TW201936379A - Polarizing plate with anti-reflection layer and method for producing same - Google Patents

Abstract

The present invention provides a polarizing plate with an anti-reflection layer, which is suppressed in the occurrence of appearance defects (yellow unevenness, whitening) even in a high-temperature high-humidity environment. A polarizing plate with an anti-reflection layer according to the present invention is provided with: a polarizing plate which comprises a polarizer and a protective layer that is provided on one surface of the polarizer; a base material which is bonded to the protective layer; and an anti-reflection layer which is directly formed on the base material. The base material and the protective layer contain a resin; and the relative energy difference RED between the resin and oleic acid based on the Hansen solubility parameters is 1.05 or more. In an embodiment of the present invention, this polarizing plate with an anti-reflection layer has a water vapor permeability of 0.2 g/m2/24 h or less, while the base material has a water vapor permeability of 150 g/m2/24 h or less.

Description

Polarizing plate with anti-reflection layer and manufacturing method thereof

The present invention relates to a polarizing plate with an antireflection layer and a method of manufacturing the same.

In an image display device (for example, a liquid crystal display device, an organic EL display device, or a quantum dot display device), a polarizing plate is disposed on at least one side of the display unit in many cases due to an image forming method. . It is widely known that an anti-reflection layer (anti-reflection treatment) is provided on the viewing side in order to prevent external light from being reflected on the display screen in the polarizing plate disposed on the viewing side of the image display device. When the antireflection layer is formed by performing antireflection treatment on the substrate, the thickness of the antireflection layer can be made thin, and the thickness of the polarizing plate can be reduced. In the antireflection layer, damage is likely to occur on the surface of the antireflection layer. As a result, there is a case where the polarizing plate having such an anti-reflection layer is placed in a high-temperature and high-humidity environment, and the difference in the color difference between the portion near the damage and the other portion is considered to be uneven (yellow unevenness). . Further, in the polarizing plate with the antireflection layer formed on the substrate with the antireflection layer, the chemical resistance of the substrate is improved, and the appearance of the polarizing plate whitening occurs in a high temperature and high humidity environment. situation.
Prior art document patent document

Patent Document 1: Japanese Patent Laid-Open Publication No. 2012-27322

[The problem that the invention wants to solve]

The present invention has been made to solve the above problems, and a main object thereof is to provide a polarizing plate with an antireflection layer capable of suppressing occurrence of poor appearance (for example, yellow unevenness and whitening) even in a high-temperature and high-humidity environment.
[Technical means to solve the problem]

The polarizing plate with an antireflection layer of the present invention includes: a polarizing plate having a polarizing element and a protective layer disposed on one side of the polarizing element; a substrate attached to the protective layer; and an antireflection layer directly Formed on the substrate. The substrate and the protective layer contain a resin. The relative energy difference RED based on the Hansen solubility parameter of the resin and oleic acid is 1.05 or more. The polarizing plate with the antireflection layer has a moisture permeability of 0.2 g/m ² /24 h or less, and the substrate has a moisture permeability of 150 g/m ² /24 h or less.
In one embodiment, the base material and the protective layer comprise at least one resin selected from the group consisting of a (meth)acrylic resin, a polycarbonate resin, and a polyester resin.
In one embodiment, the difference Δ between the amount of change in the hue of the monomer hue after the polarizing plate with the antireflection layer is maintained at 65° C. and 90% RH for 72 hours is 1.0 or less, and at 65° C. and 90% RH. The difference Δ between the amounts of change in the hue b value of the monomer after holding for 120 hours was 0.8 or less.
In another aspect of the invention, a method of fabricating a polarizing plate with an anti-reflective layer is provided. The manufacturing method includes: forming a polarizing element laminated body including a polarizing element and a protective layer; forming an antireflection layer on the substrate to form an antireflection laminate; and bonding the antireflection laminate to the surface of the protective layer of the polarizing element laminate; The substrate.
In one embodiment, the antireflection layer is formed by sputtering.
[Effects of the Invention]

According to the present invention, a resin comprising a resin having a relative energy difference RED of 1.05 or more based on a Hansen solubility parameter of a resin and oleic acid is used as a substrate of an antireflection layer and a protective layer of a polarizing plate, and an antireflection layer is attached thereto. The moisture permeability of the polarizing plate is set to 0.2 g/m ² /24 h or less, and the moisture permeability of the substrate for forming the antireflection layer is 150 g/m ² /24 h or less, thereby achieving high temperature and high humidity environment. A polarizing plate with an anti-reflection layer which is also inferior in appearance (yellow unevenness and whitening) is also suppressed. Further, the optical reliability of the polarizing plate with the antireflection layer can be maintained.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the embodiments.

A. Overall Configuration of Polarizing Plate with Antireflection Layer FIG. 1 is a schematic cross-sectional view of a polarizing plate with an antireflection layer according to an embodiment of the present invention. The polarizing plate 100 with an antireflection layer is provided with a polarizing plate 10 having a polarizing element 11 and a protective layer 12, a substrate 20, and an antireflection layer 30. The base material 20 is typically bonded to the protective layer 12 of the polarizing plate 20 via any appropriate adhesive layer (adhesive layer, adhesive layer: not shown). The layer is typically an acrylic adhesive layer. The anti-reflection layer 30 is formed directly on the substrate 20. In the present specification, "directly" means that the layer is not interposed. In one embodiment, the substrate 20 may have a hard coat layer and/or an adhesive layer (none of which is shown) on the surface of the anti-reflective layer 30 side. This configuration is also included in the form of "the antireflection layer is formed directly on the substrate." An antifouling layer (not shown) may be provided on the surface of the antireflection layer 30 as needed.

In the embodiment of the present invention, the polarizing plate with the antireflection layer has a moisture permeability of 0.2 g/m ² /24 h or less, preferably 0.15 g/m ² /24 h or less, more preferably 0.1 g/m. ² / 24 h or less. Further, the moisture permeability of the polarizing plate with the antireflection layer is, for example, 0.001 g/m ² /24 h or more. Further, the substrate has a moisture permeability of 150 g/m ² /24 h or less, preferably 100 g/m ² /24 h or less, more preferably 10 g/m ² /24 h or less. Further, the lower the moisture permeability of the substrate, the better, and it is preferably 0 g/m ² /24 h. In this way, the moisture permeability of the substrate directly formed by the antireflection layer and the moisture permeability of the obtained polarizing plate with the antireflection layer are set to an appropriate range, even if the polarizing plate with the antireflection layer is placed thereon. In the case of high temperature and high humidity, it is also possible to prevent appearance defects such as yellow unevenness.

In the illustrated example, the protective layer 12 is provided only on one side of the polarizing element 11, but another protective layer may be provided on the side opposite to the protective layer 12 depending on the purpose. In this case, a protective layer may be provided on both sides of the polarizing element, or the protective layer 12 may be omitted and only another protective layer may be provided. When only another protective layer is provided, the substrate 30 can function as a viewing side protective layer. Further, any appropriate functional layer may be provided depending on the purpose. Typical examples of the functional layer include a retardation layer and a conductive layer. The type, number, combination, arrangement position, and characteristics of the functional layer (for example, refractive index characteristics, in-plane phase difference, thickness direction phase difference, and optical characteristics of the Nz coefficient) can be appropriately set depending on the purpose. In one embodiment, a first retardation layer (not shown) having a refractive index characteristic of nx>ny>nz may be provided on the opposite side of the polarizing element 11 from the protective layer 12. In this case, it is preferable to further provide a second retardation layer having a refractive index characteristic of nz>nx>ny on the side opposite to the polarizing element of the first retardation layer. The first retardation layer may also serve as a protective layer on the opposite side to the viewing side of the polarizing element. In the case where the phase difference layer is provided, the angle formed by the retardation layer (in the presence) of the phase difference layer and the absorption axis of the polarizing element may be in accordance with the in-plane phase difference, the thickness direction phase difference, and the refractive index of the phase difference layer. Characteristics and other settings are appropriate. Further, a conductive layer may be provided on the side of the polarizing element 11 opposite to the protective layer 12. By providing the conductive layer at such a position, the polarizing plate with the anti-reflection layer can be preferably used for the internal touch panel type input display device. In this case, the phase difference layer may or may not exist.

The polarizing plate 100 with the anti-reflection layer preferably has a change in the h phase b value of the damaged portion and a change in the h h value of the non-damaged portion of the polarized portion after being left at 65 ° C and 90% RH for 72 hours. The difference Δ of the amount is 1.0 or less. Further, it is preferable that the polarizing plate 100 with the antireflection layer has a difference Δ between the amounts of change in the h color b value of the monomer after being left at 65 ° C and 90% RH for 0.6 hours. If the difference Δ between the amounts of change in the h phase b value of the polarizing plate with the antireflection layer is such a range, the difference between the damaged portion and the non-damaged portion of the antireflection layer is small, and it can be prevented from being regarded as being The appearance of poor appearance caused by uneven yellowness. Furthermore, in the present specification, the single hue b value refers to the monomer hue specified by the National Bureau of Standards (NBS). Further, in the present specification, the amount of change in the h h value of the monomer hue refers to the initial value (the value of the monomer h phase b measured in the state before being placed under the humidification condition of 65 ° C and 90% RH) and at 65 The difference between the b-values of the individual hue measured after a certain period of time under humidified conditions of °C and 90% RH. The difference Δ between the amount of change in the h color b value of the monomer and the amount of change can be calculated from the b value of the monomer hue measured by the method described in the examples.

The protective layer 12 and the substrate 20 of the polarizing plate 10 contain a resin, and the relative energy difference RED based on the Hansen solubility parameter of the resin and oleic acid is 1.05 or more. By including such a resin in the protective layer 12 and the substrate 20, the chemical resistance of the polarizing plate with the antireflection layer is improved, and the whitening of the polarizing plate with the antireflection layer in a high temperature and high humidity environment can be prevented. The RED is preferably 1.3 or more, more preferably 1.5 or more.

The Hansen Solubility parameter (hereinafter also referred to as the HSP value) divides the Hildebrand solubility parameter into a dispersion force (δ _D ), a permanent dipole intermolecular force (δ _P ), and a hydrogen bonding force (δ). _H ) 3 components, and these are represented by vectors drawn in three-dimensional space. It can be judged that the vector similarities have high solubility to each other. That is, the degree of similarity of solubility can be judged based on the distance (HSP distance) of the HSP values of each other. The definition and calculation of Hansen solubility parameters are described in Charles M. Hansen's Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007).

The HSP value has a known value for various resins and solvents, and can be used as it is, or can be calculated using HSPiP (Hansen Solubility Parameters in Practice) as a computer software. Furthermore, the HSPiP also has a database of resins and solvents. In the present specification, the HSP value of the resin in which the resin film is formed using HSPiP is calculated in the following order using the Hansen solubility ball method. First, the solubility of the resin to be evaluated is evaluated using a solvent having a known solubility parameter. In the present specification, methyl ethyl ketone (MEK) is used as a good solvent, and n-hexane, methanol, trichlorobenzene, and γ-butyrolactone are used as poor solvents, and in these good solvents and poor solvents. The solubility in the mixed solvent was evaluated. Details of the evaluation method are as described in the following examples. Then, based on the results of the obtained solubility evaluation, δ _D , δ _P , and δ _H were calculated using HSPiP and three-dimensionally plotted, and Hansen solubility spheres were obtained from the coordinates. The central coordinate of the Hansen solubility sphere is the HSP value of the resin to be evaluated, and the radius of the Hansen solubility sphere is the interaction radius R ₀ of the resin.

The relative energy difference RED between the resin and oleic acid can be calculated by the formula (1).
Relative energy difference RED=Ra/R ₀ (1)
(In the formula (1), Ra is the distance between the HSP value of the resin and the HSP value of the oleic acid, and R ₀ is the interaction radius of the resin).
Further, the HSP distance Ra of the resin (HSP value: δ _DP , δ _PP , δ _HP ) and oleic acid (HSP value: δ _DO , δ _PO , δ _HO ) can be calculated by the formula (2).
Ra={4×(δ _DP -δ _DO ) ² +(δ _PP -δ _PO ) ² +(δ _HP -δ _HO ) ² } ^1/2 (2)
(In formula (2), δ _DP represents the dispersing power of the resin, δ _PP represents the permanent dipole intermolecular force of the resin, δ _HP represents the hydrogen bonding force of the resin, δ _DO represents the dispersing power of oleic acid, and δ _PO represents the oleic acid The permanent dipole intermolecular force, δ _HO represents the hydrogen bonding force of oleic acid).

Hereinafter, constituent elements of the polarizing plate with the antireflection layer will be described.

B. Polarizing Plate The polarizing plate with an antireflection layer of the present invention has a polarizing element and a protective layer provided on one side of the polarizing element. In the embodiment of the present invention, the water content of the polarizing plate 10 is preferably 0.5% by weight or more, more preferably 0.6% by weight or more, still more preferably 0.8% by weight or more, and particularly preferably 1.0% by weight or more. The water content of the polarizing plate is, for example, 1.5% by weight or less. The moisture content is higher than the moisture content of the polarizing plate in the polarizing plate with the antireflection layer. By having such a high water content of the polarizing plate, the moisture absorption expansion of the polarizing plate in a high temperature and high humidity environment can be remarkably suppressed. As a result, the dimensional change of the polarizing plate in a high-temperature and high-humidity environment (especially, the dimensional change of the absorption axis direction of the polarizing element) can be remarkably suppressed. For example, in the polarizing plate with an antireflection layer according to the embodiment of the present invention, the dimensional change rate of the polarizing element in the absorption axis direction after holding at 65 ° C and 90% RH for 500 hours is preferably less than 0.10%, more preferably 0.08. % or less, further preferably 0.06% or less. Further, since the polarizing plate has such a high water content, the polarizing plate with the antireflection layer according to the embodiment of the present invention is curled even in a high-temperature and high-humidity environment, and the direction of the curl is also opposite to the usual direction. . Specifically, the polarizing plate with an antireflection layer according to the embodiment of the present invention may be curled on the side opposite to the antireflection layer after being held at 65 ° C and 90% RH for 500 hours (the opposite side to the viewing side) ) Raised. Further, in the polarizing plate to which the antireflection layer is usually attached, in many cases, the film is curled on the side of the antireflection layer. As a result, even if the polarizing plate with the antireflection layer according to the embodiment of the present invention is curled, the adverse effect on the image display device may be small. Thus, by using the synergistic effect of the suppression of the dimensional change obtained by the polarizing plate having a high water content and the curling direction, the polarizing plate with an antireflection layer according to the embodiment of the present invention can be applied to an image display device. The warpage, peeling, and/or deterioration of display characteristics in a high-temperature and high-humidity environment are remarkably suppressed.

B-1. Polarizing Element The polarizing element 11 is typically a resin film including a dichroic substance.

As the resin film, any appropriate resin film which can be used as a polarizing element can be used. The resin film is typically a polyvinyl alcohol-based resin (hereinafter referred to as "PVA-based resin") film.

As the PVA-based resin that forms the PVA-based resin film, any appropriate resin can be used. For example, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are mentioned. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer. The degree of saponification of the PVA-based resin is usually from 85 mol% to 100 mol%, preferably from 95.0 mol% to 99.95 mol%, more preferably from 99.0 mol% to 99.93 mol%. The degree of saponification can be determined in accordance with JIS K 6726-1994. By using such a saponification degree PVA-based resin, a polarizing element excellent in durability can be obtained. When the degree of saponification is too high, there is a gelation.

The average degree of polymerization of the PVA-based resin can be appropriately selected depending on the purpose. The average degree of polymerization is usually from 1,000 to 10,000, preferably from 1200 to 4,500, and more preferably from 1,500 to 4,300. Further, the average degree of polymerization can be determined in accordance with JIS K 6726-1994.

Examples of the dichroic substance contained in the resin film include iodine, an organic dye, and the like. These may be used alone or in combination of two or more. It is preferred to use iodine.

The resin film may be a single layer of a resin film, or may be a laminate of two or more layers.

Specific examples of the polarizing element including the resin film of a single layer include those in which the PVA resin film is subjected to dyeing treatment by iodine and stretching treatment (typically, uniaxial stretching). The above dyeing with iodine is carried out, for example, by immersing the PVA-based film in an aqueous iodine solution. The stretching ratio of the uniaxial stretching is preferably from 3 to 7 times. The stretching can be carried out after the dyeing treatment, or can be carried out while dyeing one side. Further, it is also possible to perform dyeing after stretching. The PVA-based resin film may be subjected to a swelling treatment, a crosslinking treatment, a washing treatment, a drying treatment, or the like as needed. For example, by immersing the PVA-based resin film in water and washing the water before dyeing, not only the dirt or the anti-caking agent on the surface of the PVA-based film can be washed, but also the PVA-based resin film can be swollen to prevent uneven dyeing.

Specific examples of the polarizing element obtained by using the laminated body include a laminate of a resin substrate and a PVA-based resin layer (PVA-based resin film) laminated on the resin substrate, or a resin substrate and coating. A polarizing element obtained by laminating a PVA-based resin layer of a resin substrate. A polarizing element obtained by using a resin substrate and a laminate of a PVA-based resin layer formed on the resin substrate can be produced, for example, by applying a PVA-based resin solution to a resin substrate and drying the same. A PVA-based resin layer is formed on a resin substrate to obtain a laminate of a resin substrate and a PVA-based resin layer, and the laminate is stretched and dyed to form a PVA-based resin layer as a polarizing element. In the present embodiment, the stretching is typically carried out by immersing the layered body in an aqueous boric acid solution. Further, the extension may be carried out in the air at a high temperature (for example, 95 ° C or higher) before extending in the aqueous boric acid solution as needed. The laminated body of the obtained resin substrate/polarizing element can be used as it is (that is, the resin substrate can also be used as a protective layer of the polarizing element), or the resin substrate can be peeled off from the laminated body of the resin substrate/polarizing element, and The stripping area layer is used in accordance with any suitable protective layer for the purpose. The details of the method for producing such a polarizing element are described, for example, in Japanese Laid-Open Patent Publication No. 2012-73580. The entire disclosure of this publication is incorporated herein by reference.

The thickness of the polarizing element is preferably 15 μm or less, more preferably 1 μm to 12 μm, still more preferably 3 μm to 10 μm, and particularly preferably 3 μm to 8 μm. When the thickness of the polarizing element is in this range, it is possible to contribute to the reduction in thickness of the polarizing plate with the antireflection layer (resulting as an image display device). Further, it is possible to satisfactorily suppress curling during heating and to obtain excellent appearance durability at the time of heating.

The polarizing element preferably exhibits absorption dichroism at any wavelength from 380 nm to 780 nm. The monomer transmittance of the polarizing element is preferably from 43.0% to 46.0%, more preferably from 44.5% to 46.0%. The degree of polarization of the polarizing element is preferably 97.0% or more, more preferably 99.0% or more, still more preferably 99.9% or more.

B-2. Protective Layer As the protective layer 12, a resin film can be used. As a material for forming the resin film, a resin having a relative energy difference RED of 1.05 or more based on the Hansen solubility parameter of the resin and oleic acid can be used. The resin having a relative energy difference RED of the resin and oleic acid is 1.05 or more, and examples thereof include an acrylic resin, a polycarbonate resin, a polyester resin, and a cycloolefin resin. In the case of using an acrylic resin, it is preferred to use an acrylic resin containing a modified skeleton. Examples of the modified skeleton include a lactone ring structure, a maleic anhydride skeleton, an acrylonitrile skeleton, and a styrene skeleton. The modified skeleton is contained in the acrylic resin at an appropriate ratio, and the relative energy difference RED between the resin and the oleic acid is 1.05 or more. Specific examples of such resins are described in C term (substrate). In addition, "(meth)acrylic resin" means an acrylic resin and/or a methacrylic resin.

Further, in the polarizing plate 100 with the antireflection layer, another protective layer may be formed on the surface of the polarizing element 11 on which the protective layer 12 is not laminated. Examples of the resin that forms the protective layer include a (meth)acrylic resin, a cellulose resin such as diethyl phthalocyanine or triethylene fluorene cellulose, a cycloolefin resin such as a decene-based resin, and polypropylene. An ester resin such as an olefin resin or a polyethylene terephthalate resin, a polyamide resin, a polycarbonate resin, or the like.

In one embodiment, as the (meth)acrylic resin, a (meth)acrylic resin having a quinodiimine structure can be used. A (meth)acrylic resin having a pentylene quinone imine structure (hereinafter also referred to as a glutarylene imide resin) is disclosed in, for example, JP-A-2006-309033, JP-A-2006-317560 Japanese Patent Laid-Open No. Hei. No. 2006-328329, Japanese Patent Laid-Open No. Hei. No. 2006-328334, Japanese Patent Laid-Open No. Hei. No. 2006-337491, Japanese Patent Laid-Open No. Hei. No. 2006-337492, and Japanese Patent Laid-Open No. Hei. No. 2006-337493 Japanese Patent Laid-Open No. Hei. No. 2006-337569, Japanese Patent Laid-Open No. Hei. No. 2007-009182, Japanese Patent Laid-Open No. 2009-161744, and Japanese Patent Laid-Open No. 2010-284840. These records are incorporated herein by reference.

The moisture permeability of the protective layer 12 is preferably 1.0 g/m ² /24 h or less, more preferably 0.8 g/m ² /24 h or less, further preferably 0.6 g/m ² /24 h or less, particularly preferably 0.4 or less. g/m ² /24 h or less. If the moisture permeability of the protective layer is in this range, the dimensional change in a high-temperature and high-humidity environment can be further suppressed.

The thickness of the protective layer is typically from 10 μm to 100 μm, preferably from 20 μm to 40 μm. The protective layer is typically laminated to the polarizing element via an adhesive layer (specifically, an adhesive layer or an adhesive layer). The subsequent agent layer is typically formed of a PVA-based adhesive or an active energy ray-curable adhesive. The adhesive layer is typically formed of an acrylic adhesive.

C. Substrate
C-1. Substrate Body Substrate 20 is used to form anti-reflective layer 30. As described below, by forming the antireflection layer on the substrate and bonding the laminate of the substrate/antireflection layer to the polarizing plate, it is not necessary to provide the polarizing plate to the antireflection layer forming process (typically, sputtering). As a result, since the polarizing plate is not exposed to a high temperature, the moisture content of the polarizing plate can be maintained within the above-described desired range.

As described above, the moisture permeability of the substrate is 150 g/m ² /24 h or less. By the moisture permeability of the substrate being 150 g/m ² /24 h or less, even when the surface of the antireflection layer directly formed on the substrate is damaged, it is possible to prevent the water vapor invading from the damaged portion from reaching the polarized light. element. Therefore, it is possible to prevent the polarizing element directly under the damaged portion from being promoted to be humidified, and to suppress the difference in color between the polarizing element directly under the damaged portion and the other portion (the polarizing element directly under the non-damaged portion). As a result, it is possible to prevent the appearance of poor (yellow unevenness).

As the substrate, a resin film can be used. As the resin forming the resin film, a resin having a relative energy difference RED of 1.05 or more based on the Hansen solubility parameter of the resin and oleic acid can be used. The resin having a relative energy difference RED of the resin and oleic acid is 1.05 or more, and examples thereof include an acrylic resin, a polycarbonate resin, a polyester resin, and a cycloolefin resin. In the case of using an acrylic resin, it is preferred to use an acrylic resin containing a modified skeleton. Examples of the modified skeleton include a lactone ring structure, a maleic anhydride skeleton, an acrylonitrile skeleton, and a styrene skeleton. The modified skeleton is contained in the acrylic resin at an appropriate ratio, and the relative energy difference RED between the resin and the oleic acid is 1.05 or more. The resin forming the resin film as the substrate may be the same as or different from the resin forming the resin film as the protective layer.

Examples of the (meth)acrylic resin include poly(meth)acrylate such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymer, and methyl methacrylate-( Methyl) acrylate copolymer, methyl methacrylate-acrylate-(meth)acrylic acid copolymer, methyl (meth) acrylate-styrene copolymer (MS resin, etc.), polymerization with an alicyclic hydrocarbon group (for example, methyl methacrylate - cyclohexyl methacrylate copolymer, methyl methacrylate - methyl methacrylate copolymer, etc.), (meth)acrylic acid having a lactone ring structure Resin.

As the cycloolefin resin, a norbornene-based resin can be preferably used. Examples of the norbornene-based resin include a ring-opening (co)polymer of a norbornene-based monomer, an addition polymer of a norbornene-based monomer, a norbornene-based monomer, and an α such as ethylene or propylene. A copolymer of an olefin (typically a random copolymer), and a graft modified body obtained by modifying the unsaturated carboxylic acid or a derivative thereof, and the like. Examples of the norbornene-based monomer include norbornene, and alkyl and/or alkylene substituents thereof, for example, 5-methyl-2-northene, 5-dimethyl-2-nor Terpene, 5-ethyl-2-northene, 5-butyl-2-northene, 5-ethylidene-2-norbornene, etc., polar substituents such as halogen; Pentadiene, 2,3-dihydrodicyclopentadiene, etc.; dimethylene octahydronaphthalene, alkyl and/or alkylene substituent thereof, and polar substituent such as halogen, for example, 6-methyl -1,4:5,8-Dimethylene-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4:5,8-di-nethylene Base-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethylene-1,4:5,8-dimethylene-1,4,4a,5,6 , 7,8,8a-octahydronaphthalene, 6-chloro-1,4:5,8-dimethylene-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6- Cyano-1,4:5,8-dimethylene-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-pyridyl-1,4:5,8-di Methylene-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4:5,8-dimethylene-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, etc.; a trimer to tetramer of cyclopentadiene, such as 4,9:5,8-dimethylene-3a, 4,4a,5, 8,8a,9,9a-octahydro-1H-indole, 4,11:5,10:6,9- Trimethylene-3a,4,4a,5,5a,6,9,9a,10,10a,11,11a-dodecyl-1H-cyclopentafluorene.

Examples of the polyester-based resin include PET (polyethylene terephthalate), PAR (polyarylate), PEN (polyethylene naphthalate), and PBT (polybutylene terephthalate). Ester), such modified or copolymers, mixtures of these with other resins (polymer alloys). It is preferred to use PET.

Further, as the substrate, an inorganic glass or a laminate having a resin layer formed of a resin having a RED of 1.05 or more and an inorganic glass layer may be used. As the inorganic glass constituting the inorganic glass film, any appropriate inorganic glass can be employed. Examples of the composition of the inorganic glass include soda lime glass, boric acid glass, aluminosilicate glass, and quartz glass. Examples of the classification of the alkaline component include alkali-free glass and low-alkali glass. The content of the alkali metal component (for example, Na ₂ O, K ₂ O, and Li ₂ O) of the inorganic glass is preferably 15% by weight or less, more preferably 10% by weight or less.

As the inorganic glass film, a commercially available product can be used as it is, or a commercially available inorganic glass film can be ground to a desired thickness. Specific examples of the commercial product include "Willow Glass", "7059", "1737" or "EAGLE2000" manufactured by Corning Incorporated, "AN100" manufactured by Asahi Glass Co., Ltd., and "NA-35" manufactured by NH TECHNO GLASS Co., Ltd. "G-Leaf" or "OA-10" manufactured by Nippon Electric Glass, "D263" or "AF45" manufactured by Schott.

For the details of the inorganic glass film and the laminate having the resin layer and the inorganic glass layer, for example, Japanese Patent Laid-Open No. 2010-132526, Japanese Patent Laid-Open No. 2010-284964, and Japanese Patent Laid-Open No. 2011-016708 Japanese Laid-Open Patent Publication No. 2011-088789, Japanese Patent Laid-Open No. 2011-104998, Japanese Patent Laid-Open No. Hei No. Hei. To this manual.

The thickness of the substrate can be appropriately set depending on the purpose. The thickness of the substrate is usually from 20 μm to 200 μm, preferably from 25 μm to 100 μm. In the case where an inorganic glass film is used as the substrate, the thickness of the substrate is typically 10 μm to 100 μm.

C-2. Hard coat layer As described above, a hard coat layer may be formed on the surface of the anti-reflection layer side of the substrate. By forming a hard coat layer, there is an advantage that the adhesion between the substrate and the antireflection layer can be improved. Further, by appropriately adjusting the refractive index difference between the hard coat layer and the antireflection layer, the reflectance can be further lowered.

The hard coat layer preferably has sufficient surface hardness, excellent mechanical strength, and excellent light transmittance. The hard coat layer may be formed of any appropriate resin as long as it has such desired characteristics. Specific examples of the resin include a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, an electron beam curing resin, and a two-liquid mixing resin. It is preferably an ultraviolet curable resin. The reason for this is that the hard coat layer can be formed with a simple operation and high efficiency.

Specific examples of the ultraviolet curable resin include polyester-based, acrylic-based, urethane-based, guanamine-based, anthrone-based, and epoxy-based ultraviolet-curable resins. The ultraviolet curable resin contains an ultraviolet curable monomer, oligomer, or polymer. The preferred ultraviolet curable resin is a resin composition containing an acrylic monomer component or an oligomer component preferably having two or more, more preferably three to six ultraviolet polymerizable functional groups. Typically, a photopolymerization initiator is formulated in the ultraviolet curable resin.

The hard coat layer can be formed by any suitable method. For example, the hard coat layer can be formed by applying a resin composition for forming a hard coat layer on a substrate, drying it, and irradiating the dried coating film with ultraviolet rays to cure it.

The thickness of the hard coat layer is, for example, 0.5 μm to 20 μm, preferably 1 μm to 15 μm.

The details of the hard coat layer and the adhesion structure of the hard coat layer and the antireflection layer are described in, for example, Japanese Laid-Open Patent Publication No. 2016-224443. The description of this publication is incorporated herein by reference.

D. The antireflection layer may be any suitable structure as the antireflection layer. Typical examples of the antireflection layer include: (1) a single layer of a low refractive index layer having an optical film thickness of 120 nm to 140 nm and a refractive index of about 1.35 to 1.55; and (2) depending on the substrate side. The layered body having a medium refractive index layer, a high refractive index layer and a low refractive index layer; and (3) an alternating multilayer laminated body of a high refractive index layer and a low refractive index layer.

Examples of the material capable of forming the low refractive index layer include cerium oxide (SiO ₂ ) and magnesium fluoride (MgF ₂ ). The refractive index of the low refractive index layer is typically from about 1.35 to about 1.55. Examples of the material capable of forming the high refractive index layer include titanium oxide (TiO ₂ ), cerium oxide (Nb ₂ O ₃ or Nb ₂ O ₅ ), tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO). , ZrO ₂ -TiO ₂ . The refractive index of the high refractive index layer is typically from about 1.60 to about 2.20. Examples of the material capable of forming the medium refractive index layer include titanium oxide (TiO ₂ ), a mixture of a material capable of forming a low refractive index layer, and a material capable of forming a high refractive index layer (for example, a mixture of titanium oxide and cerium oxide). ). The refractive index of the medium refractive index layer is typically about 1.50 to 1.85. The thickness of the low refractive index layer, the medium refractive index layer, and the high refractive index layer can be set in such a manner as to achieve an appropriate optical film thickness corresponding to the layer structure of the antireflection layer, the required antireflection performance, and the like.

The antireflection layer is typically formed by a dry process. Specific examples of the dry process include a PVD (Physical Vapor Deposition) method and a CVD (Chemical Vapor Deposition) method. Examples of the PVD method include a vacuum deposition method, a reactive vapor deposition method, an ion beam assist method, a sputtering method, and an ion plating method. As the CVD method, a plasma CVD method can be cited. It is preferably a sputtering method. The reason for this is that film formation with a small film thickness unevenness and uniformity can be achieved.

The thickness of the antireflection layer is, for example, about 20 nm to 300 nm.

The difference between the maximum reflectance and the minimum reflectance of the antireflection layer in the wavelength range of 400 nm to 700 nm is preferably 2.0% or less, more preferably 1.9% or less, still more preferably 1.8% or less. When the difference between the maximum reflectance and the minimum reflectance is in such a range, the chromatic aberration of the reflected light can be satisfactorily prevented.

An antifouling layer may be provided on the surface of the antireflection layer as needed. The antifouling layer is, for example, an organic compound containing a fluorine-containing decane-based compound (for example, an alkoxydecane compound having a perfluoropolyether group) or a fluorine-containing group. The antifouling layer preferably exhibits a water repellency of a water contact angle of 110 degrees or more.

E. Method for Producing Polarizing Plate with Antireflection Layer A method for producing a polarizing plate with an antireflection layer according to an embodiment of the present invention includes the steps of: producing a polarizing element laminate including a polarizing element and a protective layer; The antireflection layer is formed with an antireflection laminate; and the substrate of the antireflection laminate is bonded to the surface of the protective layer of the polarizer laminate.

The polarizing element laminate can be produced by any suitable method. In the case of using a polarizing element composed of a single-layer resin film, the polarizing element and the resin film constituting the protective layer may be bonded via any appropriate adhesive layer (adhesive layer or adhesive layer). When a laminate of a resin substrate and a PVA-based resin layer (PVA-based resin film) laminated on the resin substrate is used, the laminate may be subjected to dyeing and stretching treatment, and the PVA-based resin layer may be used as a polarizing element. This laminate is directly used as a polarizing element laminate. Alternatively, a resin film constituting the protective layer may be bonded to the surface of the polarizing element of the laminate. In this case, the resin substrate may or may not be peeled off. In the case of using a polarizing element obtained by coating a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate, it may be as described in the above item B-1 (for example, Japanese Patent Laid-Open No. 2012) A laminate of a resin substrate and a polarizing element is produced as described in the '735 publication, and the laminate is directly used as a polarizing element laminate. Alternatively, a resin film constituting the protective layer may be bonded to the surface of the polarizing element of the laminate. In this case, the resin substrate may or may not be peeled off.

The antireflection laminate is produced by forming an antireflection layer on the substrate. When the antireflection layer is formed, a surface treatment may be applied to the substrate in advance as needed. Examples of the surface treatment include low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, and acid or alkali treatment. Alternatively, an adhesion layer containing, for example, SiOx may be formed on the surface of the substrate. As described above, the antireflection layer is typically formed by a dry process such as sputtering. For example, when the antireflection layer is an alternate multilayer laminate of a high refractive index layer and a low refractive index layer, a film such as a Nb ₂ O ₅ film (high refractive index layer) is sequentially formed by sputtering on the surface of the substrate, An SiO ₂ film (low refractive index layer), a Nb ₂ O ₅ film (high refractive index layer), and an SiO ₂ film (low refractive index layer) can thereby form an antireflection layer.

Finally, the polarizing plate with the antireflection layer can be obtained by bonding the substrate of the antireflection laminate to the surface of the protective layer of the polarizing element laminate via any appropriate adhesive layer (for example, an adhesive layer or an adhesive layer). As apparent from the above description, according to this manufacturing method, the polarizing plate is not provided in the formation process of the antireflection layer (dry process). Therefore, since the polarizing plate is not exposed to high temperatures, the moisture content of the polarizing plate can be maintained within the above-mentioned desired range. As a result, the dimensional change of the polarizing plate with the antireflection layer obtained in a high-temperature and high-humidity environment is suppressed, and even if a curl is assumed, the curl is oriented toward the side opposite to the viewing side. . Therefore, when the polarizing plate with the antireflection layer is applied to the image display device, it is possible to remarkably suppress the warpage, the peeling, and/or the deterioration of the display characteristics in a high-temperature and high-humidity environment.

F. Image Display Device A polarizing plate with an antireflection layer according to an embodiment of the present invention can be applied to an image display device. Typically, the polarizing plate with the antireflection layer is disposed on the viewing side of the image display device such that the antireflection layer is on the viewing side. Typical examples of the image display device include a liquid crystal display device, an organic electroluminescence (EL) display device, and a quantum dot display device.
[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Furthermore, the measurement method of each characteristic is as follows.

(1) Transmittance of polarizing plate The polarizing plate (polarizing element laminate) used in the examples and the comparative examples was cut into a circular shape of 10 cmφ to obtain a measurement sample. The measurement sample was allowed to stand under the conditions of a temperature of 40 ° C and a humidity of 92% RH for 24 hours, and then the moisture permeability was measured under the test conditions of a temperature of 40 ° C and a humidity of 90% RH using "MOCON" manufactured by Hitachi, Ltd.
(2) Moisture permeability of the substrate The film used as the substrate in the examples and the comparative examples was measured in a temperature of 40 ° C and a humidity of 92% RH in accordance with the moisture permeability test (cup method) of JIS Z0208. The amount of water vapor (g) of a sample having an area of 1 m ^{2 in} 24 hours.
(3) The single-color b-value of the polarizing plate with the anti-reflection layer was made. The polarizing plate (100 mm × 50 mm) with the anti-reflection layer obtained in the examples and the comparative examples was passed through an adhesive (manufactured by Nitto Denko Corporation, acrylic acid). The adhesive is bonded to the glass plate so that the antireflection layer is on the upper side. Then, using a sandpaper (#1200) carrying a weight of 1 kg, reciprocating once in the MD direction of the polarizing element, scraping the surface of one half (50 mm × 50 mm) of the antireflection layer of the polarizing plate with the antireflection layer, and Causes damage. Thereafter, the polarizing plate with the antireflection layer was placed in an environment of a temperature of 65 ° C and a humidity of 90% RH. Using a spectrophotometer (Murako Color Technology Research Institute Co., Ltd. product name "DOT-3"), before the humidification environment of the polarizing plate with anti-reflection layer is put in (0 hours), 72 hours and 120 hours after the input. The 250-hour NBS-based monomer hue b value was measured for the portion (damaged) and the portion where no damage occurred (no damage) on the surface of the polarizing plate with the antireflection layer. The difference between the single-color h-value measured at each portion and the single-color b-value (initial value) of each portion measured before the introduction of the humidification environment at each time was calculated as the amount of change.
Change amount = (basic h phase b value (initial value) before humidification environment input) - (basic h phase b value measured at each time)
Further, the difference between the amount of change in the portion where the damage occurred and the amount of change in the portion where no damage occurred (the difference Δ between the amounts of change) is calculated by the following equation.
The difference between the changes Δ = (the amount of change in the part that caused the damage) - (the amount of change in the portion where no damage occurred)

(4) HSP distance Ra of resin and oleic acid, interaction radius R _{0 of} resin, and relative energy difference RED
The solubility of the base material of the polarizing plate with the antireflection layer of Examples 1 to 5 and Comparative Examples 1 to 4 and the resin forming the protective layer in a solvent known by HSP was evaluated by the following method.
Specifically, 0.02 parts by weight of each resin is in a ratio of 100:0, 90:10, 80:20, 70:30, 60:40, 40:60, 20:80, 0:100, respectively. The ethyl ethyl ketone (good solvent) was immersed in a mixed solvent of n-hexane, methanol, γ-butyrolactone or trichlorobenzene (poor solvent) for 24 hours. The conditions of the resin after immersion for 24 hours were visually classified by evaluation of (i) dissolution, (ii) swelling, and (iii) insoluble three stages. The information on the solubility obtained in each solvent is input to the HSP value calculation software (HSPiP version 4.1.0.7 (Hansen Solubility Parameters in Practice)), and δ _D , δ _P , and δ _{H of} each resin are respectively calculated by three-dimensional The Hansen dissolution sphere of each resin was obtained by drawing. The interaction radius R _{0 of} the resin was determined from the obtained solute balls. Similarly, the HSP distance Ra and the relative energy difference RED with oleic acid (δ _D :16, δ _P : 2.8, δ _H : 6.2) were calculated by the HSP calculation software.
(5) Whitening test The polarizing plate with the antireflection layer obtained in the examples and the comparative examples was cut into 5 cm × 5 cm samples, bonded to a glass plate, and placed in an autoclave. After autoclaving, oleic acid was applied to the entire side of the sample and placed in an environmental test oven at 65 ° C and 90% RH for 72 hours. Then, the sample was taken out to visually confirm the presence or absence of whitening of the portion coated with oleic acid. The peripheral portion of the sample (the portion coated with oleic acid) was evaluated as 〇, and the whitened person was evaluated as ×.

<Production Example 1> Preparation of Acrylic Resin Film 1 Methyl methacrylate (MMA), 2-(hydroxymethyl)acrylic acid was added to a reaction vessel equipped with a stirring device, a temperature sensor, a condenser, and a nitrogen introduction tube. The methyl ester (MHMA) and toluene were subjected to a cyclization condensation reaction and devolatization in an extruder at 250 ° C to obtain a transparent lactone ring-containing acrylic resin particle. The obtained pellets were mixed with an acrylonitrile-styrene resin, melt-kneaded at a cylinder temperature of 240 ° C using a twin-screw extruder, and regranulated.
The obtained pellets were placed in a uniaxial extruder, melt-mixed, and formed into a film by a T-die.
The obtained extruded film was simultaneously biaxially stretched to 2 times in the longitudinal direction and the width direction at an extension temperature of 160 ° C. The thickness of the obtained film was 40 μm. The resin composition ratio of the obtained film was confirmed by NMR (nuclear magnetic resonance), and as a result, MMA 61%, lactone ring 26.7%, styrene 7.6%, and acrylonitrile 4.7%.

<Production Example 2> Preparation of Acrylic Resin Film 2 Methyl methacrylate (MMA), 2-(hydroxymethyl)acrylic acid was added to a reaction vessel equipped with a stirring device, a temperature sensor, a condenser, and a nitrogen introduction tube. The methyl ester (MHMA), toluene, and polystyrene were subjected to a cyclization condensation reaction and devolatization in an extruder at 250 ° C to obtain a transparent lactone ring-containing acrylic resin particle. The obtained pellets were placed in a uniaxial extruder, melt-mixed, and formed into a film by a T-die. The obtained extruded film was simultaneously biaxially stretched to 2 times in the longitudinal direction and the width direction at an extension temperature of 160 ° C. The thickness of the obtained film was 40 μm. The resin composition ratio of the obtained film was confirmed by NMR, and as a result, MMA 76%, lactone ring 19%, and styrene 5%.

<Production Example 3> Preparation of Polycarbonate Resin Film A commercially available polycarbonate resin containing a structural unit derived from a dihydroxy compound (manufactured by Mitsubishi Chemical Corporation, trade name DURABIO T7450A, Tg: 132 ° C, iso Yamanashi The ester structural unit 62 mol%, tricyclodecane dimethanol structural unit 38 mol%) was vacuum dried at 80 ° C for 5 hours, and then used with a single-axis extruder (ISUZU Chemical Co., Ltd., spiral diameter 25 mm) , cylinder setting temperature: 250 ° C), T-die (width 200 mm, set temperature: 250 ° C), cooling roll (set temperature: 120 ~ 130 ° C) and winding machine film making device, thickness 160 μm Polycarbonate resin film. The produced resin film was further extended to obtain a film having a thickness of 40 μm.

<Production Example 4> Preparation of Acrylic Resin Film 3 An acrylic resin (product name: CM-205) manufactured by CHIMEI was placed in a uniaxial extruder, melt-mixed, and formed into a film by a T-die. The obtained extruded film was simultaneously biaxially stretched to 2 times in the longitudinal direction and the width direction at an extension temperature of 160 ° C. The thickness of the obtained film was 40 μm. The resin composition ratio of the obtained film was confirmed by NMR, and as a result, MMA was 73.5%, maleic anhydride was 17.6%, and styrene was 6.9%.

[Example 1]
1. Production of a polarizing plate (polarizing element laminate) As a resin substrate, an amorphous, terephthalic acid copolymerized polyethylene terephthalate (IPA) having a long water absorption ratio of 0.75% and a Tg of 75 ° C was used. Copolymerized PET) film (thickness: 100 μm). Corona treatment is applied to one side of the substrate, and the coating is applied at 25 ° C at a ratio of 9:1 to include polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and ethyl acetate An aqueous solution of a thiol-modified PVA (having a degree of polymerization of 1200, a degree of modification of acetonitrile, 4.6%, a degree of saponification of 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z200"), and drying it, A PVA-based resin layer having a thickness of 11 μm was formed to produce a laminate.
The obtained laminate was uniaxially stretched to 2.0 times (air assisted extension) in the longitudinal direction (longitudinal direction) between the rolls having different peripheral speeds in an oven at 120 °C.
Then, the laminate was immersed in an insoluble bath at a liquid temperature of 30 ° C (a boric acid aqueous solution obtained by dispersing 4 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (insolubilization treatment).
Then, in the dye bath at a liquid temperature of 30 ° C, the iodine concentration and the immersion time were adjusted while the polarizing plate was made to have a specific transmittance, and immersed in the dye bath. In the present embodiment, the iodine aqueous solution obtained by blending 0.2 parts by weight of iodine with respect to 100 parts by weight of water and blending 1.5 parts by weight of potassium iodide was immersed for 60 seconds (dyeing treatment).
Then, it was immersed for 30 seconds (crosslinking treatment) in a crosslinking bath at a liquid temperature of 30 ° C (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide with respect to 100 parts by weight of water and 3 parts by weight of boric acid).
Thereafter, the laminate was immersed in a boric acid aqueous solution (4 parts by weight of boric acid and 5 parts by weight of potassium iodide added to 100 parts by weight of water) at a liquid temperature of 70 ° C, and was placed between rolls having different peripheral speeds. Uniaxial stretching (water extension) was performed in such a manner that the total stretching ratio was 5.5 times in the longitudinal direction (longitudinal direction).
Thereafter, the laminate was immersed in a washing bath at a liquid temperature of 30 ° C (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) (washing treatment).
Then, on the surface of the PVA-based resin layer (polarizing element) of the laminate, the adhesive agent shown below was applied so that the thickness of the adhesive layer after curing was 1.0 μm, and the methacrylic resin film was bonded (thickness: 40 μm, moisture permeability: 100 g/m ² /24 h, the acrylic resin film 2) obtained in Production Example 2 was used as a protective layer, and the temperature was 50 ° C from the side of the methacrylic resin film using an IR heater. The following ultraviolet rays are irradiated to harden the adhesive. Thereafter, the substrate was peeled off from the PVA-based resin layer to obtain a polarizing element laminate (a polarizing plate having a configuration of a polarizing element/protective layer). Further, the thickness of the polarizing element was 5 μm, and the monomer transmittance was 42.3%. Further, the obtained polarizing plate had a water content of 1.0% by weight.
(adhesive composition)
40 parts by weight of N-hydroxyethyl acrylamide (HEAA), 60 parts by weight of propylene porphyrin (ACMO), and 3 parts by weight of a photoinitiator "IRGACURE 819" (manufactured by BASF Corporation) were mixed to prepare a pre-hardening layer. Adhesive with a viscosity of 40 mPa·s.
(UV)
Use of ultraviolet light (metal halide lamp enclosed in gallium, irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., bulb: V BULB, peak illuminance: 1600 mW/cm ² , cumulative irradiation amount 1000/mJ/cm ² (wavelength) 380 ~ 440 nm)) as the active energy line. Further, the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.

2. Preparation of anti-reflection laminate A hard coating (HC) layer (thickness: 7 μm) was formed on one side of a PET-based resin film (product name: CosmoFine, thickness: 80 μm) manufactured by Toyobo Co., Ltd. by hard coating treatment. Thereby, an HC-PET film (thickness: 87 μm) was obtained. This HC-PET film was used as a substrate for forming an antireflection layer. An adhesion layer (thickness: 10 nm) containing SiOx is formed on the surface of the HC layer of the substrate by sputtering, and a Nb ₂ O ₅ film (high refractive index layer) and SiO ₂ are sequentially formed on the adhesion layer. A film (low refractive index layer), a Nb ₂ O ₅ film (high refractive index layer), and a SiO ₂ film (low refractive index layer) were used to form an antireflection layer (total thickness of 4 layers: 200 nm). Further, an antifouling layer (thickness: 10 nm) containing an alkoxydecane compound having a perfluoropolyether group was formed on the antireflection layer to prepare an antireflection laminate.

3. Production of a polarizing plate with an antireflection layer as a cyclic olefin film of the first retardation layer (refractive index characteristics: nx>ny>nz, in-plane phase difference: 116 nm), and as a second phase difference The modified polyethylene film of the layer (refractive index characteristics: nz>nx>ny, in-plane phase difference: 35 nm) was sequentially bonded to the surface of the polarizing element of the polarizing element laminate. The same ultraviolet curing adhesive as described above was used for the bonding. Further, the retardation axis of the first retardation layer is at an angle of 0° with respect to the absorption axis of the polarizing element, and the slow phase axis of the second retardation layer is at an angle of 90° with respect to the absorption axis of the polarizing element. fit. Furthermore, the HC-TAC film of the antireflection laminate was bonded to the surface of the protective layer (methacrylic resin film) of the polarizing element laminate via an acrylic adhesive (thickness: 20 μm) to obtain an antireflection layer. Polarizer. The obtained polarizing plate with an antireflection layer was subjected to the above evaluation. The results are shown in Tables 1 and 2.

[Embodiment 2]
A polarizing plate with an antireflection layer was produced in the same manner as in Example 1 except that the acrylic resin film 1 obtained in Production Example 1 was used as a protective layer of a substrate and a polarizing element laminate. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.

[Example 3]
A polarizing plate with an antireflection layer was produced in the same manner as in Example 1 except that the acrylic resin film 2 obtained in Production Example 2 was used as a protective layer of a substrate and a polarizing element laminate. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.

[Example 4]
A polarizing plate with an antireflection layer was produced in the same manner as in Example 1 except that the polycarbonate resin film obtained in Production Example 3 was used as a protective layer for the substrate and the polarizing element laminate. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.

[Example 5]
A polarizing plate with an antireflection layer was produced in the same manner as in Example 1 except that the acrylic resin film 3 obtained in Production Example 4 was used as a protective layer for the substrate and the polarizing element laminate. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 1)
A polarizing plate with a reflective layer was produced in the same manner as in Example 1 except that a TAC film (product name: Fujitac, thickness: 100 μm) manufactured by Fuji Film Co., Ltd. was used as the substrate. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 2)
A polarizing plate with a reflective layer was produced in the same manner as in Example 1 except that a TAC film (product name: TD80-UL, thickness: 80 μm) manufactured by Fuji Film Co., Ltd. was used as the substrate. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 3)
A polarizing plate with a reflective layer was produced in the same manner as in Example 1 except that a TAC film (product name: KC4UY, thickness: 40 μm) manufactured by Konica Minolta Co., Ltd. was used as the substrate. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 4)
A polarizing plate with an antireflection layer was produced in the same manner as in Example 1 except that an acrylic resin film (product name: CAT film, thickness: 40 μm) manufactured by Nitto Denko Corporation was used as the substrate. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.

[Table 1]

[Table 2]

As is clear from Table 1, by setting the moisture permeability of the substrate on which the antireflection layer is formed and the polarizing plate with the antireflection layer to an appropriate value, it is possible to suppress polarization of the antireflection layer in a high-temperature and high-humidity environment. Poor appearance of the board (yellow unevenness). Further, as is clear from Table 2, in the polarizing plate with antireflection layers of Examples 1 to 5 in which the resin having a relative energy difference RED of oleic acid of 1.05 or more was used for the substrate and the protective layer, high temperature and high humidity were observed. The occurrence of whitening in the environment has also been suppressed.
[Industrial availability]

The polarizing plate with an antireflection layer of the present invention can be preferably used for an image display device such as a liquid crystal display device, an organic EL display device, or a quantum dot display device.

10‧‧‧Polar plate

11‧‧‧Polarized components

12‧‧‧Protective layer

20‧‧‧Substrate

30‧‧‧Anti-reflective layer

100‧‧‧Polarizer with anti-reflection layer

Fig. 1 is a schematic cross-sectional view showing a polarizing plate with an antireflection layer according to an embodiment of the present invention.

Claims (5)

A polarizing plate with an anti-reflection layer, comprising: a polarizing plate having a polarizing element and a protective layer disposed on one side of the polarizing element; a substrate attached to the protective layer; and an anti-reflection layer directly Formed on the substrate; the substrate and the protective layer comprise a resin, and the relative energy difference RED based on the Hansen solubility parameter of the resin and oleic acid is 1.05 or more; the moisture permeability of the polarizing plate with the anti-reflection layer is 0.2 g/m ² /24 h or less, and the substrate has a moisture permeability of 150 g/m ² /24 h or less. The polarizing plate with an antireflection layer according to claim 1, wherein the substrate and the protective layer comprise at least one selected from the group consisting of a (meth)acrylic resin, a polycarbonate resin, and a polyester resin. Resin. The polarizing plate with the antireflection layer of claim 1 or 2, wherein the difference Δ of the change in the hue value of the monomer hue after being left at 65 ° C and 90% RH for 72 hours is 1.0 or less, and at 65 ° C and 90 The difference Δ between the amounts of change in the hue b of the monomer after standing for 120 hours at %RH was 0.8 or less. A method of manufacturing a polarizing plate with an anti-reflection layer, which is a method for producing a polarizing plate with an anti-reflection layer according to any one of claims 1 to 3, comprising: Producing a polarizing element laminate including a polarizing element and a protective layer; Forming an anti-reflection layer on the substrate to form an anti-reflection laminate; and A substrate of the anti-reflection laminate is bonded to the surface of the protective layer of the polarizing element laminate. The manufacturing method of claim 4, wherein the antireflection layer is formed by sputtering.