WO2020166505A1 (en) |
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| TW202045349A (en) | 2020-12-16 |
| JP7288465B2 (en) | 2023-06-07 |
| JPWO2020166505A1 (en) | 2021-10-21 |
| WO2020166505A1 (en) | 2020-08-20 |
| KR20210127928A (en) | 2021-10-25 |
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